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  • Electrocatalytic Oxidative Transformation of Organic Acids for Carbon–Heteroatom and Sulfur–Heteroatom Bond Formation
    ChemSusChem (IF 7.804) Pub Date : 2020-02-21
    Man Li; Junting Hong; Wei Xiao; Yang Yang; Di Qiu; Fanyang Mo
    更新日期:2020-02-21
  • Continuous‐Flow Amide and Ester Reductions Using Neat Borane Dimethylsulfide Complex
    ChemSusChem (IF 7.804) Pub Date : 2020-02-20
    Sándor B. Ötvös; C. Oliver Kappe
    更新日期:2020-02-20
  • Progress of Two‐Dimensional Ti3C2Tx in Supercapacitors
    ChemSusChem (IF 7.804) Pub Date : 2020-02-20
    Lu Li; Jing Wen; Xitian Zhang
    更新日期:2020-02-20
  • Approaches to The Hagfeldt Donor and Use of Next Generation Bulky Donor Designs in Dye‐Sensitized Solar Cell Dyes
    ChemSusChem (IF 7.804) Pub Date : 2020-02-20
    Alexandra Baumann; Christine Curiac; Jared Heath Delcamp

    'The Hagfeldt donor' is a bulky triarylamine building block with 4 alkyl chains in a 3‐dimensional arrangement which is used with organic dyes in dye‐sensitized solar cells (DSCs) in over 140 manuscripts. Many of the highest performing DSC devices in literature make use of this group due to exceptional TiO2 surface protection properties which slows recombination of electrons in TiO2 with the electrolyte. Importantly, record‐setting cobalt and copper redox shuttle based‐DSCs require exceptional surface protection to slow a facile recombination of electrons to these positively charged redox shuttles. Several syntheses have emerged for the Hagfeldt donor due to the need for iterative aryl‐halide cross couplings complicating a straight forward route. The six synthetic strategies found in literature are described along with the challenges of each route. A recent method that has been put forward in the literature as a scalable, regioisomerically pure route is highlighted.

    更新日期:2020-02-20
  • Molecular Engineering of Pure 2D Lead‐Iodide Perovskite Solar Absorbers Displaying Reduced Band Gaps and Dielectric Confinement
    ChemSusChem (IF 7.804) Pub Date : 2020-02-20
    Benny Febriansyah; Yulia Lekina; Biplab Ghosh; Padinhare Cholakkal Harikesh; Teck Ming Koh; Yongxin Li; Zexiang Shen; Nripan Mathews; Jason England

    Pure 2D lead‐iodide perovskites typically demonstrate poor charge transport and compromised visible light absorption, relative to their 3D congeners. This hinders their potential use as solar absorbers. Herein, we report systematic tuning of pyridinium‐based templating cations to introduce intermolecular interactions that provide access to a series of new 2D lead‐iodide perovskites with reduced inter‐octahedral distortions (largest Pb‐( μ ‐I)‐Pb bond angles of 170 – 179°) and very short inorganic interlayer separations (shortest I···I contacts ≤ 4.278 – 4.447 Å). These features manifest in reduced band gaps (2.35 – 2.46 eV) and relaxed dielectric confinement (excitonic binding energies of 130 – 200 meV). As a consequence, they demonstrate (more than 10‐fold) improved photo‐ and electrical conductivities relative to conventional 2D lead‐iodide perovskites, such as that templated by 2‐(1‐naphthyl)ethylammonium). Through computational studies, the origin of this behaviour was shown to derive from a combination of short iodoplumbate layer separations and the aromaticity of the organic dications.

    更新日期:2020-02-20
  • Anodically Triggered Aldehyde Cation Autocatalysis for Alkylation of Heteroarenes
    ChemSusChem (IF 7.804) Pub Date : 2020-02-19
    Caiyan Liu; Zihui Xiao; Shuhua Wu; Yongli Shen; Kedong Yuan; Yi Ding
    更新日期:2020-02-19
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  • 更新日期:2020-02-19
  • Recent Advances of Two‐Dimensional (2D) Mxenes and Phosphorene for High‐Performance Rechargeable Batteries
    ChemSusChem (IF 7.804) Pub Date : 2020-02-19
    Li Jingsha; Guo Chunxian; Chang Ming Li

    Designing and developing advanced electrode materials for high‐performance rechargeable batteries have been subjected to extensive studies. Very recently, two‐dimensional (2D) nanomaterials have become promising candidates for batteries due to their unique physicochemical properties. In particular, MXenes and phosphorene that exhibit tailored electrical conductivity and ion storage capability have attracted increasing atentions. In this review, we present a comprehensive summary of recent advances of 2D MXenes and phosphorene as electrode materials for high‐performance batteries. Their physicochemical properties that include structural configurations and electronic properties of MXenes, and direct bandgap and anisotropic properties of phosphorene are firstly discussed. Then, synthesis methods of the two materials are introduced. Following this, their applications as electrode materials in batteries including lithium‐ion batteries (LIBs), sodium‐ion batteries (SIBs), potassium‐ion batteries (PIBs), lithium‐sulfur (Li‐S) batteries and metal‐air batteries are summarized and discussed in details. An emphasis is placed on analyzing performance enhancement mechanisms to to elucidate fundamental understanding. Finally, challenges and opportunities ahead for MXenes and phosphorene as electrode materials for batteries are featured.

    更新日期:2020-02-19
  • Regulating Hydrogenation Chemoselectivity of α,β‐Unsaturated Aldehydes by Combination of Transfer and Catalytic Hydrogenation
    ChemSusChem (IF 7.804) Pub Date : 2020-02-18
    Yangyang Zhou; Zihao Li; Yanbo Liu; Jia Huo; Chen Chen; Qiling Li; Songyang Niu; Shuangyin Wang
    更新日期:2020-02-18
  • Gelless Secondary Growth of Zeolitic Aluminophosphate Membranes on Porous Supports with High Performance in CO2/CH4 Separation
    ChemSusChem (IF 7.804) Pub Date : 2020-02-18
    Quang Thanh Le; Duy Hoai‐Phuong Nguyen; Nha Minh Nguyen; Duy Phuc‐Hoang Nguyen; Ty Minh Nguyen; Tung Ngoc Nguyen; Tung Cao‐Thanh Pham
    更新日期:2020-02-18
  • Direct Catalytic Conversion of Furfural to Furan‐derived Amines in the Presence of Ru‐based Catalyst
    ChemSusChem (IF 7.804) Pub Date : 2020-02-18
    Shi Jiang; Wahiba Ramdani; Eric Muller; Changru Ma; Marc Pera‐Titus; François Jerôme; Karine De Oliveira Vigiera
    更新日期:2020-02-18
  • BiVO4/Bilirubin Oxidase Photo(bio)electrochemical Cells for Unbiased Light‐Triggered Electrical Power Generation
    ChemSusChem (IF 7.804) Pub Date : 2020-02-18
    Dina Mukha; Yifat Cohen; Omer Yehezkeli

    A construction of bias‐free, donor‐free photobioelectrochemical cells for the generation of light‐triggered electrical power is presented. The developed oxygen reduction biocathodes are based on bilirubin oxidase (BOD) originates from Myrothecium verrucaria (MvBOD) and a thermophilic Bacillus pumilus (BpBOD). Methods to entrap the bilirubin oxidase with ABTS redox molecules in a polydopamine layer are presented. A pH‐independent, positively charged pyrenebetaine linker has been synthesized and utilized, leading to 3 folds bioelectrocatalytic current improvement. Both developed polydopamine/ABTS/MvBOD and the pyrene‐betaine/BpBOD biocathodes were further coupled with BiVO4/cobalt‐phosphate water oxidation photoanodes to construct biotic/abiotic photobioelectrochemical cells, generating power outputs of 0.74mW/cm 2 and 0.85 mW/cm 2 , respectively. The presented methods are versatile, showing the strength of biotic/abiotic hybrids and can be further used for coupling different redox enzymes with electrodes.

    更新日期:2020-02-18
  • Intrinsic effect of carbon supports on the activity and stability of precious metal group (PMG)‐based catalysts for electrocatalytic alcohol oxidation of fuel cells
    ChemSusChem (IF 7.804) Pub Date : 2020-02-18
    San Ping Jiang; Jin Zhang; Shanfu Lu; Yan Xiang

    Electrocatalyst supports, in particular carbonaceous materials, play critical roles in the electro‐catalytic activity and stability of precious metal group (PMG)‐based catalysts such as Pt, Pd and Au for the electrochemical alcohol oxidation reaction (AOR) of fuels such as methanol and ethanol in polymer electrolyte membrane fuel cells (PEMFCs). Carbonaceous supports such as high surface area carbon provide electronic contact throughout the catalyst layer, isolate PMG nanoparticles (NPs) to maintain the high electrochemical surface area, and provide hydrophobic properties to avoid the flooding of the catalyst layer by liquid water produced. Compared to high surface area carbon, PMG catalysts supported on 1D and 2D carbon materials such as graphene and carbon nanotubes show enhanced activity and durability due to the intrinsic effect of underlying carbonaceous supports on the electronic states of PMG NPs. The modification of the electronic environment in particular the d‐band centers of PMG NPs weakens the adsorption of AOR intermediates and facilitates the breaking of the C‐C bonds, thus enhancing the electrocatalytic activity of PMG catalysts. The doping of heteroatoms further facilitates the electrocatalytic activity for the AOR via the structural, bifunctional and electronic effect, in addition to the enhanced dispersion of PMG NPs in the carbon support. The prospect of the development of effective PMG‐based catalysts for the high performance alcohol fuels‐based PEMFCs is discussed.

    更新日期:2020-02-18
  • Synthesis of Fluorinated Dialkyl Carbonates from Carbon Dioxide as a Carbonyl Source
    ChemSusChem (IF 7.804) Pub Date : 2020-02-17
    Masafumi Sugiyama; Midori Akiyama; Kohei Nishiyama; Takashi Okazoe; Kyoko Nozaki

    Fluorinated dialkyl carbonates, which serve as environmentally benign phosgene substitutes, were successfully produced from carbon dioxide either directly or indirectly. Nucleophilic addition of 2,2,2‐trifluoroethanol to carbon dioxide and subsequent reaction with 2,2,2‐trifluoroethyltriflate ( E OTf ) afforded bis (2,2,2‐trifluoroethyl) carbonate ( 1 ) in up to 79%. Additionally, carbonate 1 was obtained by the stoichiometric reaction of E OTf and cesium carbonate. Although bis (1,1,1,3,3,3‐hexafluoro‐2‐propyl) carbonate ( 3 ) was difficult to be obtained by either of the above two methods, it could be synthesized by the transesterification of carbonate 1 .

    更新日期:2020-02-18
  • Cobalt‐Catalyzed Oxidative C−H Activation: Strategies and Concepts
    ChemSusChem (IF 7.804) Pub Date : 2020-02-17
    Ruhuai Mei; Uttam Dhawa; Ramesh C. Samanta; Wenbo Ma; Joanna Wencel-Delord; Lutz Ackermann

    Inexpensive cobalt‐catalyzed oxidative C−H functionalization has emerged as a powerful tool for the construction of C−C and C−Het bonds, which offers unique potential for transformative applications to modern organic synthesis. In the early stage, these transformations typically required stoichiometric and toxic transition metals as the sacrificial oxidants, thus the formation of metal‐containing waste was inevitable. In contrast, naturally abundant molecular O 2 has more recently been successfully employed as a green oxidant in cobalt catalysis, thus, considerably improving the sustainability of such transformations. Recently, a significant monument was gained by the use of electricity as a sustainable and environmentally benign redox reagent in cobalt‐catalyzed C−H functionalization, thereby, preventing the consumption of cost‐intensive chemicals, while at the same time addressing the considerable safety hazard related to the use of molecular oxygen in combination with flammable organic solvents. Considering the unparalleled potential of the aforementioned approaches for sustainable green synthesis, this review summarizes the recent progress in cobalt‐catalyzed oxidative C−H activation until early 2020.

    更新日期:2020-02-18
  • Recycling of CO2 via hydrogenation of carbonate derivatives to methanol: tuning copper‐oxide promotion effects in supported catalysts
    ChemSusChem (IF 7.804) Pub Date : 2020-02-15
    Jonglack Kim; Norbert Pfänder; Gonzalo Prieto

    The hydrogenation of organic carbonates to methanol is a relevant transformation to realize flexible processes for the recycling of waste CO2 with renewable H2 mediated by condensed CO2 surrogates. Oxide‐supported copper nanoparticles (NPs) are promising solid catalysts for this selective hydrogenation. However, essential for their optimization is to rationalize the prominent impact of the oxide support on performance. Herein, the role of Lewis acid centers, exposed on the oxide support at the periphery of the Cu NPs is systematically assessed. For the hydrogenation of propylene carbonate, as a model cyclic carbonate, the conversion rate, the apparent activation energy as well as the selectivity to methanol correlate with the Lewis acidity of the coordinatively unsaturared cationic sites (cus) exposed on the oxide carrier. Lewis sites of markedly low and high electron withdrawing character promote decarbonylation and decarboxylation unselective reaction pathways, respectively. Supports exposing Lewis sites of intermediate acidity maximize the selectivity to methanol while inhibiting secondary, acid‐catalyzed reactions of the propanediol product, enabling its recovery in cyclic processes of CO2 hydrogenation mediated by condensed carbonate derivatives. These findings help rationalize metal‐support promotion effects which determine the performance of supported metal NPs in this and other selective hydrogenations of significance in the context of sustainable chemistry.

    更新日期:2020-02-18
  • Insight into the superior lithium storage properties of ultrafine CoO nanoparticles confined in 3D bimodal ordered mesoporous carbon CMK‐9 anode
    ChemSusChem (IF 7.804) Pub Date : 2020-02-15
    Diganta Saikia; Juti Rani Deka; Cheng-Wei Lin; Yuan-Hung Lai; Yu-Hao Zeng; Po-Hung Chen; Hsien-Ming Kao; Yung-Chin Yang

    Ultrafine CoO particles immobilized into the mesopores of three dimensional cubic bimodal ordered mesoporous carbon CMK‐9 is successfully prepared by using a combination of nanocasting and wet‐impregnation methods. It is found that cubic bimodal interconnected mesoporous framework of CMK‐9 plays a crucial role in achieving excellent electrochemical performances by assisting the rapid mass and charge transfer. Among the prepared nanocomposites, CoO(10)@CMK‐9 delivers a discharge capacity of 830 mA h g ‐1 after 200 cycles at a current density of 100 mA g ‐1 in lithium‐ion batteries. At a higher current density of 1000 mA g ‐1 , the anode presents an outstanding discharge capacity of 636 mA h g ‐1 after 200 cycles. In sodium‐ion batteries, the anode provides a discharge capacity of 296 mA h g ‐1 after 250 cycles at a current density of 100 mA g ‐1 . The remarkable performances of CoO(10)@CMK‐9 demonstrate the promising potentials of the nanocomposite as the anode for rechargeable batteries.

    更新日期:2020-02-18
  • C2–H Arylation of indoles catalyzed by Palladium containing Metal‐Organic‐Framework (Pd‐MOF) in bioderived γ‐valerolactone (GVL)
    ChemSusChem (IF 7.804) Pub Date : 2020-02-15
    Luigi Vaccaro; Ioannis Anastasiou; Niels Van Velthoven; Elena Tomarelli; Aurora Lombi; Daniela Lanari; Dirk De Vos; Pei Liu; Sara Bals

    Herein we report an efficient and selective procedure for the direct C2‐H arylation of indoles using a Metal‐Organic‐Framework (MOF) containing palladium as heterogeneous catalyst and the non‐toxic biomass derived solvent GVL (γ‐valerolactone) as reaction medium. The developed method allows to reach excellent yields and C‐2 selectivity and tolerates various substitutions on the indole scaffold. The established conditions ensure stability of the catalyst as well as recoverability, reusability and low metal leaching into solution.

    更新日期:2020-02-18
  • Biomass‐derived carbons for sodium‐ion batteries and sodium‐ion capacitors
    ChemSusChem (IF 7.804) Pub Date : 2020-02-15
    Libo Deng; Jianhui Zhu; James Roscow; Sundaram Chandrasekaran; Peixin Zhang; Tingshu He; Kuo Wang; Licong Huang

    In the past decade, the rapid development of portable electronic devices, electric vehicles and electrical devices has stimulated extensive interests in fundamental research and commercialization of electrochemical energy storage systems. Biomass‐derived carbon has garnered significant research attention as an efficient, inexpensive and eco‐friendly active material for energy storage systems. Therefore, high‐performance carbonaceous materials, derived from renewable sources, have been utilized as electrode materials in sodium‐ion batteries and sodium‐ion capacitors. In this review, we summarize the charge storage mechanism and utilization of biomass‐derived carbon for sodium storage in batteries and capacitors. In particular, the structure‐performance relationship of biomass‐derived carbon for sodium storage in the form of batteries and capacitors is discussed. Despite the fact that further research is required to optimize the process and application of biomass‐derived carbon in energy storage devices, the current review demonstrates the potential of carbonaceous materials for next‐generation sodium‐involved energy storage applications.

    更新日期:2020-02-18
  • Phendione‐Transition Metal Complexes with Bipolar Redox for Lithium Batteries
    ChemSusChem (IF 7.804) Pub Date : 2020-02-14
    Alae Eddine Lakraychi; Simon De Kreijger; Deepak Gupta; Benjamin Elias; Alexandru Vlad

    1,10‐Phenanthroline‐5,6‐dione (Phendione) ‐ based transition metal complexes are known for their use in pharmacological and catalysis applications. However, their application in electrochemical energy storage has not been investigated thus far. Herein we prove the feasibility of employing phendione ‐ transition metal complexes for electrochemical charge storage by taking advantage of the reversible redox of both, carbonyl groups and transition metal center, contributing thus to augmented charge storage. Interestingly, the chemistry of the counter ion in the studied complexes effectively tunes the solubility and improves the cycling stability. Whereas further studies are required to limit the solubility and active species shuttle, this study explores the bottlenecks of phendione ‐ transition metal complexes as electrode materials for solid electrode format batteries.

    更新日期:2020-02-18
  • Tuning the electrochemical properties of organic battery cathode materials: Insights from evolutionary algorithm DFT calculations
    ChemSusChem (IF 7.804) Pub Date : 2020-02-14
    Rodrigo P. Carvalho; Cleber F. N. Marchiori; Daniel Brandell; C. Moyses Araujo

    Several forms of organic materials are arising as promising candidates for future active electrode materials for Li‐ion and post Li‐ion batteries due to a series of key features that encompasses sustainability, accessibility and tunable electrochemical properties by molecular modifications. In this context, we here explore a series of organic electrode materials (OEMs) candidates to further understand their thermodynamic and electronic properties. Through an evolutionary algorithm approach interplayed with first‐principles calculations, we have predicted the crystal structure of lithiated and delithiated phases of these OEMs and their respective NO 2 ‐substituted analogues. This framework has allowed a first assessment of their electrochemical and electronic properties, and a further understanding on the effects of the nitro‐group in the substituted compounds. Our findings support that the NO 2 strongly affects structural and thermodynamic aspects during the electrochemical reaction with the reducing equivalents (Li + + e ‐ ), changing the OEM’s character from a low‐potential anode to a high‐potential cathode by creating a localization of the additional electrons, thus resulting in a better defined redox active center and leading to a shift in the potential from 0.92 V to 2.66 V vs Li/Li + .

    更新日期:2020-02-18
  • Borylation of Diazonium Salts by Highly Emissive and Crystalline Carbon Dots in Water
    ChemSusChem (IF 7.804) Pub Date : 2020-02-14
    Li-Zhu Wu; Tao Lei; Si-Meng Wei; Ke Feng; Bin Chen; Chen-Ho Tung

    Efficient borylation reaction of diazonium salts in water is realized for the first time by using easy‐prepared, highly emissive and crystalline carbon dots. Electron‐donating and withdrawing groups on diazonium salts were well tolerated with moderate to good conversion efficiency. Compared with widely used metal complexes, organic dyes and quantum dots, the approach presented in this work uses carbon dots which are nontoxic and possess good biological and medicinal compatibility and high reactivity. Therefore this approach presents a new perspective of carbon dots in green chemistry.

    更新日期:2020-02-14
  • Long‐lifespan Polyanionic Organic Cathodes for Highly Efficient Organic Sodium‐ion Batteries
    ChemSusChem (IF 7.804) Pub Date : 2020-02-14
    Di Li; Wu Tang; Yue Yong Chen; Hui Tan Zheng; Wang Chuan; Cong Fan

    An organic sodium‐ion (Na‐ion) battery is reported. The polyanionic Na2AQ26DS (130 mAh g−1) is used as the organic cathode and the Na‐intercalated state (Na4TP) of Na2TP (255 mAh g−1) is the organic anode. The resulting full cells deliver the max. discharge capacity of 131 mAh g−1cathode in 0.5‐3.2 V, simultaneously maintaining the average value of ~62 mAh g−1cathode during 1200 cycles (0.5 A g−1, ~4 C). These results are among the best organic sodium‐ion full cells reported to date.

    更新日期:2020-02-14
  • Prospects of Value‐Added Chemicals and Hydrogen via Electrolysis.
    ChemSusChem (IF 7.804) Pub Date : 2020-02-14
    Batyr garlyyev; Song Xue; Johannes Fichtner; Aliaksandr Bandarenka; Corina Andronescu

    The cost is a major drawback that limits the industrial scale hydrogen production via water electrolysis. The overall cost of this technology can be decreased by coupling the electrosynthesis of value‐added chemicals at the anode side with the electrolytic hydrogen generation at the cathode. This minireview provides a directory of anodic oxidation reactions that can be combined with the cathodic hydrogen generation. The important parameters for selecting the anodic reactions, such as choice of the catalyst material and its selectivity towards specific product are elaborated in detail. Furthermore, various novel electrolysis cell architectures for effortless separation of value‐added products from hydrogen gas are described.

    更新日期:2020-02-14
  • Poly(phenanthrene quinone)/graphene cathode material and investigation of its redox mechanism through operando ATR‐IR spectroscopy in Li‐ and Mg‐ batteries
    ChemSusChem (IF 7.804) Pub Date : 2020-02-13
    Alen Vizintin; Jan Bitenc; Anja Kopač Lautar; Jože Grdadolnik; Anna Randon-Vitanova; Klemen Pirnat

    In this article, the redox reaction mechanism of poly(phenanthrene quinone)/graphene composite (PFQ/rGO) was determined using operando attenuated total reflection infrared (ATR‐IR) spectroscopy during Li‐ and Mg‐ battery cycling. Reference phenanthrene quinone, Li‐ and Mg‐ salts of hydroquinone monomers were synthesized and their IR spectra measured. Additonally, IR spectra were calculated using density functional theory (DFT). A comparison of all three spectra: operando , chemically synthesized and DFT, allowed us to properly assign C=O and C–O – vibration bands and confirm redox mechanism quinone/Li salt of hydroquinone with radical anion formation as the intermediate product. PFQ/rGO was also tested in Mg‐battery where it showed exceptional performance: potential 1.8 V vs. Mg/Mg 2+ , maximum capacity of 186 mAh/g (335 Wh/kg per cathode material), and high capacity retention, only 8% drop/100 cycles. Operando ATR‐IR spectroscopy was performed in Mg‐organic system as well, revealing analogous redox mechanism to Li‐organic cell.

    更新日期:2020-02-13
  • Metal Catalyst‐Free Oxidative C−C Bond Cleavage of a Lignin Model Compound by H2O2 in Formic acid
    ChemSusChem (IF 7.804) Pub Date : 2020-02-12
    Yugen Zhang; Xiukai Li

    Selective cleavage of the β‐O‐4 ether bond of lignin to produce aromatics is one of the most important topics of the sustainable production of chemicals from biomass. We demonstrate a simple system for C α ‐C β bond cleavage of a β‐O‐4 ketone structured lignin model compound (LMC) by H 2 O 2 in formic acid under metal catalyst‐free conditions. In the system simply with H 2 O 2 , formic acid, and mineral acid catalyst, over 90% of product yield could be achieved in 6 h at room temperature. The reaction proceeds through the classic Baeyer‐Villiger oxidation (BVO) and the in situ generated performic acid is the key oxidant. The cleavage of alcohol LMC by the present method in a two‐step process is also successfully demonstrated.

    更新日期:2020-02-12
  • Dual‐Zinc Electrode Electrochemical Desalination
    ChemSusChem (IF 7.804) Pub Date : 2020-02-12
    fuming chen; Jinhong Dai; Jian Wang; Xianhua Hou; Qiang Ru; Qinyu He; Pattarachai Srimuk; Volker Presser

    Continuous and low‐energy desalination technologies are in high demand to enable sustainable water remediation. Our work introduces a continuous desalination process based on the redox reaction of the dual‐zinc electrode. The system consists of two zinc foils as redox electrodes with flowing ZnCl 2 electrolyte, concentrated and diluted salt streams with three membranes separated configuration (AEM|CEM|AEM). When a constant current applied, the negative zinc electrode is oxidized with electrons released to the external circuit, while the positive zinc electrode is reduced, causing salt removal in the dilution stream. The testing results show that the brackish water can be directly desalted to 380.6 ppm during the continuous batch mode process. The energy consumption can be down to 35.30 kJ∙mol ‐1 at the current density of 0.25 mA∙cm ‐2 , and this consumption is comparable to RO. In addition, the dual‐zinc electrode electrochemical desalination demonstrates the excellent rate performance, reversibility, and batch cyclability via electrode exchange regeneration. Our research provides a route for continuous low‐energy desalination based on metal redox mediators.

    更新日期:2020-02-12
  • Single Molecule Dye Organics with Multi‐electrons Redox as Cathode Material for Li Battery
    ChemSusChem (IF 7.804) Pub Date : 2020-02-12
    Hui Zhan; Fang Men; Ning Liu; Qing Lan; Yali Zhao; Jian Qin; Zhiping Song

    Dissolution loss is the biggest issue for the organic electrode material, and nowadays the most popular strategy is to synthesize polymer or add much conductive carbon. In this paper, the issue is well addressed by monomolecular organics with relatively longer chain and larger size. Dye composing of quinones and carbazoles is proposed as the cathode material for Li secondary battery. The unique structure of more than three quinones collecting by carbazole bridge bond significantly improves the cycling stability. On the other hand, in addition to the widely‐known enolization reaction of the quinone moiety, extra anion‐doping capacity is supplied by the carbazole moiety. Owing to the multiple active sites, multi‐electrons transfer redox and remarkable capacity enhancement is realized by Vet Yellow 3RT dye material. It shows stable capacity up to 340 mAh g‐1 within 300 cycles. XRD, XPS and electrochemical measurement confirm the reactivity of carbonyl group and N‐heterocycle toward Li+ and PF6‐ respectively. The work not only uncovers the new application of dye material, it also provides new avenue to address the dissolution loss and capacity breakthrough of the organics.

    更新日期:2020-02-12
  • Sodium ion capacitors: materials, mechanism and challenges
    ChemSusChem (IF 7.804) Pub Date : 2020-02-11
    Yadi Zhang; Jiangmin Jiang; Yufeng An; Langyuan Wu; Hui Dou; Jiaoxia Zhang; Yu Zhang; Shide Wu; Xiaogang Zhang; Mengyao Dong; Zhanhu Guo

    Sodium ion capacitors (SICs), as designed to deliver high energy density, rapid energy delivery, and long lifespan, have attracted much attention because of their comparable performance to lithium ion capacitors (LICs), albeit with abundant sodium sources. The conventional SICs design is based on battery窶人ike anode and capacitive cathode, in which the battery窶人ike anode materials involve various reactions such as inserted reaction, alloying reaction and conversion reaction, and the capacitive cathode materials usually depend on activated carbon (AC). However, researchers attempted to construct SICs based on battery窶人ike cathode and capacitive anode or a combination of both in recent years. Here, the charge storage mechanism and material design strategies in SICs are summarized, with a focus on battery窶人ike anode materials from inorganic to organic materials. Additionally, the challenges in the fabrication of SICs and future research directions are discussed.

    更新日期:2020-02-12
  • Synthesis of Dual‐Responsive Materials with Reversible and Switchable Phase‐Transition Properties for High‐Performance Cellulose Enzymatic Hydrolysis
    ChemSusChem (IF 7.804) Pub Date : 2020-02-11
    Xing Zhu; Yi Tian; Bin He; Ting Gan; Xiao Hu; Xuechuan Wang

    The Cover Feature shows a smart dual‐responsive material to be used as a carrier for cellulase recovery. This material can undergo reversible and switchable transitions between solution, hydrogel, and solid phases. Based on this concept, cellulase can be released from the solution‐state carrier to hydrolyze cellulose freely, and the product glucose solution can be squeezed out after the hydrogel–solid transition without cellulase. It surmounts the solid–solid phase barrier during the cellulose hydrolyzation and realizes high‐efficiency products/enzymes separation. More information can be found in the Communication by X. Zhu et al.

    更新日期:2020-02-11
  • Ion‐Enhanced Conversion of CO2 into Formate on Porous Dendritic Bismuth Electrodes with High Efficiency and Durability
    ChemSusChem (IF 7.804) Pub Date : 2020-02-11
    Guangxia Piao; Sun Hee Yoon; Dong Suk Han; Hyunwoong Park

    The Front Cover shows multi‐layered porous dendrite Bi electrocatalysts synthesized through hydrogen bubble‐assisted electrodeposition. They exhibit a faradaic efficiency (FE) of approximately 100% in the conversion of CO2 to formate. The added CsCl significantly enhances the steady‐state partial current density for formate production. A photovoltaic cell‐assisted electrocatalysis produces formate with an FE of approximately 95% at 10 mA cm−2 at an overall solar conversion efficiency of approximately 8.5 %. The Bi electrodes maintain their activity over 360 h without a change in the surface states. More information can be found in the Full Paper by G. Piao, S.‐H. Yoon, et al.

    更新日期:2020-02-11
  • Dilution of the Electron Density in the π‐Conjugated Skeleton of Organic Cathode Materials Improves the Discharge Voltage
    ChemSusChem (IF 7.804) Pub Date : 2020-02-11
    Gaole Dai; Yehua Gao; Zhihui Niu; Ping He; Xiaohong Zhang; Yu Zhao; Haoshen Zhou

    Organic compounds are promising candidates as battery materials because they can be sourced from sustainable resources, have tunable structures, and are cheap. However, the working voltage of battery cells containing organic compounds as positive electrodes is relatively lower than that of those containing an inorganic counterpart. In this work, a strategy was developed to increase the discharge voltage of battery cells by diluting the electron density of N‐based redox centers in conjugated organic materials. In electron‐rich heterocyclic compounds that utilize N as the redox center, pentatomic rings such as carbazole derivatives exhibited a higher atomic‐dipole‐moment‐corrected Hirshfeld charge population compared with hexatomic rings, which led to a significant increase in the oxidation potential. As a result, polymeric indolocarbazole derivatives showed a high discharge voltage of 3.7–4.3 V vs. Li+/Li and good cycling performance. Such a strategy can be used to design high‐voltage organic electrode materials containing other redox centers.

    更新日期:2020-02-11
  • Durable Cathodes and Electrolyzers for the Efficient Aqueous Electrochemical Reduction of CO2
    ChemSusChem (IF 7.804) Pub Date : 2020-02-11
    Uzoma O. Nwabara; Emiliana R. Cofell; Sumit Verma; Emanuela Negro; Paul J. A. Kenis

    The world emits over 14 gigatons of CO2 in excess of what can be remediated by natural processes annually, contributing to rising atmospheric CO2 levels and increasing global temperatures. The electrochemical reduction of CO2 (CO2RR) to value‐added chemicals and fuels has been proposed as a method for reusing these excess anthropogenic emissions. While state‐of‐the‐art CO2RR systems exhibit high current densities and faradaic efficiencies, research on long‐term electrode durability, necessary for this technology to be implemented commercially, is lacking. Previous reviews have focused mainly on the CO2 electrolyzer performance without considering durability. In this Review, the need for research into high‐performing and durable CO2RR systems is stressed by summarizing the state‐of‐the‐art with respect to durability. Various failure modes observed are also reported and a protocol for standard durability testing of CO2RR systems is proposed.

    更新日期:2020-02-11
  • Ion‐Enhanced Conversion of CO2 into Formate on Porous Dendritic Bismuth Electrodes with High Efficiency and Durability
    ChemSusChem (IF 7.804) Pub Date : 2020-02-11
    Guangxia Piao; Sun Hee Yoon; Dong Suk Han; Hyunwoong Park

    Invited for this month′s cover is the group of Prof. Hyunwoong Park at the Kyungpook National University. The image shows the high‐efficiency CO2 conversion to formate using multilayered porous dendrite Bi electrocatalysts. The Full Paper itself is available at 10.1002/cssc.201902581.

    更新日期:2020-02-11
  • Influence of the Synthesis Route on the Properties of Hybrid NiO–MnCo2O4–Ni6MnO8 Anode Materials and their Electrochemical Performances
    ChemSusChem (IF 7.804) Pub Date : 2020-02-11
    Jie Zhu; Guolin Cao; Yuan Zhou; Yunjiao Li; Junchao Zheng; Dianwei Zhang

    New materials with different morphologies, nanostructures, and components can have structural advantages for application in materials science. Multicomponent‐active hybrid nanostructured materials are among the best candidates for application in electrode materials. Spray pyrolysis and solvothermal synthesis are two popular methods for the preparation of multicomponent‐active hybrid nanostructured materials. In this study, the two types of NiO‐MnCo2O4‐Ni6MnO8 hybrid anode materials for use in lithium‐ion batteries were synthesized by two different methods (spray pyrolysis and solvothermal synthesis), and the differences in their physical and electrochemical properties were compared. The two types of anode material exhibited the same hierarchical hybrid composition, but some different physical characteristics, which affected their electrochemical performance.

    更新日期:2020-02-11
  • Exploration of New Biomass‐Derived Solvents: Application to Carboxylation Reactions
    ChemSusChem (IF 7.804) Pub Date : 2020-02-11
    Ashot Gevorgyan; Kathrin H. Hopmann; Annette Bayer

    A range of hitherto unexplored biomass‐derived chemicals have been evaluated as new sustainable solvents for a large variety of CO2‐based carboxylation reactions. Known biomass‐derived solvents (biosolvents) are also included in the study and the results are compared with commonly used solvents for the reactions. Biosolvents can be efficiently applied in a variety of carboxylation reactions, such as Cu‐catalyzed carboxylation of organoboranes and organoboronates, metal‐catalyzed hydrocarboxylation, borocarboxylation, and other related reactions. For many of these reactions, the use of biosolvents provides comparable or better yields than the commonly used solvents. The best biosolvents identified are the so far unexplored candidates isosorbide dimethyl ether, acetaldehyde diethyl acetal, rose oxide, and eucalyptol, alongside the known biosolvent 2‐methyltetrahydrofuran. This strategy was used for the synthesis of the commercial drugs Fenoprofen and Flurbiprofen.

    更新日期:2020-02-11
  • Synthesis of NH‐Sulfoximines by Using Recyclable Hypervalent Iodine(III) Reagents under Aqueous Micellar Conditions
    ChemSusChem (IF 7.804) Pub Date : 2020-02-11
    Guocai Zhang; Hongsheng Tan; Weichun Chen; Hong C. Shen; Yue Lu; Changwu Zheng; Hongxi Xu

    The synthesis of NH‐sulfoximines from sulfides has been first developed under mild conditions in an aqueous solution with surfactant TPGS‐750‐M as the catalyst at room temperature. In this newly developed process, a simple and convenient recycling strategy to regenerate the indispensable hypervalent iodine(III) is used. The resulting 1,2,3‐trifluoro‐5‐iodobezene can be recovered almost quantitively from the mixture by liquid–liquid extraction and then oxidized to give the corresponding iodine(III) species. This optimized procedure is compatible with a broad range of functional groups and can be easily performed on a gram scale, providing a green protocol for the synthesis of sulfoximines.

    更新日期:2020-02-11
  • Preparation of Iron‐ and Nitrogen‐Codoped Carbon Nanotubes from Waste Plastics Pyrolysis for the Oxygen Reduction Reaction
    ChemSusChem (IF 7.804) Pub Date : 2020-02-11
    Ning Cai; Sunwen Xia; Xiong Zhang; Zihan Meng; Pietro Bartocci; Francesco Fantozzi; Yingquan Chen; Hanping Chen; Paul T. Williams; Haiping Yang

    A novel method for the preparation of iron‐ and nitrogen‐codoped carbon nanotubes (Fe‐N‐CNTs) is proposed, based on the catalytic pyrolysis of waste plastics. First, carbon nanotubes are produced from pyrolysis of plastic waste over Fe‐Al2O3; then, Fe‐CNTs and melamine are heated together in an inert atmosphere. Different co‐pyrolysis temperatures are tested to optimize the electrocatalyst production. A high doping temperature improves the degree of graphite formation and promotes the conversion of nitrogen into a more stable form. Compared with commercial Pt/C, the electrocatalyst obtained from pyrolysis at 850 °C shows remarkable properties, with an onset potential of 0.943 V versus RHE and a half‐wave potential of 0.811 V versus RHE, and even better stability and anti‐poisoning properties. In addition, zinc–air battery tests are performed, and the optimized catalyst exhibits a high maximum power density.

    更新日期:2020-02-11
  • Improving Artificial Photosynthesis over Carbon Nitride by Gas–Liquid–Solid Interface Management for Full Light‐Induced CO2 Reduction to C1 and C2 Fuels and O2
    ChemSusChem (IF 7.804) Pub Date : 2020-02-11
    Yang Xia; Kai Xiao; Bei Cheng; Jiaguo Yu; Lei Jiang; Markus Antonietti; Shaowen Cao

    The activity and selectivity of simple photocatalysts for CO2 reduction remain limited by the insufficient photophysics of the catalysts, as well as the low solubility and slow mass transport of gas molecules in/through aqueous solution. In this study, these limitations are overcome by constructing a triphasic photocatalytic system, in which polymeric carbon nitride (CN) is immobilized onto a hydrophobic substrate, and the photocatalytic reduction reaction occurs at a gas–liquid–solid (CO2–water–catalyst) triple interface. CN anchored onto the surface of a hydrophobic substrate exhibits an approximately 7.2‐fold enhancement in total CO2 conversion, with a rate of 415.50 μmol m−2 h−1 under simulated solar light irradiation. This value corresponds to an overall photosynthetic efficiency for full water–CO2 conversion of 0.33 %, which is very close to biological systems. A remarkable enhancement of direct C2 hydrocarbon production and a high CO2 conversion selectivity of 97.7 % are observed. Going from water oxidation to phosphate oxidation, the quantum yield is increased to 1.28 %.

    更新日期:2020-02-11
  • Transforming Methyl Levulinate into Biosurfactants and Biolubricants by Chemoselective Reductive Etherification with Fatty Alcohols
    ChemSusChem (IF 7.804) Pub Date : 2020-02-11
    Andrea Garcia‐Ortiz; Karen S. Arias; Maria J. Climent; Avelino Corma; Sara Iborra

    The Cover Feature shows that biosurfactants and biolubricants can be produced by reaction of lignocellulose‐derived methyl levulinate and ketones with fatty alcohols in the presence of hydrogen and Pd nanoparticles. More information can be found in the Full Paper by A. Garcia‐Ortiz et al.

    更新日期:2020-02-11
  • Revisited Oxygen Reduction Reaction on Gold Surface at Different pH Values with In‐situ Surface Enhanced Raman Spectroscopy
    ChemSusChem (IF 7.804) Pub Date : 2020-02-11
    Hai-Yang Yu; Xiao-Feng Li; Tian-Heng Zhang; Jiao Liu; Jing-Hua Tian; Ruizhi Yang

    The mechanisms of oxygen reduction reaction (ORR) on gold surfaces are revisited in electrolytes at different pH values by the combination of electrochemical and in‐situ Surface Enhanced Raman Scattering measurements. Surprisingly, the in‐situ Raman signal of O‐O stretching vibration has been detected during ORR process on Au surface unusually by using a 785 nm laser. Both the intermediate products of O 2 ‐ and H 2 O 2 could be detected, indicating that the difficulty of further reduction H 2 O 2 , thus resulting in a lower electron transfer number, especially in neutral and acid electrolytes. The weak absorption ability of HO 2 on Au surface may explain the poor catalytic performances of ORR in neutral and acid electrolytes. This work could not only provide a deep insight to understand the reduction mechanisms of O 2 on Au in electrolytes at different pH values, but also supply a new idea for the selection and optimization of the electrolytes and efficient electrocatalysts for oxygen reduction.

    更新日期:2020-02-11
  • Organic Cathode Materials for Rechargeable Zinc Batteries: Mechanisms, Challenges and Perspectives
    ChemSusChem (IF 7.804) Pub Date : 2020-02-11
    Jin Cui; Zhaowei Guo; Jin Yi; Xiaoyu Liu; Kai Wu; Pengcheng Liang; Qian Li; Yuyu Liu; Yonggang Wang; Yongyao Xia; Jiujun Zhang

    Energy and environmental issues have given rise to the development of advanced energy storage devices worldwide. Electrochemical energy technologies, such as rechargeable batteries, have been considered to be the most reliable and efficient candidates. Compared with other batteries, zinc‐based batteries seem promising due to their advantages including inherent safety, cost‐effectiveness and environmental‐friendliness. As potential alternatives to conventional inorganic cathodes, organic cathodes for zinc‐organic batteries have become the research hotspot owing to their favorable characteristics, such as easy structure design, controllable synthesis and environmental benignancy. In this paper, we provide a systematical overview on the fundamentals of organic cathode materials for zinc batteries including material design, electrochemical mechanisms, technical advances and challenge analysis. Furthermore, the perspectives and corresponding research directions are offered in order to facilitate the future development of organic cathode materials for zinc batteries toward practical applications.

    更新日期:2020-02-11
  • Reversible Hybrid Aqueous Li‐CO2 Batteries with High Energy Density and HCOOH Production
    ChemSusChem (IF 7.804) Pub Date : 2020-02-10
    Rui Yang; Zhen Peng; Jiafang Xie; Yiyin Huang; Rahul Anil Borse; Xueyuan Wang; Maoxiang Wu; Yaobing Wang

    Metal‐CO 2 batteries, an attractive technology for both energy storage and CO 2 utilization, are typically classified into organic Li(Na)‐CO 2 batteries with a high energy density/output voltage and aqueous Zn‐CO 2 batteries with flexible chemical production. However, achieving high‐efficiency energy storage and flexible chemical production simultaneously is still challenging. Herein, we proposed and realized a reversible hybrid aqueous Li‐CO 2 battery integrating Li with aqueous phase, exhibiting not only a high operating voltage and energy density, but also highly selective HCOOH production simultaneously. Based on a Li plate as the anode, NaCl solution as aqueous electrolyte, solid electrolyte Li 1.5 Al 0.5 Ge 1.5 P 3 O 12 (LAGP) as separator and Li + transporter, and a bifunctional Pd‐based electrocatalyst as the cathode, the resulting battery possessed the high discharge voltage up to 2.6 V, the outstanding energy conversion efficiency higher than 80%, and the remarkable selectivity of CO 2 ‐to‐HCOOH conversion up to 97%. The related reaction mechanism was proposed as CO 2 +2Li+2H + ⇋HCOOH+2Li + .

    更新日期:2020-02-10
  • Redox‐Active Functional Electrolyte for High‐Performance Seawater Batteries
    ChemSusChem (IF 7.804) Pub Date : 2020-02-09
    Seyoung Lee; Il Young Cho; Dowan Kim; Nam Kyu Park; Jaehyun Park; Yongil Kim; Seok Ju Kang; Youngsik Kim; Sung You Hong

    Rechargeable seawater batteries have gained recognition as key sustainable electrochemical systems by employing the near‐infinite and eco‐friendly catholyte, seawater. However, their practical applications have been limited due to the low chemical and electrochemical stabilities of anode component. Herein, we unveil stability‐secured approach using sodium‐biphenyl‐dimethoxyethane solution as a redox‐active functional anolyte for high‐performance seawater batteries. This anolyte system shows high electrochemical stability, superior cycle performance, and cost‐effectiveness over conventional electrolyte systems.

    更新日期:2020-02-10
  • Viologen Derivatives Extended with Aromatic Rings Acting as Negative Electrode Materials for Use in Rechargeable Molecular Ion Batteries
    ChemSusChem (IF 7.804) Pub Date : 2020-02-09
    MINAMI KATO; Hikaru Sano; Tetsu Kiyobayashi; Masaru Yao

    Abstract : Many types of batteries have been proposed as next‐generation energy storage systems. One candidate is a rocking chair type ‘molecular ion battery’ in which a molecular ion, instead of Li+ , works as a charge carrier. We have previously reported a viologen‐type derivative as a negative electrode material that releases and receives PF6− anions during the charge/discharge process; however, its redox potential was not satisfactorily low. The two potential plateaus of this material, of which the difference is 0.5 V, should also be reduced. In this study, PF6− salts of viologen (bipyridinium) derivatives extended by aromatic rings were synthesized to obtain a negative electrode material with a lower redox potential and small potential change during the charge and discharge processes. Some of the synthesized viologen derivatives were fluorescent, even in the solid‐state electrodes. In the battery test with a half‐cell, the prepared negative electrode materials showed average voltages of approximately 2 V (vs. Li), which is lower than conventional viologen derivatives.

    更新日期:2020-02-10
  • Recent Advances on Rational Design and Synthesis of Two‐Dimensional Materials for Multivalent Ion Batteries
    ChemSusChem (IF 7.804) Pub Date : 2020-02-07
    Lianmeng Cui; Limin Zhou; Yong-Mook Kang; Qinyou An

    With the progressive increasing of device requirements, rechargeable lithium‐ion batteries are facing tremendous challenges in large‐scale application due to high price and gradual shortage of lithium sources. In contrast, multivalent ion batteries, such as Al, Mg, and Zn, are promising candidates for the next‐generation energy storage systems because of their high volume energy density, safe operation, and abundant reserves. The strong intercalation between multivalent ions and the host materials, however, will cause a lower ion diffusion kinetics and poor discharge capacity. One of the main challenges is to searching a suitable cathode material with a high capacity and good structure stability to overcome above problems. Two‐dimensional (2D) layered materials, characteristic of unique structural features, good conductivity, and high electrochemically active surface, have attracted attentions of researchers during the past decade. In this review, we summarize the design approach and synthesis routine of the 2D materials served as a cathode for multivalent ion batteries in detail, including interlayer engineering, 2D heterostructures, pore/hole engineering, and heteroatom doping. Meanwhile, the relationship between configuration design and optimized electrochemical performance is rationally and systematically presented. Besides, the perspectives of sustainable synthesis for cathode materials are proposed for multivalent metal ion chemistry.

    更新日期:2020-02-10
  • Optimizing Electron Densities of Ni‐N‐C Complexes by Hybrid Coordination for Efficient Electrocatalytic CO2 Reduction
    ChemSusChem (IF 7.804) Pub Date : 2020-02-06
    Zhong‐Li Wang; Jaecheol Choi; Mingquan Xu; Xianfeng Hao; Hao Zhang; Zheng Jiang; Ming Zuo; Jeonghun Kim; Wu Zhou; Xianguang Meng; Qing Yu; Zhihu Sun; Shiqiang Wei; Jinhua Ye; Gordon G. Wallace; David L. Officer; Yusuke Yamauchi

    Metal‐N‐C is a type of attractive electrocatalyst for efficient CO2 reduction to CO. Because of the ambiguity in their atomic structures, the active sites and catalytic mechanisms of the catalysts have remained under debate. Here, the effects of N and C hybrid coordination on the activity of Ni‐N‐C catalysts were investigated, combining theoretical and experimental methods. The theoretical calculations revealed that N and C hybrid coordination greatly enhanced the capability of single‐atom Ni active sites to provide electrons to reactant molecules and strengthens the bonding of Ni to N and C in the Ni‐N‐C complexes. During the reaction process, the C and N coordination synergistically optimized the reaction energies in the conversion of CO2 to CO. A good agreement between theoretical calculations and electrochemical experiments was achieved based on the newly developed Ni‐N‐C electrocatalysts. The activity of hybrid‐coordination NiN2C2 was more than double that of single‐coordination NiN4.

    更新日期:2020-02-07
  • Interdigitated Hierarchical Integration of an Efficient Lateral Perovskite Single‐Crystal Solar Cell
    ChemSusChem (IF 7.804) Pub Date : 2020-02-06
    Jinseon Park; Yeong Eun Bak; Lynn Lee; Hyosung Choi; Mahmood Alam Khan; Myung M. Sung

    Single‐crystal perovskite thin films were prepared by a scalable, one‐step, geometrically confined lateral crystal growth (GC‐LCG) method on a patterned rolling mold and used for a photovoltaic study. A record solar cell efficiency of 9.50 % under 0.1 sun with an electrode spacing of 1.5 μm is attained in lateral single‐crystal perovskite materials. Moreover, successful integration for high‐source‐power‐generation interdigitated electrode units patterned in series (1×4), parallel (4×1), and combination (4 series×4 parallel) configurations is devised and affords maximum efficiencies of 7.99, 8.19, and 7.96 %, respectively. Additionally, the cell performances under various illumination intensities (0.1, 0.2, 0.4, 0.6, 0.8, 1.0 sun) to mimic daily sunshine angles and an indoor environment at 1000 lux are elucidated for which short‐circuit current (JSC) values (19.60 mA cm−2 and η=7.43 %) under 1.0 sun and a significant efficiency of 8.13 % under indoor conditions are obtained. This work represents a significant step towards next‐generation, efficient, lateral photovoltaics for possible module integration.

    更新日期:2020-02-07
  • 3 D NiO Nanowall Hole‐Transporting Layer for the Passivation of Interfacial Contact in Inverted Perovskite Solar Cells
    ChemSusChem (IF 7.804) Pub Date : 2020-02-06
    Xin Yin; Jifeng Zhai; Pingfan Du; Ni Li; Lixin Song; Jie Xiong; Frank Ko

    Nickel oxide (NiO) materials with excellent stability and favorable energy bands are desirable candidates for hole‐selective contact (HSC) of inverted perovskite solar cell (PSC). However, studies that focus on addressing interfacial issues, which are induced by the poor NiO/perovskite contact or other defects, are scarce. In this study, a facile one‐step hydrothermal strategy is demonstrated for the development of a 3 D NiO nanowall (NW) film as a promising HSC. The new NiO NWs HSC exhibits a robust and homogenous mesoporous network structure, which improved the NiO/perovskite interface contact, passivated the interfacial defect and improved the quality of the perovskite film. The optimized interface features enabled a power conversion efficiency (PCE) approaching 18 %. A diethanolamine (DEA) interlayer was introduced to further passivate the intrinsic defect of the NiO surface, resulting in better charge transfer with suppressed recombination loss. As a result, the champion PCE of the NiO NWs/DEA‐based device was increased to 19.16 % with a high open‐circuit voltage (≈1.11 V) and fill factor (>80 %), which is prominent in methylammonium lead iodide‐based inverted PSCs. Furthermore, the device exhibited better stability and lower hysteresis behavior than a conventional solution‐based NiO nanocrystal device.

    更新日期:2020-02-07
  • Atomic Force Microscopy and Molecular Dynamics Simulations for Study of Lignin Solution Self‐Assembly Mechanisms in Organic–Aqueous Solvent Mixtures
    ChemSusChem (IF 7.804) Pub Date : 2020-02-06
    Jingyu Wang; Yong Qian; Libo Li; Xueqing Qiu

    Lignin‐based nanomaterials fabricated by solution self‐assembly in organic–aqueous solvent mixtures are among the most attractive biomass‐derived products. To accurately control the structure, size, and properties of lignin‐based nanomaterials, it is important to achieve fundamental understanding of its dissolution and aggregation mechanisms. In this work, atomic force microscopy (AFM) and molecular dynamics (MD) simulations are employed to explore the dissolution and aggregation behavior of enzymatic hydrolysis lignin (EHL) in different organic–aqueous solvent mixtures at molecular scale. EHL was found to dissolve well in appropriate organic–aqueous solvent mixtures, such as acetone–water mixture with a volume ratio of 7:3, whereas it aggregated in pure water, ethanol, acetone, and tetrahydrofuran. The interactions between the EHL‐coated AFM probe and the substrate were 1.21±0.18 and 0.75±0.35 mN m−1 in water and acetone, respectively. In comparison, the interaction decreased to 0.15±0.08 mN m−1 in acetone–water mixture (7:3 v/v). MD simulations further indicate that the hydrophobic skeleton and hydrophilic groups of lignin could be solvated by acetone and water molecules, respectively, which significantly promoted its dissolution. Conversely, only the hydrophobic skeleton or the hydrophilic groups were solvated in organic solvent or water, respectively, inducing serious aggregation of lignin.

    更新日期:2020-02-07
  • Effect of Continuous Capacity Rising Performed by FeS/Fe3C/C Composite Electrodes for Lithium‐Ion Batteries
    ChemSusChem (IF 7.804) Pub Date : 2020-02-06
    Chengping Li; Angelina Sarapulova; Kristina Pfeifer; Sonia Dsoke

    FeS‐based composites are sustainable conversion electrode materials for lithium‐ion batteries, combining features like low cost, environmental friendliness, and high capacities. However, they suffer from fast capacity decay and low electron conductivity. Herein, novel insights into a surprising phenomenon of this material are provided. A FeS/Fe3C/C nanocomposite synthesized by a facile hydrothermal method is compared with pure FeS. When applied as anode materials for lithium‐ion batteries, these two types of materials show different capacity evolution upon cycling. Surprisingly, the composite delivers a continuous increase in capacity instead of the expected capacity fading. This unique behavior is triggered by a catalyzing effect of Fe3C nanoparticles. The Fe3C phase is a beneficial byproduct of the synthesis and was not intentionally obtained. To further understand the effect of interconnected carbon balls on FeS‐based electrodes, complementary analytic techniques are used. Ex situ X‐ray radiation diffraction and ex situ scanning electron microscopy are employed to track phase fraction and morphology structure. In addition, the electrochemical kinetics and resistance are evaluated by cyclic voltammetry and electrochemical impedance spectroscopy. These results reveal that the interconnected carbon balls have a profound influence on the properties of FeS‐based electrodes resulting in an increased electrode conductivity, reduced particle size, and maintenance of the structure integrity.

    更新日期:2020-02-07
  • Electrochemically Driven Formation of Sponge‐like Porous Ag Nanocubes toward Efficient CO2 Electroreduction to CO
    ChemSusChem (IF 7.804) Pub Date : 2020-02-05
    Tingting Fan; Qiuling Wu; Zhou Yang; Yipeng Song; Jiguang Zhang; Pingping Huang; Zhou Chen; Yunyun Dong; Weiping Fang; Xiaodong Yi

    Electrochemical conversion of carbon dioxide into valuable products by utilizing renewable electricity is a thriving research field. For electrochemical reduction of CO 2 to CO, uniform sponge‐like porous Ag nanocubes (SPC‐Ag) integrated on carbon papers are prepared by electrochemically driven method. SPC‐Ag process three dimensional (3D) porous structure and large specific surface area, which afford abundant active sites for CO 2 RR as well as reduce impedance to accelerate faster CO 2 RR kinetics. Such a distinctive organization affords SPC‐Ag with outstanding electrocatalytic performance for CO 2 reduction to CO. High Faradaic efficiency (FE) (>90%) and large partial current density for CO with excellent durability are observed in a wide potential window, accompanied by a maximum value of 93% at ‐0.9 V vs. RHE.

    更新日期:2020-02-06
  • Catalytic Semi‐Water Gas Shift Reaction: A Simple Green Path to Formic Acid Fuel
    ChemSusChem (IF 7.804) Pub Date : 2020-02-05
    Jairton Dupont; Muhammed Irfan Qadir; Marcus V Castegnaro; Felipe F; Mario Samperi; Jesum A Fernandes; Jonder Morais

    Formic acid (FA) is a promising CO and hydrogen energy carrier and currently its generation is mainly centred on the hydrogenation of CO 2 . However, it can also be obtained by the hydrothermal conversion of CO with H 2 O at very high pressures (>100 bar) and temperatures (>200°C) and requiring days to complete. Herein, we demonstrate that use of a nano‐Ru/Fe alloy embedded in an ionic liquid (IL)‐hybrid silica in the presence of the appropriate IL in water, CO can be catalytically converted into free FA (0.73 M) under very mild reactions conditions (10 bar at 80°C) with TON up to 1269. The catalyst was prepared by simple reduction/decomposition of Ru and Fe complexes in the IL, and it was then embedded into an IL‐hybrid silica [1‐n‐butyl‐3‐(3‐trimethoxysilylpropyl)‐imidazolium cations associated with hydrophilic (acetate, SILP‐OAc) and hydrophobic (bis((trifluoromethyl)sulfonyl)amide, (SILP‐NTf 2 ) anions]. The location of the alloy NPs on the support is strongly related with the nature of the anion, i.e., in the case of hydrophilic SILP‐OAc, RuFe NPs are more exposed to the support surface than in the case of the hydrophobic SILP‐NTf 2 , as determined by RBS (Rutherford backscattering spectrometry). This catalytic membrane in the presence of H 2 O/CO and an appropriate IL, namely, 1,2‐dimethyl‐3‐n‐butylimidazolium 2‐methyl imidazolate (BMMIm.MeIm), is stable and recyclable for at least 5 runs, yielding a total of 4.34 M of free FA.

    更新日期:2020-02-06
  • A High‐Power Aqueous Zinc‐Organic Radical Battery with Tunable Operating Voltage Triggered by Selected Anions
    ChemSusChem (IF 7.804) Pub Date : 2020-02-05
    Yuwen Luo; Feipeng Zheng; Luojia Liu; Kaixiang Lei; Xuesen Hou; Gang Xu; Hui Meng; Jifu Shi; Fujun Li

    Unlike traditional rechargeable rock‐chair metal‐ion batteries, dual‐ion batteries (DIBs) involve redox reactions with anions rather than cations in p‐type cathodes. In principle, regulating the electrochemical performance of the DIB by different anion species is highly feasible. Herein, the anion effect on the electrochemical performance of a DIB, aqueous Zn‐organic radical battery (Zn‐ORB) consisting of poly(2,2,6,6‐tetramethylpiperidinyloxy‐4‐yl vinyl ether) cathode and Zn anode, is firstly investigated by density functional theory (DFT) calculations. SO 4 2‐ , CF 3 SO 3 ‐ and ClO 4 ‐ with different molecular electrostatic potential values are selected as anion models. DFT calculations reveal that the stronger electrostatic interaction of the anion with the organic radical, the higher operating voltage of the Zn‐ORB, which are well consistent with experimental results. It brings new insight into the redox chemistry of p‐type organic radical with anions and will promote the development of high‐power aqueous Zn‐ORBs as well as inspire more investigations for anion effect towards novel battery designs.

    更新日期:2020-02-06
  • A Flexible Interpenetrated Zirconium‐Based Metal‐Organic Framework with High Affinity toward Ammonia
    ChemSusChem (IF 7.804) Pub Date : 2020-02-05
    Yuanyuan Zhang; Xuan Zhang; Zhijie Chen; Ken-ichi Otake; Gregory Peterson; Yongwei Chen; Xingjie Wang; Louis Redfern; Subhadip Goswami; Peng Li; Timur Islamoglu; Bo Wang; Omar K Farha

    Flexible metal‐organic frameworks (MOFs) are highly attractive porous crystalline materials presenting structural changes when exposed to external stimuli, the mechanism of which is often difficult to glean, owing to their complex and dynamic nature. Herein, we report a flexible, interpenetrated Zr‐MOF, NU‐1401, composed of rare 4‐connected Zr6 nodes and tetratopic naphthalenediimide (NDI)‐based carboxylate linkers. The intra‐framework pore opening deformation and inter‐framework motions, when subjected to different solvent molecules, are investigated by single‐crystal X‐ray diffraction. It is shown that the distance and overlap angle between the stacked NDI pairs in the entangled structure can be finely tuned, and the interactions between NDI and solvent molecules lead to a solvochromism property. Furthermore, the presence of electron‐deficient NDI units and Lewis acidic Zr(IV) site in the interpenetrated porous structure offers high density of adsorption sites for ammonia molecules, resulting in high uptake at low pressures.

    更新日期:2020-02-06
  • Plasma‐driven in situ production of hydrogen peroxide for biocatalysis
    ChemSusChem (IF 7.804) Pub Date : 2020-02-05
    Abdulkadir Yayci; Álvaro Gómez Baraibar; Marco Krewing; Elena Fernandez Fueyo; Frank Hollmann; Miguel Alcalde; Robert Kourist; Julia Elisabeth Bandow

    Peroxidases and peroxygenases are promising classes of enzymes for biocatalysis because of their ability to carry out one‐electron oxidation reactions and stereoselective oxyfunctionalizations. Industrial application is however limited, as the major drawback is the sensitivity towards the required peroxide substrates. Herein, we report a novel biocatalysis approach to circumvent this shortcoming: in situ production of H2O2 by dielectric barrier discharge plasma. The discharge plasma can be controlled to produce hydrogen peroxide at desired rates yielding desired concentrations. Using horseradish peroxidase, we demonstrated that hydrogen peroxide produced by plasma treatment can drive the enzymatic oxidation of model substrates. Fungal peroxygenase was then employed to convert ethylbenzene to (R)‐1‐phenylethanol with an ee of >96% using plasma‐generated hydrogen peroxide. Since direct treatment of the reaction solution with plasma resulted in reduced enzyme activity, the use of plasma‐treated liquid and protection strategies were investigated to increase total turnover. Technical plasmas present a non‐invasive means to drive peroxide‐based biotransformations.

    更新日期:2020-02-06
  • The interplay of porosity, wettability, and redox activity as determining factors for lithium‐organic electrochemical energy storage using biomolecules
    ChemSusChem (IF 7.804) Pub Date : 2020-02-05
    Ivan K Ilic; Milena Perovic; Clemens Liedel

    While several recent publications describe cathodes for electrochemical energy storage materials made from regrown biomass in aqueous electrolytes, their transfer to lithium‐organic batteries is challenging. In order to gain a deeper understanding, we therefore investigate influences on charge storage in model systems based on biomass‐derived, redox‐active compounds and comparable structures. Hybrid materials from these model polymers and porous carbon are compared in order to precisely determine causes of exceptional capacity in lithium‐organic systems. It is found that besides redox activity especially wettability greatly influences capacity of the composites. Furthermore, in addition to bio‐derived molecules with catechol functionalities, which are commonly described as redox‐active species in lithium‐bioorganic systems, this manuscript further describes guaiacol groups as a promising alternative for the first time and compares performance of respective compounds.

    更新日期:2020-02-06
  • Copper‐Catalyzed Formylation of Amines by using Methanol as the C1 Source
    ChemSusChem (IF 7.804) Pub Date : 2020-02-04
    Manuel Carmona Pichardo; Ghazal Tavakoli; Jessica E. Armstrong; Tobias Wilczek; Bradley E. Thomas; Martin H. G. Prechtl

    Cu/TEMPO catalyst systems are known for the selective transformation of alcohols to aldehydes, as well as for the simultaneous coupling of alcohols and amines to imines under oxidative conditions. In this study, such a Cu/TEMPO catalyst system is found to catalyze the N‐formylation of a variety of amines by initial oxidative activation of methanol as the carbonyl source via formaldehyde and formation of N,O‐hemiacetals and oxidation of the latter under very mild conditions. A vast range of amines, including aromatic and aliphatic, primary and secondary, and linear and cyclic amines are formylated under these conditions with good to excellent yields. Moreover, paraformaldehyde can be used instead of methanol for the N‐formylation.

    更新日期:2020-02-04
  • A Near‐Infrared Absorption Small Molecule Acceptor for High‐Performance Semitransparent and Colorful Binary and Ternary Organic Photovoltaics
    ChemSusChem (IF 7.804) Pub Date : 2020-02-04
    Chun‐Kai Wang; Bing‐Huang Jiang; Jong‐Hong Lu; Ming‐Tsang Cheng; Ru‐Jong Jeng; Yu‐Wei Lu; Chih‐Ping Chen; Ken‐Tsung Wong

    An acceptor–donor–acceptor (A–D–A)‐type non‐fullerene acceptor (NFA), PTTtID‐Cl, featuring thieno[3,2‐b]thieno[2′′′,3′′′:4′′,5′′]‐pyrrolo[2′′,3′′:4′,5′]thieno[2′,3′:4,5]thieno‐[2,3‐d]pyrrole (DTPTt) as the electron‐rich core and 2‐(5,6‐dichloro‐3‐oxo‐2,3‐dihydro‐1H‐inden‐1‐ylidene)malononitrile (ID‐Cl) as the peripheral electron‐deficient terminal group was synthesized and characterized. PTTtID‐Cl exhibited strong absorption in the range of 700–850 nm in CHCl3 and redshifted absorption centered at 881 nm in a thin film. The near infrared (NIR)‐absorption of PTTtID‐Cl was combined with a low‐bandgap polymer donor (PTB7‐Th) to achieve binary and semitransparent organic photovoltaics (OPVs) with a power conversion efficiency (PCE) of 8.9 % and 7.7 % (with an average visible transmittance (AVT) of 16.7 %), respectively. A ternary device with a ratio of PM7/PTTtID‐Cl/IT‐4F=1:0.15:0.85 (w/w) achieved a short‐circuit current density of 19.46 mA cm−2, an open‐circuit voltage of 0.87 V, and a fill factor of 71.2 %, giving a PCE of 12.0 %. In addition, by employing the Ag/ITO/Ag microcavity structure, semitransparent colorful binary organic photovoltaics (OPVs) with superior transparency of 27.9 % at 427 nm and 22.7 % at 536 nm for blue and green devices, respectively, were prepared. The semitransparent colorful devices based on the optimized ternary blend gave PCEs of 8.7 %, 8.4 %, and 9.1 % for blue, green, and red devices, respectively. These results indicate the promising potential of PTTtID‐Cl as a NIR‐absorption NFA for applications in semitransparent colorful binary and ternary OPVs.

    更新日期:2020-02-04
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