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  • Sustainable synthesis of oxalic (and succinic) acid via aerobic oxidation of C6 polyols by using M@CNT/NCNT (M=Fe, V) based catalysts in mild conditions
    ChemSusChem (IF 7.226) Pub Date : 2018-01-16
    Angela Dibenedetto, Maria Ventura, David Williamson, Francesco Lobefaro, Matthew D. Jones, Davide Mattia, Francesco Nocito, Michele Aresta

    Sustainable chemical industry encompasses the shift from fossil carbon to renewable carbon. The synthesis of chemicals from non-edible biomass (cellulosic or oily) represents one of the key steps for "greening" the chemical industry. In this paper we report the aerobic oxidation-cleavage of C6 polyols (5-HMF, glucose, fructose, sucrose) in water to oxalic acid-OA (and succinic acid-SA) under mild conditions using M@CNT/NCNT (M=Fe, V; CNT=carbon nanotubes; NCNT= N-doped CNT), which, under suitable conditions, are recoverable and reusable without any loss of efficiency. The influence of temperature, PO2, reaction time, stirring rate are discussed and the best reaction conditions are emphasized for an almost complete conversion of the starting material, with a good yield of OA equal to 48%. SA and formic acid are the only co-products. The former can be further converted into OA by oxidation in presence of formic acid allowing to reach an overall yield of OA >62%. This process is clean and does not produce organic waste nor gas emissions.

    更新日期:2018-01-16
  • Polypropylene Nonwoven Fabric@Poly(ionic liquid)s for Switchable Oil/Water Separation, Dye Absorption and Antibacterial Applications
    ChemSusChem (IF 7.226) Pub Date : 2018-01-15
    yongyuan ren, jiangna guo, dan xu, jing qin, qian lu, Feng Yan

    Pollutants in wastewater include oils, dyes, and bacteria, making wastewater cleanup difficult. Here, we propose the preparation of multifunctional wastewater treatment media, poly(ionic liquid) grafted polypropylene (PP) nonwoven fabrics (PP@PIL), prepared via a simple and scalable surface grafting process. The fabricated PP@PIL fabrics exhibited superior switchable oil/water separation (η > 99%) and dye absorption performance (q = 410 mg/g), as well as high antibacterial properties. The oil/water separation could be easily switched via anion-exchanging of PIL segments. Moreover, the multiple functions (oil/water separation, dye absorption, and antibacterial properties) occurred at the same time, and did not interfere with each other. The multifunctional fibrous filter could be easily regenerated by washing with an acid solution, and the absorption capacity is maintained after many recycling tests. These promising features make PIL grafted PP nonwoven fabric a potential one-step treatment for multicomponent wastewater

    更新日期:2018-01-15
  • Pyran-Bridged Indacenodithiophene as a Building Block for Constructing Efficient A–D–A-Type Nonfullerene Acceptors for Polymer Solar Cells
    ChemSusChem (IF 7.226) Pub Date : 2018-01-15
    Shuguang Wen, Yao Wu, Yingying Wang, Yi Li, Ling Liu, Huanxiang Jiang, Zhitian Liu, Renqiang Yang
    更新日期:2018-01-15
  • Photo-initiated Reduction of CO2 by H2 on Silica Surface
    ChemSusChem (IF 7.226) Pub Date : 2018-01-12
    Chao Liu, Justin M. Notestein, Eric Weitz, Kimberly A. Gray

    The reduction of CO2 is a promising route to produce valuable chemicals or fuels and create C-neutral resource cycles. Many different approaches to CO2 reduction have been investigated, but the ability of vacuum UV (VUV) irradiation to cleave C-O bonds has remained largely unexplored for use in processes that convert CO2 into useful products. Compared with other photo-driven CO2 conversion processes, here we demonstrate that VUV-initiated CO2 reduction can achieve much greater conversion under common photochemical reaction conditions when H2 and non-reducible oxides are present. Infrared spectroscopy provides evidence for a chain reaction initiated by VUV-induced CO2 splitting, which is enhanced in the presence of H2 and silica. When the reaction is carried out in the presence of silica or alumina surfaces, CO yields are increased and CH4 is formed as the only other detected product. CH4 production is not promoted by traditional photocatalysts such as TiO2 under these conditions. Assuming improvements in lamp and reactor efficiencies with scale up, or coupling with other available CO/CO2 hydrogenation techniques, these results reveal a potential, simple strategy by which CO2 could be valorized.

    更新日期:2018-01-13
  • Methanol-Water Aqueous Phase Reforming by the Assistant of Dehydrogenases at Near-Room Temperature
    ChemSusChem (IF 7.226) Pub Date : 2018-01-11
    Yangbin Shen, Yulu Zhan, Shuping Li, Fandi Ning, Ying Du, Yunjie Huang, Ting He, Xiaochun Zhou

    As an excellent hydrogen storage medium, methanol has many advantages, such as high hydrogen content (12.6 wt%), low-cost and availability from biomass or photocatalysis. However, conventional methanol-water reforming usually proceeds at high temperature. In this research, we successfully designed a new effective strategy to generate hydrogen from methanol at near-room temperature. The strategy involves two main procedures, which are CH3OHHCOOHH2 and NADHHCOOHH2. The first procedure (CH3OHHCOOHH2) is performed by alcohol dehydrogenase (ADH), aldehyde dehydrogenase (ALDH) and the Ir-catalyst. The second procedure (NADHHCOOHH2) is performed by formate dehydrogenase (FDH) and the Ir-catalyst. The Ir-catalyst is a reported polymer complex catalyst Cp*IrCl2(ppy), which owns high catalytic activity for formic acid decomposition at room temperature and compatibility to the enzymes, coenzyme and poisonous chemicals. This research reveals that the optimum hydrogen generation rate can reach up to 17.8 μmol h-1 g-1 under weak basic condition at 30 ℃. It will have high impact on hydrogen storage, production and applications, also provide a new inspiration for hydrogen generation from methanol.

    更新日期:2018-01-12
  • Ultrathin Bismuth nanosheets as highly efficient electrocatalyst for CO2 reduction
    ChemSusChem (IF 7.226) Pub Date : 2018-01-11
    Panpan Su, Wenbin Xu, Yanling Qiu, Taotao Zhang, Xianfeng Li, Huamin Zhang

    Electrochemical reducing CO2 to value-added products is an important and challenging reaction for sustainable energy study. In this study, bismuth nanosheets with thickness of ~10 nm were successfully prepared via electrochemical reduction of Bi3+. Ultrathin Bi nanosheets with numerous low-coordination sites can efficiently reduce CO2 to formate in aqueous solution. During the potential range of - 0.9 V to - 1.2 V vs RHE, the faradaic efficiency of formate is over 90%, which is one of the best reported Bi catalysts. At −0.7 V, the prepared Bi nanosheets exhibit much higher current for formate generation than that of bulk Bi, which is due to not only high surface area but also intrinsic electronic property change of ultrathin structure. Further, DFT calculation demonstrates that Bi nanosheets have the much higher electron state density around Fermi level than bulk counterpart, which favors the improvement of CO2 reduction on Bi nanosheets. At −1.0 V, Bi nanosheets exhibit high selectivity for formate and excellent stability during 5 hrs electrolysis measurement. The prepared Bi nanosheets with high activity and superior stability show great potential toward CO2 reduction area.

    更新日期:2018-01-11
  • Pyran-Bridged Indacenodithiophene as a Building Block for Constructing Efficient A–D–A-Type Nonfullerene Acceptors for Polymer Solar Cells
    ChemSusChem (IF 7.226) Pub Date : 2018-01-11
    Shuguang Wen, Yao Wu, Yingying Wang, Yi Li, Ling Liu, Huanxiang Jiang, Zhitian Liu, Renqiang Yang
    更新日期:2018-01-11
  • Micelle-Assisted Electrodeposition of Mesoporous Fe–Pt Smooth Thin Films and their Electrocatalytic Activity towards the Hydrogen Evolution Reaction
    ChemSusChem (IF 7.226) Pub Date : 2018-01-11
    Eloy Isarain-Chávez, Maria Dolors Baró, Carlos Alcantara, Salvador Pané, Jordi Sort, Eva Pellicer
    更新日期:2018-01-11
  • Encapsulating Co2P@C Core–Shell Nanoparticles in a Porous Carbon Sandwich as Dual-Doped Electrocatalyst for Hydrogen Evolution
    ChemSusChem (IF 7.226) Pub Date : 2018-01-11
    Yuanyuan Yang, Xiongyi Liang, Feng Li, Shuwen Li, Xinzhe Li, Siu-Pang Ng, Chi-Man Lawrence Wu, Rong Li
    更新日期:2018-01-11
  • Cellular Structure Fabricated on Ni Wire by a Simple and Cost-effective Direct-Flame Approach and Its Application in Fiber-Shaped Supercapacitors
    ChemSusChem (IF 7.226) Pub Date : 2018-01-10
    Zhihong Wang, Fenhui Cao, Kongfa Chen, Yingming Yan, Yifu Chen, Yaohui Zhang, Xingbao Zhu, Bo Wei, Yueping Xiong, Zhe Lv

    Cellular metals with the large surface-to-volume ratios and excellent electrical conductivity are widely applicable and have thus been studied extensively. It is highly desirable to develop a facile and cost-effective process for fabrication of porous metallic structures, more so for micron/nano pores. Herein, we propose a novel direct-flame strategy for in-situ fabrication of micron cellular architecture on Ni metal precursor. The flame provides required heat, but also serves as a fuel reformer providing a gas mixture of H2, CO and O2 for redox treatment of Ni metals. The redox processes at elevated temperatures allow a fast reconstruction of the metal, leading to cellular structure on Ni wire. This process is simple and clean, avoiding the use of sacrificial materials or templates. Further, nanocrystalline MnO2 is coated on the micron porous Ni wire (MPNW) to form a supercapacitor electrode. The MPNW-MnO2 electrode and the corresponding fiber-shaped supercapacitor exhibit high specific capacitance and excellent cycling stability. More importantly, this work provides a novel strategy for fabrication of cellular metals and alloys for a variety of applications, including catalysis, energy storage and conversion, and chemical sensing.

    更新日期:2018-01-10
  • Methylation of Polyols with Trimethylphosphate in the Presence of a Lewis or Brønsted Acid Catalyst
    ChemSusChem (IF 7.226) Pub Date : 2018-01-10
    Marie-Christine Duclos, Aurélien Herbinski, Anne-Sophie Mora, Estelle Métay, Marc Lemaire
    更新日期:2018-01-10
  • Pt islands on 3D nut-like PtAg nanocrystals for efficient formic acid oxidation electrocatalysis
    ChemSusChem (IF 7.226) Pub Date : 2018-01-09
    Hui Xu, Pingping Song, Bo Yan, Jin Wang, Caiqin Wang, Yukihide Shiraishi, Ping Yang, Yukou Du

    Precise control of the structure offers a great opportunity to efficiently tune the catalytic performances of nanomaterials, enabling them enhancement in both activity and durability. We herein achieve a new class of Pt islands on 3D nut-like PtAg nanocrystals by exploiting the lower electronegativity of Ag and in conjunction with the galvanic replacement of catalytically active Pt to Ag tops. Those nanostructures with Pt nanoparticles coated, exposed facet, active surface composition enhance formic acid oxidation electrocatalysis with the optimized PtAg1 nuts achieved a factor of 4.0 and 2.4 in mass and specific activities (1728.3 mA mg-1 and 3.31 mA cm-2) relative to that of the commercial Pt/C (431.2 mA mg-1 and 1.41 mA cm-2), respectively. Moreover, such 3D PtAg1 nuts also display great enhancement in durability with less decay for at last 500 cycles, showing the great potential to serve as the promising catalysts for fuel cells and beyond. Our work provides a fundamental insight on the effect of morphology towards liquid fuel electrooxidation, which may pave a new way for the fabrication of highly efficient electrocatalysts for fuel cells.

    更新日期:2018-01-09
  • Oxygen Reduction Reaction for Generating H2O2 via Piezo-catalytic Process over BiOCl
    ChemSusChem (IF 7.226) Pub Date : 2018-01-09
    Wenzhong Wang, Dengkui Shao, Ling Zhang, Songmei Sun

    Oxygen reduction reaction (ORR) for generating H2O2 via green pathways have gained much attention in recent years. Herein, we introduce a piezo-catalytic approach to obtain H2O2 over BiOCl via ORR pathway. The piezoelectric response of BiOCl was directly characterized by piezoresponse force microscope (PFM). The BiOCl exhibits efficient catalytic performance for generating H2O2 (28 µmol/h ) only from O2 and H2O, which is above the average level of H2O2 produced by solar-to-chemical process. A piezo-catalytic mechanism was proposed: with ultrasonic waves, an alternating electric field will be generated over BiOCl, which can drive charge carriers (electrons) to interact with O2 and H2O, then to form H2O2.

    更新日期:2018-01-09
  • Across the Board: Xinchen Wang
    ChemSusChem (IF 7.226) Pub Date : 2018-01-09
    Xinchen Wang

    Abstract In this series of articles, the board members of ChemSusChem discuss recent research that they consider of exceptional quality and importance for sustainability. In this entry, Prof. Xinchen Wang discusses the investigations of a printable Z-scheme system for photocatalytic water splitting by the pioneer, Prof. Kazunari Domen, who has been constantly contributing to this field for about 40 years. The recent achievement of an overall water splitting system has exceeded the solar-to-hydrogen energy efficiency of 1% by integrating efficient hydrogen and oxygen evolution photocatalysts with charge-transport channel.

    更新日期:2018-01-09
  • Hybrid-organic-inorganic anatase as a bifunctional catalyst for enhanced production of HMF from glucose in water
    ChemSusChem (IF 7.226) Pub Date : 2018-01-08
    Carlos A. S. Lanziano, Silvia F. Moya, Dean H. Barrett, Reginaldo Guirardello, Felipe de Souto da Silva, Roberto Rinaldi, Cristiane Barbieri Rodella

    Herein, we report a synthetic route for the preparation of hybrid-organic-inorganic anatase (hybrid-TiO2) via a facile hydrothermal synthesis method employing citric acid. The synthetic approach results in a high surface area nanocrystalline anatase polymorph of TiO2. The uncalcined hybrid-TiO2 is directly studied here as the catalyst for the conversion of glucose into HMF. In the presence of the hybrid-TiO2, HMF yields up to 45% at glucose conversions up to 75% were achieved in water at 130 oC in a monophasic batch reactor. As identified by Ti K-edge XANES, hybrid-TiO2 contains a large fraction of five-fold coordinatively unsaturated Ti(IV) sites, which act as the Lewis acid catalyst for the conversion of glucose into fructose. As citric acid is anchored in the structure of hybrid-TiO2, carboxylate groups seem to catalyze the sequential conversion of fructose into HMF. The fate of citric acid bounded to anatase and the Ti(IV) Lewis acid sites throughout recycling experiments is also investigated. In a broader context, the contribution outlines the importance of hydrothermal synthesis for the creation of water-resistant Lewis acid sites for the conversion of sugars. Most importantly, the utilization of the hybrid-TiO2 with no calcination step contributes to dramatically decreasing the energy consumption in the catalyst preparation.

    更新日期:2018-01-09
  • A Perspective Review on the Materials and Mechanisms of Photo-Assisted Chemical Reactions under Light and Dark: Can it be called as Day-Night Photocatalysis?
    ChemSusChem (IF 7.226) Pub Date : 2018-01-08
    Sakar Mohan, Nguyen Chinh-Chien, Vu Manh-Hiep, Trong-On Do

    The photo-assisted catalytic reaction, conventionally known as photocatalysis, is blooming into the field of energy and environmental applications. It is widely known that the discovery of TiO2-assited photochemical reactions has led to achieve several unique applications such as degradation of pollutants in water and air, hydrogen production through water splitting, fuel conversion, cancer treatment, anti-bacterial activity, self-cleaning glasses and concrete, etc. These multifaceted applications of this phenomenon can be enriched and expanded further if this process is equipped with more tools and functions. The term 'photo'-assisted catalytic reactions clearly emphasizes that the photons are required to activate the catalyst, where this can be transcended even into dark if the electrons are stored in the material for the later use to continue the catalytic reactions in the absence of light. This can be achieved by equipping the photocatalyst with a so-called electron storage material as to break the present limitations in 'photo'-assisted catalytic reactions. In this context, this perspective article sheds lights on the materials and mechanism of the materials that perform photocatalytic reactions under light and dark conditions. The manifestation of such material systems could be an unparalleled technology in near future that would possibly make foot prints in all the sphere of the catalytic sciences.

    更新日期:2018-01-08
  • Fabrication of Cu2O-based Materials for Lithium-ion Batteries
    ChemSusChem (IF 7.226) Pub Date : 2018-01-06
    Huan Pang, Qin Yuan Li, Li Zhang, Huai Guo Xue

    The improvement of the performance of advanced batteries has played a key role in the energy research community since its inception. Therefore, it is necessary to explore excellent materials for applications in advanced batteries. Among the variety of materials applied in batteries, cuprous oxide and its composites stand out because of their specific characteristics (polymorphic forms, controllable structure, high cycling capacity, etc.). Thus, cuprous oxide and its composites will be fully introduced in this review for their applications in advanced batteries. It is believed that, in the future, both the study and the impact of cuprous oxide and its composites will be much more profound and lasting.

    更新日期:2018-01-06
  • Towards Sustainable Production of Formic Acid from Biomass for Getting Hydrogen and Fuels
    ChemSusChem (IF 7.226) Pub Date : 2018-01-06
    Dmitri Bulushev, Julian R.H. Ross

    Formic acid is a widely used commodity chemical. It can be used as a safe, easily handled and transported source of hydrogen or CO for different reactions including those producing fuels. The review includes historical aspects of formic acid production. It shortly analyzes the production based on traditional sources such as CO, methanol and methane. However, the main emphasis is done to the sustainable production of formic acid from biomass and biomass-derived products via hydrolysis, wet and catalytic oxidation processes. New strategies of low temperature synthesis from biomass may lead to utilization of formic acid for production of fuel additives such as methanol, upgraded bio-oil, gamma-valerolactone and its derivatives, as well as synthesis gas used for Fischer-Tropsch synthesis of hydrocarbons. Some technological aspects are considered.

    更新日期:2018-01-06
  • Bifunctional Pyridinium-Based Ionic liquid Immobilized [In2(dpa)3(1,10-phen)2]: Efficacy of Supported Ionic Liquid Phase Metal Organic Framework Catalyst for CO2 Fixation Reactions
    ChemSusChem (IF 7.226) Pub Date : 2018-01-06
    Robin Babu, Jintu Francis Kurisingal, Jong-San Chang, Dae-Won Park

    A pyridinium-based ionic liquid-decorated 1D MOF (IL-[In2(dpa)3(1,10-phen)2]) was developed as a bifunctional heterogeneous catalyst system for CO2-oxirane coupling reactions. An aqueous-microwave route was employed as competent with the hydrothermal pathway for the synthesis of [In2(dpa)3(1,10-phen)2] MOF, and the IL-[In2(dpa)3(1,10-phen)2] catalyst was synthesized using the covalent post functionalization method. Due to the synergetic effect of dual functional sites, including Lewis acid sites (coordinatively unsaturated indium sites) and I- ion in IL functional sites, IL-[In2(dpa)3(1,10-phen)2] displayed high catalytic activity for CO2-epoxide cycloaddition reactions under mild and solvent free conditions. Microwave pulses were employed for the first time for MOF-catalyzed CO2-epoxide cycloaddition reactions resulting in a high turnover frequency (TOF), ranging from 2000 to 3100 h-1. The catalyst had excellent reusability while maintaining continuous high selectivity. Furthermore, only a small amount of leaching was observed from the spent catalyst. A plausible reaction mechanism based on the synergistic effect of dual functional sites that effectively catalyze the CO2-epoxide cycloaddition reaction is proposed.

    更新日期:2018-01-06
  • MoS2/MoOx Nanostructure Decorated Activated Carbon Cloth for Enhanced Supercapacitor Performances
    ChemSusChem (IF 7.226) Pub Date : 2018-01-04
    Fitri Nur Indah Sari, Jyh-Ming Ting

    MoS2/MoOx nanostructures have been grown on activated carbon cloth through a facile one-step microwaved-assisted hydrothermal. The growth of MoS2/MoOx on activated carbon cloth create a unique structure that favors ions intercalation. The conductive activated carbon cloth, MoO3-x, and monoclinic MoO2 provide fast electron transport while the MoS2 nanosheets/MoO3-x nanoparticles nanostructure improves the capacitance. As a result, MoS2/MoOx nanostructure decorated activated carbon cloth shows high specific capacitance of 230 F g-1 at a scan rate of 5 mV s-1 with low contact resistance ~1.91 ohm. Moreover, the activated carbon cloth acts as a template for the growth of perpendicular MoS2 layer, giving an excellent utilization rate of the active material MoS2/MoOx. We also demonstrate that MoS2/MoOx/ activated carbon cloth nanocomposite shows excellent electrochemical stability with retention up to 128% after 1500 cycles. Finally, we show that the use of microwaved-assisted hydrothermal-synthesized MoS2/MoOx/ activated carbon cloth nanocomposite an alternative and clean route to improve the kinetics of the intercalation redox reaction.

    更新日期:2018-01-04
  • A Co2P/WC Nano-Heterojunction Covered by N-Doped Carbon as High Efficient Electrocatalyst for Hydrogen Evolution Reaction
    ChemSusChem (IF 7.226) Pub Date : 2018-01-02
    Yang-Guang Li, Ya Gao, Zhong-Ling Lang, Fei-Yang Yu, Hua-Qiao Tan, Gang Yan, Yong-Hui Wang, Yuan-Yuan Ma

    Hydrogen evolution reaction (HER), which produces clean hydrogen through the electrochemical process, screams for more non-precious-metal electrocatalysts to lower the consumption of energy. Herein, we report a new Co2P/WC nano-heterojunction that consists of cobalt phosphide and tungsten carbide composite phases coated by few-layer N-doped graphitic carbon shells (abbr. Co2P/WC@NC). The composite was prepared by one-step annealing of the polyoxometalate Na9(NH4)5[{(B-α-PW9O34)Co3(OH) (H2O)2(Ale)}2Co]·35H2O (Co7P6W18) and dicyandiamide (DCA). Such preparation method realizes the simultaneous phosphorization for Co and carbonization for W in a confined space, so as to isolate a Co2P/WC nano-heterojunction phase for the first time. Co2P/WC @NC facilitates the hydrogen generation in the electrolysis process, which only needs a small overpotential of 91 mV to reach the current density of 10 mA cm-2 in the acid solution, which brings excellent HER performance, a fantastic Tafel slope (40 mV dec-1) and superior durability over a period of 50 h. Theoretical calculations show that the Co2P, WC, and NpyridinicC dopants in the material synergistically promoted the HER activity. Meanwhile, Co2P/WC@NC nano-heterojunction shows good HER performance in the whole pH range of electrolytes and considerable durability in acid media containing transition metal ions, which may attract more attention to the exploration and optimization of nano-heterojunction catalysts in HER.

    更新日期:2018-01-02
  • An efficient metal-free catalyst for oxidative dehydrogenation reaction: Activated carbon decorated with few-layer graphene
    ChemSusChem (IF 7.226) Pub Date : 2018-01-02
    Yajie Zhang, Jiangyong Diao, Junfeng Rong, Jiayun Zhang, jingxin Xie, Fei Huang, Zhimin Jia, Hongyang Liu, Dangsheng Su

    Activated carbon (AC) has been widely used in catalysis field because of its low-cost, scalable production, high specific surface area and abundant exposed edge. Due to the amorphous structure, traditional AC is unstable in presence of O2 at high temperature, which hinders the application of AC catalysts in oxidative dehydrogenation (ODH) of alkanes. In this work, partially graphitic AC decorated with few-layer graphene is facilely fabricated by the simple high-temperature calcination. The graphitic transformation significantly enhances the anti-oxidation property, long-term stability of AC during the ODH reaction, and especially increases the graphitic edge areas where the active ketonic carbonyl groups are selectively formed in the ODH reactions. A high reactivity with 41.5 % selectivity and 13.2% yield to C4 alkenes are obtained at 450oC over the optimized catalyst, which is superior to all the previous reported carbon catalysts and shows a great potential for industrial application

    更新日期:2018-01-02
  • Selective Hydrodeoxygenation of Alkyl Lactates to Alkyl Propionates with Fe-based Bimetallic Supported Catalysts
    ChemSusChem (IF 7.226) Pub Date : 2017-12-29
    Santosh Govind Khokarale, Jian He, Leonhard Schill, Song Yang, Anders Riisager, Saravanamurugan Shunmugavel

    Hydrodeoxygenation (HDO) of methyl lactate (ML) to methyl propionate (MP) were performed with various base metal supported catalysts. A high yield of 77% MP was obtained with bimetallic Fe-Ni/ZrO2 in methanol at 220 C at 50 bar H2. A synergic effect of Ni increased the yield of MP significantly when using Fe-Ni/ZrO2 instead of Fe/ZrO2 alone. Moreover, the ZrO2 support contributed to improve the yield as a phase transition of ZrO2 from tetragonal to monoclinic occurred after metal doping giving rise to fine dispersion of the Fe and Ni on the ZrO2, implying the higher catalytic activity of the material. Intriguingly, it was observed that Fe-Ni/ZrO2 also effectively catalyzed methanol reforming to produce in situ H2, followed by HDO of ML, yielding 60% MP at 220 C with 50 bar N2 instead of H2. Fe-Ni/ZrO2 also catalyzed HDO of other short chain alkyl lactates to the corresponding alkyl propionates in high yields around 70%. No loss of activity of Fe-Ni/ZrO2 occurred in five consecutive reaction runs demonstrating the high durability of the catalyst system.

    更新日期:2017-12-31
  • N-Annulated Perylene Based Hole-Transporters for Perovskite Solar Cells: the Significant Impacts of Lateral Substituents
    ChemSusChem (IF 7.226) Pub Date : 2017-12-29
    Peng Wang, Yang Li, Rui Zhu, Junting Wang, Ze-Sheng Li, Niansheng Xu, Jidong Zhang

    Perylene derivatives are a family of well-known organic electron-transporting materials with excellent photochemical and thermal stabilities, and have been widely used in various optoelectronic devices. In this work, two diphenylamine functionalized N-annulated perylenes are reported for the first time as a new class of hole-transporting materials (HTMs) for perovskite solar cells. With the aid of joint theoretical and experimental studies, we uncover that the HTM employing the methoxyphenyl lateral substituent features a closer stacking distance and a better aggregate connectivity in the solid film than the counterpart with the bulky 2-hexyldecyl lateral substituent, contributing to a higher hole mobility and a remarkably enhanced device performance of perovskite solar cells. This work demonstrates the significant influence of lateral substituents of HTMs on the intermolecular packing and solid microstructure, giving a clear clue on the molecular design of high performance organic semiconductors.

    更新日期:2017-12-31
  • Flower-like VS4/rGO Composite: an Energy Storage Material for Aluminum-ion Battery
    ChemSusChem (IF 7.226) Pub Date : 2017-12-29
    Shuqiang Jiao

    The flower-like VS4/rGO (reduced graphene oxide) composite was prepared by a typical hydrothermal method, which was investigated as cathode for aluminum-ion battery with non-inflammable and non-explosive ionic liquid electrolytes. The charge/discharge performance measurements were carried out in a voltage range of 0.1~2.0 V vs. Al/AlCl4-, which suggests the initial charge/discharge specific capacity approaching 491.57 and 406.94 mA h g-1, respectively, at a current density of 100 mA g-1. Additionally, in the cycling performance, discharge capacity has been observed to remain over 80, 70 and 60 mA h g-1 at current densities of 100, 200 and 300 mA g-1 after 100 cycles, respectively. The results of coulombic efficiency over 90% after 100 cycles and high capacity retained indicate a favorable cathode material for novel rechargeable aluminum-ion battery.

    更新日期:2017-12-31
  • Hydrothermally induced O-doping and porous structure of graphitic carbon nitride with highly ordered architecture and dramatically enhanced photocatalytic property
    ChemSusChem (IF 7.226) Pub Date : 2017-12-29
    Chao Wang, Huiqing Fan, Xiaohu Ren, Jiangwei Ma, Jiawen Fang, Weijia Wang

    As an amorphous or semi-crystalline material, graphitic carbon nitride (g-C3N4) displays poor photocatalytic activity due to the rapid recombination of photo generated charge carriers, which is mainly caused by the high density of defects in the graphitic structure. In this work, a porous O-doped g-C3N4 nanosheet (P-CNO) with highly ordered architecture is fabricated by introducing a novel hydrothermal treatment to the precursor before the final thermal condensation. The photocatalytic hydrogen evolution rate (HER) and HER per surface area of P-CNO are 13.9 times and 1.7 times higher than that of bulk g-C3N4. The improved photocatalytic activity is ascribed to the synergistic effect of O-doping, porous sheet-like morphology and increased crystallinity. This work also provides a new approach for synthesis of other polymer-based photocatalysts with high crystallinity and excellent performances.

    更新日期:2017-12-31
  • Polyethylene Glycol-[60]fullerene-based Materials for Perovskite Solar Cells with Improved Moisture Resistance and Reduced Hysteresis
    ChemSusChem (IF 7.226) Pub Date : 2017-12-28
    Juan L. Delgado, Silvia Collavini, michael saliba, wolfgang tress, philippe holzhey, sebastian voelker, konrad domanski, silver turren-cruz, amita ummadisingu, shaik zakeeruddin, anders hagfeld, Michael Graetzel

    A series of [60]fullerenes covalently functionalized with the polyethylene glycol polymer (PEG) is presented. These novel [60]fullerene-based materials have been incorporated as additives in CH3NH3PbI3 (MAPbI3), the most common organic-inorganic perovskite used in perovskite solar cells. The extensive photovoltaic study performed using these materials shows beneficial effects on the performance of these cells, reducing hysteresis and increasing stability against moisture, thereby retaining up to 97% of their initial power conversion efficiency at ambient atmosphere.

    更新日期:2017-12-29
  • A strategy to boost H2 generation ability of MOFs—inside-outside decoration for the separation of electron and holes
    ChemSusChem (IF 7.226) Pub Date : 2017-12-28
    Yang Wang, Lianjie Ling, Wei Zhang, Kejian Ding, Yu Yu, Wubiao Duan, Bo Liu

    Inhibiting the recombination of electron and holes plays an essential role in photocatalytic process, particularly for MOFs which had long been expected as high efficient photocatalysts. Herein, we introduce a new strategy to make efficient separation of electron and holes for MOFs-based photocatalyst, UiO-66-NH2. At first, encapsulate Pt NPs into UiO-66-NH2 (Pt@U6N) to shorten the electrons transport distance inside, then using graphene oxide to wrap the external surface of Pt@U6N to felicitate the superficial electrons transfer. The designed structure was found possess superior H2 generation ability than sole inside/outside decoration, highlighting the enhanced property strongly correlates with the inhibited recombination of electron and holes by the inside-outside modification strategy. These findings suggest a synergistic effect of Pt NPs and graphene oxide on UiO-66-NH2 and revealed a new modification strategy to enhance the photocatalytic activity for photocatalysts.

    更新日期:2017-12-29
  • Capacitance-Assisted Sustainable Electrochemical Carbon Dioxide Mineralisation
    ChemSusChem (IF 7.226) Pub Date : 2017-12-28
    Katie J. Lamb, Mark R. Dowsett, Konstantinos Chatzipanagis, Zhan Wei Scullion, Roland Kröger, James D. Lee, Pedro M. Aguiar, Michael North, Alison Parkin
    更新日期:2017-12-29
  • 更新日期:2017-12-29
  • A potential liquid organic hydrogen carrier: 2-(n-methylbenzyl)pyridine with fast H2 release and stable activity in consecutive hydrogenation-dehydrogenation cycles
    ChemSusChem (IF 7.226) Pub Date : 2017-12-28
    Jinho Oh, Kwanyong Jeong, Tae Wan Kim, Hyunguk Kwon, Jeong Woo Han, Ji Hoon Park, Young-Woong Suh

    For H₂ storage based on reversible hydrogenation and dehydrogenation of a liquid organic hydrogen carrier (LOHC), we herein demonstrate a potential of 2-(n-methylbenzyl)pyridine (MBP) with the H₂ storage density of 6.15 wt%. This material and the corresponding perhydro product (H12-MBP) exist in liquid state at room temperature. Remarkably, H₂ release is much faster from H12-MBP over Pd/C than from the benchmark perhydro benzyltoluene over Pt/C at lower temperatures than 270 °C due to the addition of N atom into the benzene ring. Since this positive effect is unfavorable to the hydrogenation reaction, more Ru/Al₂O₃ catalyst or prolonged reaction time would be applied for complete H₂ storage. Experiments for repeated hydrogenation/dehydrogenation cycles reveal that reversible H₂ storage and release are possible without degradation of the pair MBP/H12-MBP. The prepared MBP satisfies the requirements in chemical stability, handling properties, and cytotoxicity test.

    更新日期:2017-12-28
  • Connection between Lithium Coordination and Lithium Diffusion in Pyr12O1FTFSI Ionic Liquid Electrolytes
    ChemSusChem (IF 7.226) Pub Date : 2017-12-27
    Guinevere Giffin, Arianna Moretti, Sangsik Jeong, Kartik Pilar, Marc Brinkkoetter, Steve Greenbaum, Monika Schoenhoff, Stefano Passerini

    The use of highly concentrated ionic liquid-based electrolytes results in improved rate capability and capacity retention at 20°C, as compared to Li+-dilute systems, in Li-metal and Li-ion cells. This work explores the connection between the bulk electrolyte properties and the molecular organization to give insight into the concentration dependence of the Li+ transport mechanisms. Below 30 mol%, the Li+-containing species are primarily smaller complexes (one Li+ cation) and the Li+ ion transport is mostly derived from the vehicular transport. Above 30%, where the viscosity is substantially higher and the conductivity lower, the Li+-containing species are a mix of small and large complexes (one and more than one Li+ cation, respectively). The overall conduction mechanism likely changes to favor structural diffusion via the exchange of anions in the first Li+ solvation shell. The good rate performance is likely directly influenced by the presence of the larger Li+ complexes, which promote Li+-ion transport (as opposed to Li+-complex transport) and increase the Li+ availability at the electrode.

    更新日期:2017-12-28
  • One-step Synthesis of Nb2O5/C/Nb2C (MXene) Composites and Their Use as Photocatalysts for Hydrogen Evolution
    ChemSusChem (IF 7.226) Pub Date : 2017-12-27
    Tongming Su, Rui Peng, Zachary D. Hood, Michael Naguib, Ilia N. Ivanov, Jong Kahk Keum, Zuzeng Qin, Zhanhu Guo, Zili Wu

    Abstract: Hydrogen production through facile photocatalytic water splitting is regarded as a promising strategy for solving global energy problems. Transition metal carbides (MXenes) have recently drawn attention as potential co-catalyst candidates for photocatalysts. Here, we report niobium pentoxide/carbon/niobium carbide (MXene) hybrid materials (Nb2O5/C/Nb2C) as photocatalysts for hydrogen evolution from water splitting. The Nb2O5/C/Nb2C composites were synthesized by a one-step CO2 oxidation of Nb2CTx. Nb2O5 grew homogeneously on Nb2C after mild oxidation during which some amorphous carbon also formed. With an optimized oxidation time of 1.0 h, the Nb2O5/C/Nb2C shows the highest hydrogen generation rate (7.81 μmol*h-1gcat-1), which is 4 times as high as that of pure Nb2O5. The enhanced performance of Nb2O5/C/Nb2C can be attributed to the intimate contact between the Nb2O5 and the conductive Nb2C, and the separation of photogenerated charge carriers at the Nb2O5/Nb2C interface, showing the promise of transition metal carbide as co-catalysts for photocatalytic hydrogen production.

    更新日期:2017-12-28
  • Novel Starbon/HACS-supported N-heterocyclic carbene-iron(III) catalyst for efficient conversion of fructose to HMF
    ChemSusChem (IF 7.226) Pub Date : 2017-12-27
    Avtar Singh Matharu, Suleiman Ahmed, Badriya Al-Monthery, Duncan Macquarrie, Yoon-Sik Lee, Yohan Kim

    : Iron-nitrogen heterocyclic carbenes (Fe-NHCs) have come to the fore because of their ability to be employed in diverse catalytic applications ranging from C-C cross-coupling and C-X bond formation to substitution, reduction, polymerization, and dehydration. The detailed synthesis, characterisation and application of novel heterogeneous Fe-NHC catalysts immobilised on mesoporous expanded starch and Starbon™ 350 for facile fructose to HMF conversion is reported. Both catalyst types showed good performance for the dehydration of fructose to HMF when the reaction was explored at 100 ◦C and varying time (10 min, 20 min, 0.5 h, 1 h, 3 h and 6 h): Fe-NHC S350, highest HMF yield, 81.7 % (t=0.5 h), TOF=169 h-1, fructose conversion of 95 % and HMF selectivity of 85.7 %, and; Fe-NHC expanded HACS, highest yield, 86 % (t=0.5 h), TOF=206 h-1, fructose conversion of 87 % and HMF selectivity of 99 %. An iron-loading of 0.26 and 0.30 mmol/g was achieved for the Fe-NHC expanded starch and Fe-NHC Star-bon™ 350, respectively.

    更新日期:2017-12-27
  • 更新日期:2017-12-27
  • Bioinspired Mesoporous Chiral Nematic Graphitic Carbon Nitride Photocatalysts modulated by Polarized Light
    ChemSusChem (IF 7.226) Pub Date : 2017-12-27
    Wensheng Lin, Wei Hong, Lu Sun, Di Yu, Dingshan Yu, Xudong Chen
    更新日期:2017-12-27
  • Rapid Formation of a Disordered Layer on Monoclinic BiVO4: Co-catalyst-free Photoelectrochemical Solar Water Splitting
    ChemSusChem (IF 7.226) Pub Date : 2017-12-23
    Jung Kyu Kim, Yoonjun Cho, Myung Jin Jeong, Ben Levy-Wendt, Dongguen Shin, Yeonjin Yi, Dong Hwan Wang, Xiaolin Zheng, Jong Hyeok Park

    Surface disordered layer is plausible approach to improve the photoelectrochemical performance of TiO2. However, the formation of a crystal disordered layer in BiVO4 and its effectiveness towards photoelectrochemical water splitting has remained a big challenge. Here, we report a rapid solution process (within 5 seconds) that is capable of forming a few nanometre-thick disordered layer on the surface of BiVO4 nanoparticles using a specific solution with controllable reducing power. The disordered layer on BiVO4 alleviates charge recombination at the electrode/electrolyte interface and greatly reduces the on-set potential, which in turn results in a photocurrent density of around 2.3 mA/cm2 at 1.23 V vs. reversible hydrogen electrode (RHE). This value is 2.1 times higher than that of bare BiVO4. The enhanced photoactivity is attributed to the increased charge separation and transfer efficiencies, which provide an effective avenue for resolving an intrinsic drawback of bare BiVO4 such as short hole diffusion length of around 100 nm and poor surface oxygen evolution reactivity.

    更新日期:2017-12-27
  • Annealing-Free Cr2O3 Electron-Selective Layer for Efficient Hybrid Perovskite Solar Cells
    ChemSusChem (IF 7.226) Pub Date : 2017-12-20
    Jia Dong, jihuai Wu, Jinbiao Jia, Leqing Fan, Miaoliang Huang, Jianming Lin, Xin He, Zhang Lan

    The electron-selective layer (ESL) plays a pivotal role in the high-performance of perovskite solar cells (PSCs). In this report, amorphous dispersible chromium oxide (Cr2O3) nanosheets are synthesized by a facile solvothermal reaction, and Cr2O3 ESL is prepared by spin-coating Cr2O3 ink on FTO substrates without further annealing process. Using the Cr2O3 as electron-selective layer and Cs0.05(MA0.17FA0.83)0.95Pb(I0.83Br0.17)3 as light-absorption layer, a planar hybrid perovskite solar cell is fabricated. The spin-coating speed is optimized, the structure and morphology of samples are observed, the photoelectrical properties of ESLs are characterized and the photovoltaic behaviors of devices are measured. Results show that the as-prepared Cr2O3 layer have high optical transmittance and superb electron extraction and carrier transport property. The planar hybrid PSC based on the optimal Cr2O3 ESL achieves a power conversion efficiency of 16.23%, which is comparable with the device based on conventional high-temperature-calcined TiO2 ESL. This research demonstrate a novel, low-cost and facile Cr2O3 electron-selective material for high-effective perovskite solar cells.

    更新日期:2017-12-21
  • The Past, Present, and Future of Sustainable Chemistry
    ChemSusChem (IF 7.226) Pub Date : 2017-12-19
    David J. Smith
    更新日期:2017-12-19
  • Synthesis, Characterization and Photoelectrochemical-Catalytic Studies of a Water Stable Zinc-based Metal-organic Framework
    ChemSusChem (IF 7.226) Pub Date : 2017-12-18
    Muhammad Altaf, Manzar Sohail, Muhammad Mansha, Naseer Iqbal, Muhammad Sher, Atif Fazal, Nisar Ullah, Anverhusein A. Isab

    Metal-organic frameworks (MOFs) represent modern class of porous materials, which can be assembled in modular manner using different metal ions and organic linkers. Due to tunable structural properties, these materials are found to be useful for gas storage and separation technologies as well as catalytic applications. Herein we report the preparation of cost-effective zinc-based MOF ([Zn(bpcda)(bdc)]n) using N,N'-bis(pyridin-4-ylmethylene)cyclohexane-1,4-diamine, and benzene dicarboxylic acid linkers. Noteworthy, this new material exhibits remarkable photoelectrochemical (PEC) catalytic activity in water splitting for the evolution of oxygen. Notably, for the first time we showed that this non-noble metal-based MOF without any immobilization on other supports or containing metal particles produced highest photocurrent density, of 30 μA.cm-2 at 0.9 V with appreciable stability and negligible photo-corrosion. Advantageously, for this oxygen evolution process, no external reagents or sacrificial agents are required in the aqueous electrolyte solution.

    更新日期:2017-12-18
  • Acid-catalysed conversion of carbohydrates into value added small molecules in aqueous media and ionic liquids
    ChemSusChem (IF 7.226) Pub Date : 2017-12-17
    Iurii Bodachivskyi, Unnikrishnan Kuzhiumparambil, D. Bradley Glen Williams

    Biomass is the only realistic major alternative source (to crude oil) of hydrocarbon substrates for the commercial synthesis of bulk and fine chemicals. Within biomass, terrestrial sources are the most accessible, and therein lignocellulosic materials are most abundant. While lignin shows promise for the delivery of certain types of organic molecules, cellulose is a biopolymer with significant potential for conversion into high volume and high value chemicals. This review covers the acid-catalysed conversion of lower value (poly)carbohydrates into valorised organic building block chemicals (platform molecules). It focuses on those conversions performed in aqueous media or ionic liquids. It does this to provide the reader with a perspective on what can be considered a best case scenario, i.e. that the overall process is as sustainable as possible.

    更新日期:2017-12-18
  • Towards the Shell Biorefinery: Sustainable Synthesis of the Anti-Cancer Alkaloid Proximicin A from Chitin
    ChemSusChem (IF 7.226) Pub Date : 2017-12-16
    Jon Sperry, Ning Yan, alejandro sadiq, Xi Chen

    A shell biorefinery would involve fractionation of crustacean shells and incorporation of the components into value-added products, particularly those that contain nitrogen. In a proof-of-concept study that validates this concept, the anti-cancer alkaloid proximicin A has been synthesized from the chitin-derived platform chemical 3-acetamido-5-acetylfuran (3A5AF). This study accentuates the leading role chitin is likely to play in the sustainable production of nitrogen-containing fine chemicals that are not directly attainable from lignocellulose.

    更新日期:2017-12-16
  • Highly Efficient Gas Phase Oxidation of Renewable Furfural to Maleic Anhydride over Plate VPO Catalyst
    ChemSusChem (IF 7.226) Pub Date : 2017-12-15
    Yugen Zhang, Xiukai Li, Jogie Ko

    Maleic anhydride (MAnh) and its acids are critical intermediates in chemical industry. The synthesis of maleic anhydride from renewable furfural is one of the most sought after processes in the field of sustainable chemistry. We report a plate vanadium phosphorous oxide (VPO) catalyst synthesized by a hydrothermal method with glucose as a green reducing agent for furfural oxidation to MAnh in gas phase. The plate VPOHT catalyst has a preferentially exposed 200 crystal plane and exhibited dramatically enhanced activity, selectivity and stability as compared to conventional VPO catalysts and other state-of-the-art catalytic systems. At 360 ºC reaction temperature with air as an oxidant, about 90% yield of MAnh was achieved at 10 vol% of furfural in the feed, a furfural concentration value that is much higher than those (< 2 vol%) reported for other catalytic systems. The catalyst showed good long term stability and there was no decrease in activity and selectivity for MAnh in the time-on-steam duration of 25 h. The high efficiency and catalyst stability established this system very prominent for the synthesis of maleic anhydride from renewable furfural.

    更新日期:2017-12-15
  • Heterojunction Engineering for High Efficiency Cesium-Formamidinium Double Cation Lead Halide Perovskite Solar Cells
    ChemSusChem (IF 7.226) Pub Date : 2017-12-15
    Yihui Wu, Peng Wang, Shubo Wang, Zenghua Wang, Bing Cai, Xiaojia Zheng, Yu Chen, Ningyi Yuan, Jianning Ding, Wen-Hua Zhang

    It is essential to minimize the interfacial trap states and improve the carrier collection for high efficiency perovskite solar cells (PSCs). Herein, we present a facile method to construct a p-type graded heterojunction (GHJ) in the normal PSCs by deploying a gradient distribution of hole-transporting materials (PTAA in this case) in the shallow perovskite layer. The formation of the GHJ structure facilitates charge transfer and collection, passivates interfacial trap states, thus delivering a power conversion efficiency (PCE) of 20.05% along with steady output efficiency of 19.3%, which is among the highest efficiencies for Cs-Formamidinium (Cs,FA) lead halide PSCs. Moreover, the unencapsulated devices based on these (Cs,FA) lead halide perovskites show excellent long-term stability, more than 95% of their initial PCE can be retained after 1440 h' storage under the ambient conditions. This study may provide an effective strategy to fabricate high efficiency PSCs with great stability.

    更新日期:2017-12-15
  • Sustainable carbon/carbon supercapacitors operating down to -40°C in aqueous electrolyte made with cholinium salt
    ChemSusChem (IF 7.226) Pub Date : 2017-12-14
    Qamar Abbas, François Béguin

    Cholinium chloride at a concentration of 5 mol kg-1 in water is proposed as low cost and environmentally friendly aqueous electrolyte enabling to extend the operating range of carbon/carbon supercapacitors (SCs) down to -40°C. This solution exhibits a pH close to neutrality (pH = 6.1) and high conductivity of 88 mS cm-1 at 24°C. The supercapacitors demonstrate a high capacitance of 126 F g-1 (per mass of one electrode) and long life span at voltages up to 1.5 V. At -40°C, the carbon/carbon SCs display excellent electrochemical characteristics featured by slightly reduced capacitance of 106 F g-1 and negligible ohmic losses. As compared to previous works, where anti-freezing additives were introduced in traditional neutral electrolytes, the low solubility of the salt and related poor conductivity of the solution is no longer an issue, which makes the cholinium salt aqueous solutions very promising for SCs operating at sub-ambient temperature conditions.

    更新日期:2017-12-14
  • Achieving efficient electrocatalytic hydrogen evolution activity based on ultrafine and highly-dispersed RuPx encapsulated in N, P co-doped hollow carbon nanospheres
    ChemSusChem (IF 7.226) Pub Date : 2017-12-14
    Jing-Qi Chi, Wen-Kun Gao, Jia-Hui Lin, Bin Dong, Kai-Li Yan, Jun-Feng Qin, Bin Liu, Yong-Ming Chai, Chen-Guang Liu

    The ultrafine RuPx nanoparticles (NPs) encapsulated in uniform N, P co-doped hollow carbon nanospheres (RuPx@NPC) have been synthesized through a facile route of using aniline-pyrrole polymer nanospheres to disperse Ru ions with followed gas phosphorization process. The as-prepared RuPx@NPC exhibits uniform core-shell hollow nanospherical structures with ultrafine RuPx NPs as core and N, P co-doped carbon (NPC) as shell. So this strategy integrates many advantages of designing hollow nanostructures, providing conductive substrate and doping non-metal element. The obtained ultrathin NPC shell at high temperature can not only protect the high active phase of RuPx NPs from aggregation and corrosion in the electrolyte but also make the variation in the electronic structures and greatly improve charge transfer rate by N, P co-doping. The optimized RuPx@NPC sample at 900 °C exhibits Pt-like HER performance and long-time durability in acidic, alkaline and neutral solution. It requires a small overpotential of only 51 mV, 74 mV and 110 mV at 10 mA cm-2 in 0.5 M H2SO4, 1.0 M KOH and 1.0 M PBS, respectively. So this work provides a new way to design unique phosphide-doped carbon heterostructures through inorganic-organic hybrid method as excellent HER electrocatalysts.

    更新日期:2017-12-14
  • Cyclopentanone derivatives from 5-hydroxymethylfurfural via 1-hydroxyhexane-2,5-dione as intermediate
    ChemSusChem (IF 7.226) Pub Date : 2017-12-13
    Bartosz Wozniak, Anke Spannenberg, Yuehui Li, Sandra Hinze, Johannes Gerardus de Vries

    An efficient strategy for the conversion of biomass derived 5-hydroxymethyl-furfural (HMF) to 2-hydroxy-3-methylcyclopent-2-enone (MCP) via intramolecular aldol condensation of 1-hydroxyhexane-2,5-dione (HHD) has been developed. Further transformations of MCP towards the diol, enol acetate, levulinic acid and N-heterocyclic compounds are also reported.

    更新日期:2017-12-13
  • MnCo2O4/MoO2 Nanosheets Grown on Ni foam as Carbon- and Binder-free Cathode for Lithium-Oxygen Batteries with Long Life and High Efficiency
    ChemSusChem (IF 7.226) Pub Date : 2017-12-13
    Xuecheng Cao, Zhihui Sun, Xiangjun Zheng, Chao Jin, Jinghua Tian, Xiaowei Li, Ruizhi Yang

    Carbon is usually used as cathode material for Li-O2 batteries. However, the discharge product, such as Li2O2 and LiO2, could react with carbon to form insulating lithium carbonate layer, resulting in cathode passivation and capacity fading. To solve this problem, the development of non-carbon cathode is highly demanded. Herein, we have successfully synthesized MnCo2O4 (MCO) nanoparticles anchored on porous MoO2 nanosheets that are grown on Ni foam (current collector) (MCO/MoO2@Ni), acting as a carbon- and binder-free cathode for Li-O2 batteries, in an attempt to improve the electrical conductivity, electrocatalytic activity and durability. This MCO/MoO2@Ni electrode delivers excellent cyclability (more than 400 cycles) and rate performance (voltage gap of 0.75 V at 5000 mA g-1). Notably, the battery with this electrode exhibits a high energy efficiency (higher than 85 %). The advanced electrochemical performance of MCO/MoO2@Ni can be attributed to its high electrical conductivity, excellent stability and super electrocatalytic activity. This work offers a new strategy to fabricate high-performance Li-O2 batteries with non-carbon cathode materials.

    更新日期:2017-12-13
  • Magnetic Field Enhanced 4-electron Pathway by the Well-aligned Co3O4/ECNFs Design in the Oxygen Reduction Reaction
    ChemSusChem (IF 7.226) Pub Date : 2017-12-12
    Zheng Zeng, Tian Zhang, Yiyang Liu, Wendi Zhang, Ziyu Yin, Zuowei Ji, Jianjun Wei

    The sluggish reaction kinetics of oxygen reduction reaction (ORR) has been the limiting factor for fuel energy utilization, hence it is desirable to develop a high performance electrocatalysis with a 4-electron pathway ORR. Here, we report a constant low-current (50 μA) electrodeposition technique to develop a uniform Co3O4 film formation at the well-aligned electrospun carbon nanofibers (ECNFs) with a time-dependent growth mechanism. This work also reports a new finding of milli-Tesla (mT) magnetic field induced enhancement of electron exchange number of the ORR at glassy carbon electrode modified with the Co3O4/ECNFs catalyst. The magnetic susceptibility of the unpaired electrons in Co3O4 improves the kinetics and efficiency of electron transfer reactions in ORR, which shows a 3.92-electron pathway in the presence of a 1.32 mT magnetic field. This research presents a potential revolution of traditional electrocatalysts by simply applying an external magnetic field on metal oxides as replacement of noble metals to reduce the risk of the fuel cell degradation and maximize its energy output.

    更新日期:2017-12-13
  • Complete Depolymerization and Repolymerization of a Sugar Poly(orthoester)
    ChemSusChem (IF 7.226) Pub Date : 2017-12-13
    Lingyao Li, Sampa Maiti, Nicole A. Thompson, Ian J. Milligan, Wenjun Du
    更新日期:2017-12-13
  • Anionic Redox Chemistry in Polysulfide Electrode Materials for Rechargeable Batteries
    ChemSusChem (IF 7.226) Pub Date : 2017-12-13
    Ekaterina D. Grayfer, Egor M. Pazhetnov, Mariia N. Kozlova, Sofya B. Artemkina, Vladimir E. Fedorov
    更新日期:2017-12-13
  • Multiple-Trapping Model for the Charge Recombination Dynamics in Mesoporous-Structured Perovskite Solar Cells
    ChemSusChem (IF 7.226) Pub Date : 2017-12-13
    Hao-Yi Wang, Yi Wang, Ming-Yang Hao, Yujun Qin, Li-Min Fu, Zhi-Xin Guo, Xi-Cheng Ai, Jian-Ping Zhang
    更新日期:2017-12-13
  • Reconsidering Water Electrolysis: Producing Hydrogen at Cathodes Together with Selective Oxidation of n-Butylamine at Anodes
    ChemSusChem (IF 7.226) Pub Date : 2017-12-13
    Song Xue, Sebastian Watzele, Viktor Čolić, Kurt Brandl, Batyr Garlyyev, Aliaksandr S. Bandarenka
    更新日期:2017-12-13
  • Complete Depolymerization and Repolymerization of a Sugar Poly(orthoester)
    ChemSusChem (IF 7.226) Pub Date : 2017-12-13
    Lingyao Li, Sampa Maiti, Nicole A. Thompson, Ian J. Milligan, Wenjun Du
    更新日期:2017-12-13
  • Electrodeposition of Nickel Composite Nanoparticles for Alkaline Hydrogen Evolution Reaction: Correlating Electrocatalytic Behavior and Chemical Composition Obtained by XPS
    ChemSusChem (IF 7.226) Pub Date : 2017-12-11
    Shasha Tao, Florent Yang, Jona Schuch, Wolfram Jaegermann, Bernhard Kaiser

    Ni Nanoparticles (NPs) consisting of Ni, NiO and Ni(OH)2 have been formed on Ti substrates by electrodeposition as electrocatalysts for the hydrogen evolution reaction (HER) in alkaline solution. The deposition parameters including the potential range and the scan rate were varied, and the resulting NPs were investigated by scanning electron microscopy and X-ray photoelectron spectroscopy. Additionally, the chemical composition of the NPs changes using different conditions, and it was found that the catalytic activity increases with an increasing amount of NiO. From these data optimized NPs have been synthesized; the best sample shows an onset potential of ~ 0 V and an overpotential (η) of 197 mV at a cathodic current density of 10 mA cm-2 as well as a small Tafel slope of 88 mV dec-1 in 1 M KOH, which are comparable values to a Pt-foil. These NPs consist of about 25% Ni and Ni(OH)2 each, as well as of about 50% of NiO. This implies, that in order to obtain a successful HER electrocatalyst, active sites with differing composition have to be close to each other to promote different reaction steps. Long-time measurements (30h) show an almost complete transformation of the highly active catalyst compound consisting of Ni0, NiO and Ni(OH)2 to the less active Ni(OH)2 phase. Nevertheless, the here employed electrodeposition of non-precious metal/metal oxide combination compounds represents a promising alternative to Pt-based electrocatalysts for the water reduction to hydrogen.

    更新日期:2017-12-12
  • Front Cover: A Strategy for the Simultaneous Synthesis of Methallyl Alcohol and Diethyl Acetal with Sn-β (ChemSusChem 23/2017)
    ChemSusChem (IF 7.226) Pub Date : 2017-12-08
    Wenda Hu, Yan Wan, Lili Zhu, Xiaojie Cheng, Shaolong Wan, Jingdong Lin, Yong Wang

    The Front Cover shows a strategy to simultaneously produce two important chemicals, namely, methallyl alcohol and diethyl acetal. They are produced from methacrolein in ethanol solvent at low temperature on Beta zeolites modified by tin (Sn-β catalysts). The catalyst pre-calcined in Ar (Sn-β-Ar) enables more Sn species to be exchanged into the framework as isolated tetrahedral Sn(IV), thus enhancing the catalytic activity of the Meerwein–Ponndorf–Verley reaction. The findings of Sn-β fine-tuned through different treatments are of great significance toward understanding and manipulating the complex reaction between α,β-unsaturated aldehydes and primary alcohols. More information can be found in the Full Paper by Hu et al. on page 4715 in Issue 23, 2017 (DOI: 10.1002/cssc.201701435).

    更新日期:2017-12-11
  • Revealing the Chemistry between Bandgap and Binding Energy for Pb/Sn-based Trihalide Perovskite Solar Cell Semiconductors
    ChemSusChem (IF 7.226) Pub Date : 2017-12-08
    Arpita Varadwaj, Pradeep R. Varadwaj, Koichi Yamashita

    A relationship between reported experimental bandgaps (solid) and presently DFT-calculated binding energies (gas) is established for the first time for each of the four ten-membered lead (or tin) trihalide perovskite solar cell semiconductor series examined in this study, including CH3NH3PbY3, CsPbY3, CH3NH3SnY3 and CsSnY3, where Y = I(3 - x)Brx=1-3, I(3 - x)Clx=1-3, Br(3-x)Cl x=1-3, and IBrCl. The relationship unequivocally provides a new dimension for the fundamental understanding of the optoelectronic features of the solid state solar cell thin films using the 0 K gas-phase energetics of their corresponding molecular building blocks.

    更新日期:2017-12-11
  • Towards Sustainable H2 Production: Rational Design of Hydrophobic Triphenylamine-based Dyes for Sensitized Ethanol Photoreforming
    ChemSusChem (IF 7.226) Pub Date : 2017-12-11
    Alessio Dessì, Matteo Monai, Matteo Bessi, Tiziano Montini, Massimo Calamante, Alessandro Mordini, Gianna Reginato, Cosimo Trono, Paolo Fornasiero, Lorenzo Zani

    Donor-acceptor dyes are a well-established class of photosensitizers, used to enhance visible light harvesting in solar cells and in direct photocatalytic reactions, such as H2 production by photoreforming of sacrificial electron donors (SEDs). Amines - typically triethanolamine (TEOA) - are commonly employed as SEDs in such reactions. Dye-sensitized photoreforming of more sustainable, biomass-derived alcohols, on the other hand, was only recently reported using methanol as the electron donor. In this work, several rationally designed donor-acceptor dyes were used as sensitizers in H2 photocatalytic production, comparing the efficiency of TEOA and EtOH as SEDs. In particular, the effect of hydrophobic chains in the spacer and/or the donor unit of the dyes was systematically studied. The H2 production rates were higher when TEOA was used as SED, while the activity trends were dependent on the SED used. With TEOA, the best performance was obtained using a sensitizer (AD418) endowed with just one bulky hydrophobic moiety, propylenedioxythiophene (ProDOT), placed on the spacer unit. In the case of EtOH, the best performing sensitizers (TTZ4-5) were the ones featuring a thiazolo[5,4-d]thiazole internal unit, needed for enhancing light harvesting, and carrying alkyl chains on both the donor part and the spacer unit. The results are discussed in terms of reaction mechanism, interaction with SED and structural/ electrochemical properties of the sensitizers.

    更新日期:2017-12-11
  • Molecular Design of Efficient Organic D-A-π-A Dye Featuring Triphenylamine as Donor Fragment for Application in Dye-Sensitized Solar Cells
    ChemSusChem (IF 7.226) Pub Date : 2017-12-11
    Anders Hagfeldt, Parnian Ferdowsi, Yasemin Saygili, Weiwei Zhang, Tomas Edvinsson, Ladislav Kavan, Javad Mokhtari, Shaik M. Zakeeruddin, Michael Grätzel

    We designed, synthesized and characterized a novel metal-free organic sensitizer, suitable for the application in dye-sensitized solar cells (DSSCs), both experimentally and theoretically. The structure of the novel donor-acceptor-π-bridge-acceptor (D-A-π-A) dye has triphenylamine (TPA) segment and 4-(Benzo[c][1,2,5] thiadiazol-4-ylethynyl) benzoic acid (BTEBA). The triphenylamine unit is widely used as electron donor for the photosensitizers due to its outstanding characteristics, i.e. the non-planar molecular configuration and excellent electron donating capability while 4-(Benzo[c][1,2,5] thiadiazol-4-ylethynyl) benzoic acid is used as electron acceptor unit. We investigated the influence of iodide/triiodide, Cobalt(bpy)32+/3+ and Copper(tmby)22+/+complexes as redox electrolytes on the DSSC device performance. The maximal monochromatic incident photon to current conversion efficiency (IPCE) reached up to 81%. The solar light to electrical energy conversion efficiency of the devices with Cu(tmby)22+/+ reached up to 7.15%. The devices with Co(bpy)3 and Iodide/triiodide electrolytes showed 5.22% and 6.14% efficiency, respectively. The lowest device performance of Co(bpy)33+/2+ based electrolyte is attributed to the increased charge recombination process.

    更新日期:2017-12-11
  • Tracking Ionic Rearrangements and Interpreting Dynamic Volumetric Changes in Two-Dimensional Metal Carbides Supercapacitors: A Molecular Dynamics Simulation Study
    ChemSusChem (IF 7.226) Pub Date : 2017-12-06
    Kui Xu, Zifeng Lin, Céline Merlet, Pierre-Louis Taberna, Ling Miao, Jianjun Jiang, Patrice Simon

    We present a molecular dynamics simulation study achieved on two-dimensional (2D) Ti3C2Tx MXenes in an [EMIM]+[TFSI]- ionic liquid electrolyte. Our simulations reproduce the different patterns of volumetric change observed experimentally for both the negative and positive electrodes. The analysis of ionic fluxes and structure rearrangements in the 2D material provide an atomic scale insight into the charge and discharge processes in the layer pore and confirm the existence of two different charge storage mechanisms at the negative and positive electrodes. The ionic number variation and the structure rearrangement contribute to the dynamic volumetric changes of both electrodes: negative electrode expansion and positive electrode shrinkage.

    更新日期:2017-12-06
Some contents have been Reproduced with permission of the American Chemical Society.
Some contents have been Reproduced by permission of The Royal Society of Chemistry.
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