显示样式:     当前期刊: ChemSusChem    加入关注       排序: 导出
我的关注
我的收藏
您暂时未登录!
登录
  • 更新日期:2018-06-22
  • Flexible TiO2/SiO2/C Film Anodes for Lithium‐Ion Batteries
    ChemSusChem (IF 7.226) Pub Date : 2018-05-22
    Ying Jiang; Shi Chen; Daobin Mu; Zhikun Zhao; Chunli Li; Zepeng Ding; Chaoxiang Xie; Feng Wu
    更新日期:2018-06-22
  • A dual‐functional Zr‐MSU‐3 catalyst for cascade MPV reduction and dehydration of 4'‐methoxypropiophenone to anethole
    ChemSusChem (IF 7.226) Pub Date : 2018-06-21
    Hongwei Zhang; Candy Li-Fen Lim; Muhammad Zaki bin Ali; Stephan Jaenicke; Gaik-Khuan Chuah

    Anethole is an ingredient in many flavour, fragrance and pharmaceutical formulations. To reduce the dependence of its supply from natural oils, a green route for anethole synthesis is designed based on Meerwein‐Pondorf‐Verley reduction and dehydration of 4'‐methoxypropiophenone. The one‐pot cascade reactions were heterogeneously catalysed by dual‐functional Zr‐MSU‐3, a predominantly Lewis acid catalyst with Si/Zr ratio of 10 and pores in the range of 3.2 ‐ 4.2 nm. The use of 2‐pentanol as solvent and hydrogen donor for the MPV reduction was advantageous as its high boiling point enhanced the rate of reactions, especially the dehydration of the MPV product, 1‐(4‐methoxyphenyl)‐propan‐1‐ol. This dispenses with the need for a strong acid catalyst that could cause acid‐catalyzed by‐products. Anethole yields of 91 % with trans:cis isomer ratio ~ 92:8, similar to that of natural anethole, were obtained. In comparison, use of microporous Zr‐Beta (Si/Al 12.5) gave lower activity due to pore size constraints. Hence, through design of the reactions and catalyst, 4'‐methoxypropiophenone could be efficiently converted to anethole in a sustainable and green manner.

    更新日期:2018-06-22
  • Embedded Graphene Nanofibers in Perovskite layer of Perovskite Solar Cell
    ChemSusChem (IF 7.226) Pub Date : 2018-06-21
    yun Li; Wallace Woon-Fong Leung

    The application of graphene‐derived nanomaterials in electron transport layer(ETL)/hole transport layer(HTL) or top electrode for the perovskite solar cell(PSC) has been studied in recent years. However,the research of inserting such materials in the perovskite layer has not been fully investigated. In this paper,pristine graphene nanofibers have been introduced in the perovskite layer of PSC for the first time. The quality of the graphene nanofibers has been optimized by controlled centrifugation on the graphene sheets in the precursor suspension that are used for producing electrospun nanofibers. Under optimal condition, the device PCE increased from 17.51% without graphene to 19.83% with graphene nanofibers,representing a 13% increase. First,due to the introduction of graphene nanofibers into the perovskite layer,the grain size of the perovskite layer can be increased dramatically to over 2 microns,due to improved nucleation and crystallization on the nanofiber interface,which leads to much higher FF and Jsc. Second,the significant increase in Jsc and Voc are attributed to the improved charge transport property from the graphene nanofibers with superb charge conductivity introduced in the perovskite layer. The latter was independently verified by the measured electron transport time. The stability of the device has also been improved. In summary,an effective approach to improve the performance of PSCs by using pure graphene nanofibers has been developed for the first time.

    更新日期:2018-06-22
  • Towards Sustainable High‐Performance Thermoplastics: Synthesis, Characterization and Enzymatic Hydrolysis of Bisguaiacol‐based Polyesters
    ChemSusChem (IF 7.226) Pub Date : 2018-06-20
    Silvio Curia; Antonino Biundo; Isabel Fischer; Verena Braunschmid; Georg M. Gübitz; Joseph Stanzione

    The utilization of wood‐derived building blocks (xylochemicals) to replace fossil‐based precursors is an attractive research subject of modern polymer science. Here, we demonstrate that bisguaiacol (BG), a lignin‐derived bisphenol analogue, can be used to prepare bio‐based polyesters with remarkable thermal properties. BG has been reacted with different activated diacids to investigate the effect of co‐monomer structures on the physical properties of the products. Namely, derivatives of adipic acid, succinic acid and 2,5‐furandicarboxylic acid were used. Moreover, a terephthalic acid derivative was used for comparison purposes. The products were characterized by 1H‐NMR, ATR‐FTIR, GPC, TGA and DSC to assess their structural and thermal properties in detail. The polymers show Tgs ranging up to 160 °C and thermal stabilities in excess of 300 °C. Furthermore, the susceptibility of the polyester to enzymatic hydrolysis was investigated to assess the potential for further surface functionalization and/or recycling and biodegradation. Indeed, hydrolysis with two different enzymes from the bacteria Thermobifida Cellulosilytica lead to the release of monomers, as quantified via HPLC. The results of this study indicate that our new polyesters represent promising renewable and biodegradable alternatives to petroleum‐based polyesters currently employed in the plastics industry, specifically for applications where high‐temperature stability is essential to ensure overall system integrity.

    更新日期:2018-06-22
  • One‐Step Lignocellulose Fractionation by using 2,5‐Furandicarboxylic Acid as a Biogenic and Recyclable Catalyst
    ChemSusChem (IF 7.226) Pub Date : 2018-05-23
    Dennis Weidener; Holger Klose; Walter Leitner; Ulrich Schurr; Björn Usadel; Pablo Domínguez de María; Philipp M. Grande
    更新日期:2018-06-20
  • Self‐Assembly of Antisite Defectless nano‐LiFePO4@C/Reduced Graphene Oxide Microspheres for High‐Performance Lithium‐Ion Batteries
    ChemSusChem (IF 7.226) Pub Date : 2018-05-18
    Hongbin Wang; Lijia Liu; Runwei Wang; Xiao Yan; Ziqi Wang; Jiangtao Hu; Haibiao Chen; Shang Jiang; Ling Ni; Hailong Qiu; Haitong Tang; Yingjin Wei; Zongtao Zhang; Shilun Qiu; Feng Pan
    更新日期:2018-06-20
  • Bismuth Vanadate with Electrostatically Anchored Three‐dimensional Carbon Nitride Nano‐networks as Efficient Photoanodes for Water Oxidation
    ChemSusChem (IF 7.226) Pub Date : 2018-06-19
    Jie Zhang; Peng Luan; Ying Zhang; Xiaolong Zhang; Zhijun Li; Ragesh Prathapan; Udo Bach

    In this study, we report a photoanode consisting of polymeric/inorganic nanojunction between novel nanostructured three‐dimensional (3D) C3N4 nano‐networks and BiVO4 substrate. This nanojunction is formed in the way that 3D C3N4 nano‐networks with a positively charged surface are efficiently anchored on BiVO4 photoanodes with a negatively charged surface. This electrostatic self‐assembly can initiate and contribute to an intimate contact at their interfaces, leading to an enhanced photoelectrochemical activity and stability compared to that fabricated by non‐electrostatic assembly. Meanwhile, the C3N4 nano‐networks/BiVO4 photoanode achieved a remarkable photocurrent density of 4.87 mA∙cm‐2 for water oxidation at 1.23 V vs. RHE after depositing FeOOH/NiOOH as oxygen evolution cocatalyst, which is among the highest photocurrent densities reported so far for BiVO4‐based photoanodes.

    更新日期:2018-06-20
  • Shape Engineering of Biomass‐Derived Nanoparticles from Hollow Spheres to Bowls via Solvent‐Induced Buckling
    ChemSusChem (IF 7.226) Pub Date : 2018-06-19
    Chunhong Chen; Xuefeng Li; Deng Jiang; Zhe Wang; Yong Wang

    To realize the asymmetry for the hollow carbonaceous nanostructures remains to be a great challenge, especially when biomass is chosen as the carbon resource via hydrothermal carbonization (HTC). Herein, a simple and straightforward solvent induced buckling strategy is demonstrated for the synthesis of asymmetric spherical and bowllike carbonaceous nanomaterials. The formation of the bowllike morphology was attributed to the buckling of the spherical shells induced by the dissolution of the oligomers. The bowllike particles made by this solvent‐driven approach demonstrated a well‐controlled morphology and a uniform particle size of ~360 nm. The obtained nanospheres and nanobowls can be loaded with CoS2 nanoparticles to act as novel heterogeneous catalysts for the selective hydrogenation of aromatic nitro compounds. With the bowllike structure in hand, as expected, the CoS2/nanobowls catalyst showed good tolerance to a wide scope of reducible groups and afforded both high activity and selectivity in almost all the tested substrates (14).

    更新日期:2018-06-20
  • 更新日期:2018-06-20
  • Efficient Biomass Fuel Cell Powered by Sugar with Photo‐ and Thermal‐Catalysis by Solar Irradiation
    ChemSusChem (IF 7.226) Pub Date : 2018-06-19
    Wei Liu; Yutao Gong; Weibing Wu; Weisheng Yang; Congmin Liu; Yulin Deng; Zi‐sheng Chao
    更新日期:2018-06-20
  • Exploring MXenes as Cathodes for Non‐Aqueous Lithium–Oxygen Batteries: Design Rules for Selectively Nucleating Li2O2
    ChemSusChem (IF 7.226) Pub Date : 2018-06-19
    Andrew Lee; Dilip Krishnamurthy; Venkatasubramanian Viswanathan
    更新日期:2018-06-20
  • Enhanced Furfural Yields from Xylose Dehydration in the γ‐Valerolactone/Water Solvent System at Elevated Temperatures
    ChemSusChem (IF 7.226) Pub Date : 2018-06-19
    Canan Sener; Ali Hussain Motagamwala; David Martin Alonso; James A. Dumesic
    更新日期:2018-06-20
  • 更新日期:2018-06-20
  • Enhanced Crystallization by Methanol Additive in Antisolvent for Achieving High‐Quality MAPbI3 Perovskite Films in Humid Atmosphere
    ChemSusChem (IF 7.226) Pub Date : 2018-06-19
    Fu Yang; Muhammad Akmal Kamarudin; Putao Zhang; Gaurav Kapil; Tingli Ma; Shuzi Hayase
    更新日期:2018-06-20
  • Potential‐Dependent, Switchable Ion Selectivity in Aqueous Media Using Titanium Disulfide
    ChemSusChem (IF 7.226) Pub Date : 2018-05-01
    Pattarachai Srimuk; Juhan Lee; Simon Fleischmann; Mesut Aslan; Choonsoo Kim; Volker Presser
    更新日期:2018-06-20
  • Facile Modification of TiO2 with Nickel Sulfide and Sulfate Species for Photoreformation of Cellulose into H2
    ChemSusChem (IF 7.226) Pub Date : 2018-06-19
    Hongchang Hao; Ling Zhang; Wenzhong Wang; Shuwen Zeng

    Photocatalytic cellulose reformation is regarded as a potential and affordable route for sustainable H2 evolution. However, the direct photoreformation still suffers from challenges such as the limited solubility of cellulose and dependence on catalytic activity of noble‐metals. Herein, we reported a novel photoreformation of cellulose into H2 over TiO2 which is synchronously modified with nickel sulfide (NixSy) and chemisorbed sulfate species (SO42‐) by a one‐pot approach. A significant elevation in photocatalytic hydrogen evolution rate is achieved, with the maximal value of 3.02 mmol/g/h during the first three hours, almost 76‐fold higher than that of P25 and comparable to Pt‐P25. Aided by systematic investigation, it is proposed that nickel sulfide and sulfate modification synergistically contribute to the remarkably raised efficiency of biomass transformation. Specifically, NixSy serves as co‐catalyst for photocatalytic H2 production, while SO42‐ ions are inferred to promote cellulose hydrolyzation and consequent accessibility of biomass to catalysts. Further, the accumulated formate intermediates are found to have a poison effect on catalysts, desorption of which can be controlled by tuning aqueous alkalinity. Overall, our strategy for modifying TiO2 with SO42‐ and NixSy provides a novel perspective of concurrently accelerating cellulose hydrolyzation process and supplementing hydrogen evolution sites, for efficient photocatalytic reformation of cellulose into H2.

    更新日期:2018-06-20
  • Role of heteroatoms in S, N‐codoped nanoporous carbons in CO2 (photo)electrochemical reduction
    ChemSusChem (IF 7.226) Pub Date : 2018-06-19
    Teresa Bandosz; Wanlu Li

    Thiourea‐modified wood‐based activated carbons were evaluated as catalysts for CO2 electrochemical reduction reaction (CO2ERR). The materials obtained at 950oC showed a long stability. The results indicated that thiophenic sulfur provides catalytic activity for CO formation. However, it was not as active for CH4 formation as was pyridinic‐N. Tafel plots suggested that the nanoporous structure enhanced the kinetics for CO2 reduction. The electric conductivity limited the activity for CO2ERR in the materials modified at 600, 800 and 900oC. The effect of visible light on CO2ERR was also investigated in this study. Upon irradiation, photocurrent was generated, and a current density increased during CO2 reduction process. Combined with a band‐gap alignment, the results indicate that thiophenic‐S in the carbon matrix contributed to sample's photoactivity in visible light. These species enhance the overall reduction process promoting both hydrogen evolution reaction and CO2 reduction to CO.

    更新日期:2018-06-19
  • Solution‐proceed Air‐stable Copper Bismuth Iodide CuBiI₄ for Photovoltaics
    ChemSusChem (IF 7.226) Pub Date : 2018-06-19
    Zhaosheng Hu; Zhen Wang; Gaurav Kapil; Tingli Ma; Satoshi Iikubo; Takashi Minemoto; Kenji Yoshino; Taro Toyoda; Qing Shen; Shuzi Hayase

    Bismuth based solar cells have been under intensive interest as an efficient non‐toxic absorber in photovoltaics. Within this new family of semiconductors, we herein, report a new, long‐term stable material copper bismuth iodide (CuBiI₄). A solution‐processed method is provided under air atmosphere. The adopted HI assisted Dimethylacetamide (DMA) co‐solvent can completely dissolve CuI and BiI₃ powders with high concentration compared to other organic solvent. Moreover, high vapor pressure of Tributyl phosphate, we select for the solvent vapor annealing (SVA), enables the whole low‐temperature (≤70⁰C) film preparation. It results in a stable, uniform dense CuBiI₄ film. The average grains size increasing with precursor concentration, greatly enlarge the PL life time and hall mobility. And carrier lifetime of 3.03 ns as well as an appreciable hall mobility of 110 cm²/Vs were obtained. X‐ray diffraction illustrates that the crystal structure is cubic (space group Fd3m) and favored in [1, 1, 1] direction. Moreover, the photovoltaic performance of CuBiI₄ was also investigated. A wide‐bandgap (2.67 eV) solar cell with 0.82 % performance is presented, which shows an excellent long‐term stability at least over 1008 hours under ambient conditions. This air‐stable material may give an application in future tandem solar cells as a stable short‐wavelength light absorber.

    更新日期:2018-06-19
  • Panchromatic Sensitization Using Zn(II) Porphyrin‐Based Photosensitizers for Light‐Driven Hydrogen Production in Water
    ChemSusChem (IF 7.226) Pub Date : 2018-06-19
    Po-Yu Ho; Michael F. Mark; Yi Wang; Sze-Chun Yiu; Wai-Hong Yu; Cheuk-Lam Ho; David W. McCamant; Richard Eisenberg; Shuping Huang

    Three molecular photosensitizers (PSs) with carboxylic acid anchors for attachment to platinized titanium dioxide nanoparticles were studied for light‐driven hydrogen production from a fully aqueous medium with ascorbic acid (AA) as the sacrificial electron donor. Two zinc(II) porphyrin (ZnP) based PSs (ZnP‐dyad and YD2‐o‐C8) were used to examine the effect of panchromatic sensitization in promoting photocatalytic H2 generation. A dyad molecular design was used to construct the Bodipy‐conjugated ZnP PS (ZnP‐dyad) and another one was featured with an electron‐donating diarylamino moiety (YD2‐o‐C8). In order to probe the good use of the ZnP scaffold in this particular energy conversion process, an organic PS without the ZnP moiety (Bodipy‐dye) was also synthesized for comparison. Ultrafast transient absorption spectroscopy was adopted to map out the energy transfer processes occurring in the dyad and establish the Bodipy‐based antenna effect. In particular, the systems with YD2‐o‐C8 and ZnP‐dyad achieve a remarkable initial activity in H2 production with an initial turnover frequency (TOFi) larger than 300 h‐1 under white light irradiation. In brief, the use of ZnP PSs in dye‐sensitized photocatalysis for H2 evolution reaction in this study indicates the importance of panchromatic sensitization capability for the development of light absorbing PSs.

    更新日期:2018-06-19
  • A CsPbBr3/TiO2 Composite for Visible‐Light‐Driven Photocatalytic Benzyl Alcohol Oxidation
    ChemSusChem (IF 7.226) Pub Date : 2018-05-23
    Stefan Schünemann; Maurice van Gastel; Harun Tüysüz
    更新日期:2018-06-18
  • 更新日期:2018-06-15
  • How to Harvest Grotthuss Diffusion in Protic Ionic Liquid Electrolyte Systems
    ChemSusChem (IF 7.226) Pub Date : 2018-06-14
    Johannes Ingenmey; Sascha Gehrke; Barbara Kirchner
    更新日期:2018-06-15
  • How to Harvest Grotthuss Diffusion in Protic Ionic Liquid Electrolyte Systems
    ChemSusChem (IF 7.226) Pub Date : 2018-05-09
    Johannes Ingenmey; Sascha Gehrke; Barbara Kirchner
    更新日期:2018-06-15
  • Catalytic Transformation of Cellulose and Its Derivatives into Functionalized Organic Acids
    ChemSusChem (IF 7.226) Pub Date : 2018-04-30
    Shi Li; Weiping Deng; Shanshan Wang; Pan Wang; Dongli An; Yanyun Li; Qinghong Zhang; Ye Wang
    更新日期:2018-06-15
  • Green Layer‐by‐layer Method for the Preparation of Polyacrylonitrile‐Supported Zn(BDC) Membranes
    ChemSusChem (IF 7.226) Pub Date : 2018-06-14
    Hui Min Tham; Susilo Japip; Dan Hua; Tai-Shung Chung

    Ultrafiltration‐level polyacrylonitrile (PAN) flat sheet membranes were chemically modified via cross‐linking and hydrolysis to provide a suitable surface for the growth of a selective layer composed of Zn‐benzene‐1,4‐dicarboxylic acid (Zn(BDC)) metal‐organic framework (MOF). Unlike typical membrane modification methods or conventional MOF synthesis procedures, deionized (DI) water was the only solvent used for each of the modification steps involved. To better understand the layer‐by‐layer MOF growth, several MOF growth conditions were also studied, including the effects of solution concentration, growth temperature, membrane immersion time and the number of layers. Subsequently, organic solvent nanofiltration (OSN) was used as a means of testing the effectiveness of the modifications and comparing the performances of the fabricated membranes. With a proper combination of MOF growth conditions, the layer‐by‐layer method was able to produce an OSN membrane with an isopropanol (IPA) permeance of 2.39 L m‐2 h‐1 bar‐1 and an 86% rejection of the dye Brilliant Blue R (Mw 825.97 g mol‐1).

    更新日期:2018-06-15
  • Towards Hydrogen Storage through an Efficient Ruthenium‐Catalyzed Dehydrogenation of Formic Acid
    ChemSusChem (IF 7.226) Pub Date : 2018-05-03
    Zhuo Xin; Jiahui Zhang; Katerina Sordakis; Matthias Beller; Chen‐Xia Du; Gabor Laurenczy; Yuehui Li
    更新日期:2018-06-14
  • Synthesis and Characterization of Carboxyethylated Lignosulfonate
    ChemSusChem (IF 7.226) Pub Date : 2018-06-13
    KHatereh Barhpaima; Pedram Fatehi

    Lignosulfonate is a by‐product of sulfite pulping process with a limited use in industry. The main objective of this study was to investigate the carboxyethylation of lignosulfonate (LS) as a means to increase its charge density for broadening its application. The carboxyethylation of lignosulfonate was optimized under the conditions of 30 wt% NaOH, 2.0 mol mol‐1 of 2‐cholropropinic acid/lignosulfonate, 90 °C, 0.5 h and 0.03 mol of 2‐cholropropinic acid, which produced carboxyethylated lignosulfonate (CELS) with the charge density and molecular weight of ‐3.51 meq g‐1 and 46,493 g mol‐1, respectively. The mechanism of carboxyethylation reaction using 2‐cholropropinic acid via an SN1 pathway in an alkaline solution was fundamentally discussed in this work. Methylation was also used as a means to mask phenolic hydroxides of lignosulfonate to investigate if carboxyethylation occurred on aliphatic hydroxide groups of lignosulfonate. The produced carboxyethylated lignosulfonate was further characterized via Fourier transform infrared (FT‐IR), nuclear magnetic resonance (NMR), gel permeation chromatography (GPC), as well as elemental and functional group analyses. The basic 1H‐1H 2D COSY NMR diagram was used for recording the coupled spins of carboxyethyl group on CELS. The information of 1D 1H‐NMR and 2D NMR COSY techniques provided evidence for the existence of 1‐carboxyethyl group on the CELS structure.

    更新日期:2018-06-14
  • NiO Nanoparticles Anchored on Phosphorus‐Doped α‐Fe2O3 Nanoarrays: An Efficient Hole Extraction p–n Heterojunction Photoanode for Water Oxidation
    ChemSusChem (IF 7.226) Pub Date : 2018-05-16
    Feng Li; Jing Li; Jie Zhang; Lili Gao; Xuefeng Long; Yiping Hu; Shuwen Li; Jun Jin; Jiantai Ma
    更新日期:2018-06-13
  • Iron(III) N,N‐Dialkylcarbamates Catalyze the Formation of Cyclic Carbonates from Carbon Dioxide and Epoxides at Ambient Conditions via Dynamic CO2 Trapping as Carbamato Ligand
    ChemSusChem (IF 7.226) Pub Date : 2018-06-13
    Guido Pampaloni; Giulio Bresciani; Marco Bortoluzzi; Fabio Marchetti

    Abstract. Easily available and inexpensive Fe(III) carbamates was employed in the solventless synthesis of a series of cyclic carbonates from epoxides, by reaction with CO2 at room temperature and atmospheric pressure, in the presence of a co‐catalyst. Different experimental conditions (type and concentration of catalyst and co‐catalyst, as well as reaction time) were investigated: Fe(O2CNEt2)3 and NBu4Br acted as the best catalyst/co‐catalyst combination, allowing the formation of propylene carbonate and 1,2‐butylene carbonate with quantitative yield and selectivity during 24 h of reaction time. According to NMR and DFT studies, the reaction proceeds with the dynamic trapping of carbon dioxide as a carbamato ligand.

    更新日期:2018-06-13
  • Nanostructured FeNi3 incorporated by multi‐non‐metal‐doped carbon for oxygen evolution reaction
    ChemSusChem (IF 7.226) Pub Date : 2018-06-12
    Zong Liu; Xu Yu; Huaguang Yu; Huaiguo Xue; Ligang Feng

    The sluggish oxygen evolution reaction (OER) is still tricky in water electrolysis technique. Herein, a facile approach to fabricate highly efficient nanostructured FeNi3 incorporated by multi‐non‐metal elements doped carbon (FeNi3/M‐C) is proposed by annealing an in situ polymerized metal‐complex from economical precursors. Temperature dependence of structure and catalytic performance for OER is probed and the best pyrolysis temperature is 800oC in which the fabricated material exhibits the highest catalytic performance for OER. Specifically, an overpotential as low as 246 mV (No IR Correction) can afford 10 mA cm‐2 with a low Tafel slope of 40 mV dec‐1, exceeding the best noble catalyst IrO2 and other similar Fe‐Ni alloys. High catalytic efficiency and anti‐corrosion ability towards OER are displayed in terms of high specific surface area, rapid kinetics, high stability and specific activity. The excellent performance can be correlated to its structure of modest graphitization degree of carbon and a proper ratio of graphitic‐N to pyridinic‐N and the collaboration of Fe‐Ni alloy active sites with conducting carbon doped by multi‐non‐metal elements. Moreover, as a powder catalyst, it is more applicable in a real polymer electrolyte membrane electrolyzer. This result is helpful in understanding the catalytic activity and promoting the catalyst efficiency of Fe‐Ni alloy materials for OER.

    更新日期:2018-06-12
  • A Novel Bimetallic NiMo Carbide Nanowire Array for Efficient Hydrogen Evolution
    ChemSusChem (IF 7.226) Pub Date : 2018-06-12
    Lixia Guo; Jianying Wang; Xue Teng; Yangyang Liu; Xiaoming He; Zuofeng Chen

    Design and fabrication of noble metal‐free hydrogen evolution electrocatalysts with high activity is significant to future renewable energy systems. In this work, self‐supported NiMo carbide nanowires have been developed on carbon cloth (Ni3Mo3C@NPC NWs/CC; NPC is N,P‐doped carbon) through an electropolymerization‐assisted procedure. During the synthesis process, NiMoO4 nanowires were first grown on CC through a hydrothermal reaction which is free of any polymer binder like Nafion. The as‐prepared NiMoO4 NWs/CC was then coated by a layer of polypyrole (PPy) by electropolymerization that serves as carbon source for the subsequent conversion to Ni3Mo3C@NPC NWs/CC by carbothermal reduction. The experimental results indicate that the judicious choices of the amount of coated PPy and the pyrolysis temperature are essential for obtaining pure phase and nanowire array structure of Ni3Mo3C@NPC NWs/CC. Benefitting from the pure phase of bimetallic carbide, the unique architecture of nanowire array and the self‐supported merit, the optimized Ni3Mo3C@NPC NWs/CC electrode exhibits excellent HER performance in both acidic and alkaline media. It requires low overpotentials of 161 mV and 215 mV to afford a high current density of 100 mA cm‐2 toward the HER in acidic and alkaline media, respectively, and the catalytic activity is maintained for at least 48 h, which makes it among the best HER electrocatalysts based on metallic carbides yet reported.

    更新日期:2018-06-12
  • 1,4‐Dioxane‐tuned Catalyst‐free Methylation of Amines using CO2 and NaBH4
    ChemSusChem (IF 7.226) Pub Date : 2018-06-12
    Chanjuan Xi; Zhiqiang Guo; Bo Zhang; Xuehong Wei

    A catalyst‐free reductive functionalization of CO2 with amines and NaBH4 was achieved. This protocol realized the N‐methylation of amines using CO2 as a C1‐building block in the 1,4‐dioxane as solvent. Notably, the six‐electron reduction of CO2 to the methyl with formation of C‐N bond was attained simultaneously.

    更新日期:2018-06-12
  • HCOOH‐induced Controlled‐release Hydrolysis of Microalgae (Scenedesmus) to Lactic Acid over Sn‐Beta Catalyst
    ChemSusChem (IF 7.226) Pub Date : 2018-06-12
    Yifan Zan; Yuanyuan Sun; Lingzhao Kong; Gai Miao; Liwei Bao; Hao Wang; Shenggang Li; Yuhan Sun

    Formic acid induced controlled‐release hydrolysis of sugar‐rich microalgae (Scenedesmus) over the Sn‐Beta catalyst was found to be a highly efficient process for producing lactic acid as a platform chemical. One‐pot reaction with a very high lactic acid yield of 83.0% was realized in a batch reactor using water as the solvent. Under the attack of formic acid, the cell wall of Scenedesmus was disintegrated, and hydrolysis of the starch inside the cell was strengthened in a controlled‐release mode, resulting in a stable and relatively low glucose concentration. Subsequently, the Sn‐Beta catalyst was employed for the efficient conversion of glucose into lactic acid with stable catalytic performance through isomerization, retro‐aldol and de‐/rehydration reactions. Thus, the hydrolysis of polysaccharides and the catalytic conversion of the monosaccharide into lactic acid was realized by the synergy between an organic Brønsted acid and a heterogeneous Lewis acid catalyst.

    更新日期:2018-06-12
  • A Two‐Step Process for the Synthesis of Hydroxytyrosol
    ChemSusChem (IF 7.226) Pub Date : 2018-05-14
    Paolo Ziosi; Claudio Paolucci; Francesco Santarelli; Tommaso Tabanelli; Sauro Passeri; Fabrizio Cavani; Paolo Righi
    更新日期:2018-06-12
  • Early‐Stage Sustainability Evaluation of Nanoscale Cathode Materials for Lithium Ion Batteries
    ChemSusChem (IF 7.226) Pub Date : 2018-05-07
    Roland Hischier; Nam Hee Kwon; Jean‐Pierre Brog; Katharina M. Fromm
    更新日期:2018-06-12
  • Simultaneous Stabilization of LiNi0.76Mn0.14Co0.10O2 Cathode and Lithium Metal Anode by Lithium Bis(oxalato)borate as Additive
    ChemSusChem (IF 7.226) Pub Date : 2018-06-11
    Wengao Zhao; Lianfeng Zou; Jianming Zheng; Haiping Jia; Junhua Song; Mark H. Engelhard; Chongmin Wang; Wu Xu; Yong Yang; Ji‐Guang Zhang
    更新日期:2018-06-12
  • Facile Formation of Nanostructured Manganese Oxide Films as High‐performance Catalysts for Water Oxidation
    ChemSusChem (IF 7.226) Pub Date : 2018-06-11
    Matthias Driess; Carsten Walter; Prashanth Menezes; Holger Dau; Stefan Loos

    The development of inexpensive, earth abundant and bioinspired oxygen evolution (water oxidation) electrocatalysts that are easily accessible and scalable is a principal requirement regarding the feasibility of water splitting for large‐scale chemical energy storage. Here we present a unique, versatile and scalable approach to fabricate manganese oxide films starting from single layers to multi‐layers, with controlled thickness and high reproducibility. The resulting MnOx films are comprised of small nanostructures that are assembled closely, in form of porous sponge‐like layers. The films were investigated for the electrochemical oxygen evolution reaction in alkaline media and demonstrate a remarkable activity as well as superior stability of over 60 h. To elucidate the catalytically active species as well as their striking structural characteristics, the films were further examined by in‐depth SEM, TEM, XPS as well as quasi in‐situ EXAFS and XANES. The MnOx catalyst films excel by a favorably high fraction of Mn3+ ions that are retained even after operation at oxidizing potentials. Upon exposure to oxidizing potentials in strongly alkaline aqueous electrolytes, the catalyst material maintains its structural integrity at the nanostructural, morphological and atomic level.

    更新日期:2018-06-12
  • Electrochemical hydrogen evolution reaction efficiently catalyzed by Ru2P nanoparticles
    ChemSusChem (IF 7.226) Pub Date : 2018-06-11
    Yuan Wang; Zong Liu; Hui Liu; Nian-Tzu Suen; Xu Yu; Ligang Feng

    Developing Pt alternative catalyst is prerequisite to cost‐effectively produce hydrogen. Herein, we demonstrate Ru2P nanoparticles (without any doping and modifications) as a highly efficient Pt‐like catalyst for hydrogen evolution reaction (HER) in different pH electrolytes. Transferring hexagonal close‐packed crystal structure of Ru to orthorhombic structure of Ru2P, a greatly improved catalytic activity and stability toward HER is found due to Ru‐P coordination. The electronic state change originates from the P‐Ru bonding structures would account for the HER activity improvement compared with Ru nanoparticles. Specifically, Ru2P nanoparticles can drive 10 mA cm−2 at a very low overpotential of 55 mV, only 8 mV more compared with Pt/C in an acidic solution; and an extremely low overpotential of ca. 50 mV is needed in alkaline solution, ca. 20 mV less than Pt/C catalyst. Volmer−Tafel mechanism is indicated on Ru2P nanoparticles with the typical Tafel slope of 30 mV dec−1 of Pt metal indicating a Pt‐like catalytic ability. Ru2P is more active in Ru‐P family as H atom prefers to adsorb on Ru atom rather than on P element according to theory calculation. Considering the low price of Ru (20% of Pt), anti‐corrosion in the electrolyte, safe and reliable fabrication approach, powder Ru2P nanoparticles catalyst is an excellent HER catalyst with great promise for large‐scale water electrolysis applications.

    更新日期:2018-06-12
  • Hierarchical Ni‐Co Based Transition Metal Oxide Catalysts for Electrochemical Conversion of Biomass into Valuable Chemicals
    ChemSusChem (IF 7.226) Pub Date : 2018-06-09
    Lifang Gao; Yu Bao; Shiyu gan; Zhonghui Sun; Zhongqian Song; Dongxue Han; Fenghua Li; Li Niu

    Biomass upgrading into sustainable and valuable fine chemicals is alternative to the state‐of‐the‐art petrochemicals. Typically, conversion of 5‐hydroxymethylfurfural (HMF) biomass derivative into 2,5‐furandicarboxylic acid (FDCA) has been recognized as an economic and green approach to replace current polyethylene terephthalate‐based plastic industry. However, this reaction mostly relies on noble‐based catalysts for sluggish aerobic oxidation of alcohol groups. In this work, we report a series of hierarchical Ni‐Co based transition metal oxide catalysts for HMF oxidation by electrocatalysis. Comprehensive material characterizations and electrochemical evaluations have been performed. 90% FDCA yield, nearly 100% Faradaic efficiency and robust stability were achieved for NiCo2O4 nanowires. As non‐precious catalysts, Ni‐Co based transition metal oxide may open up a type of potential materials for highly efficient electrochemical biomass upgrading.

    更新日期:2018-06-10
  • Mechanistic Studies of the Cu(OH)+‐Catalyzed Isomerization of Glucose into Fructose in Water
    ChemSusChem (IF 7.226) Pub Date : 2018-06-09
    Joel Mensah; Irina Delidovich; Peter J.C. Hausoul; Laurent Weisgerber; Wolfgang Schrader; Regina Palkovits

    The isomerization of glucose to fructose is a crucial interim step in the processing of biomass to renewable fuels and chemicals. This study investigates the copper catalyzed glucose‐fructose‐isomerization in water focusing on insights into the roles of dissolved copper species. Depending on the pH, the thermodynamic equilibrium is shifted towards one or a few copper species namely Cu2+, Cu(OH)+, and Cu(OH)2. According to thermodynamics, the highest concentration of Cu(OH)+ is found at pH 5.3 for which also the highest fructose yield of 19% is achieved. The obtained fructose yields strongly correlate with the concentration of Cu(OH)+. Due to the formation of acidic by‐products, a pH decrease by 2‐3 units was observed during the reaction resulting in the deactivation of the catalyst through hydrolysis in acidic media. Based on the results of catalytic experiments and spectrometric studies we propose Cu(OH)+ as active Lewis acidic species following an intramolecular 1,2‐hydride shift.

    更新日期:2018-06-10
  • Transition‐metal‐free CO2 fixation into new carbon‐carbon bonds
    ChemSusChem (IF 7.226) Pub Date : 2018-06-08
    Marcella Bonchio; Alessio Cherubini-Celli; Javier Mateos; Luca Dell’Amico; Xavier Companyó

    CO2 is the ultimate, renewable, carbon source on Earth and the essential C1‐building block for carbohydrate biosynthesis in photosynthetic organisms. Modern synthetic chemistry is facing the key challenge of developing fundamental transformations such as C‐C bond formation, in sustainable and efficient manner from renewable sources. We review herein the most significant methods recently reported for CO2 fixation under transition‐metal‐free conditions. The manuscript is organised into three different chapters, according to the nature of the chemical transformation that forge the new C‐C bond. This perspective focuses on the mechanistic aspects of the different CO2 activation modes, with specific attention to those systems that successfully operate under catalytic conditions

    更新日期:2018-06-08
  • Electrochemically Deposited Nickel Oxide from Molecular Complexes for Efficient Water Oxidation Catalysis
    ChemSusChem (IF 7.226) Pub Date : 2018-06-08
    Karsten Meyer; Lianpeng Tong; Andreas Scheurer; Karsten Kuepper; Wenling Wu

    A facile method for the electrodeposition of amorphous nickel oxyhydroxide is described and discussed, where well‐defined nickel complexes with pyridinedimethanol ligands are employed as single‐source molecular precursors. No buffering agent is required to assist the anodic deposition process. The deposited nickel oxyhydroxide shows high robustness and efficiency for electrocatalytic water oxidation.

    更新日期:2018-06-08
  • Rational design of low cost and high energy lithium batteries through tailored fluorine‐free electrolyte and nanostructured sulfur/carbon composite
    ChemSusChem (IF 7.226) Pub Date : 2018-06-07
    Marco Agostini; Du Hyun Lim; Matthew Sadd; Jang-Yeon Hwang; Segio Brutti; Jungwon Heo; Jou-Hyeon Ahn; Yang-Kook Sun; Aleksandar Matic

    We report a new lithium/sulfur cell concept based on an optimized fluorine‐free catholyte solution and a high loading nanostructured carbon/sulfur composite cathode. The Li2S8 present in the electrolyte ensures both buffering against active material dissolution and Li+ conduction. The high sulfur loading is obtained by confining elemental sulfur (~80%) in the mesopores of a highly ordered CMK3 carbon. With this concept we demonstrate stabilization of high energy density and excellent cycling performance over 500 cycles. The Li‐S cell has a specific capacity that reaches over 1000 mAh g‐1, with an overall sulfur loading of 3.6 mg cm‐2 and low electrolyte volume, i.e. 10 µl cm‐2, resulting in a practical energy density of 365 Wh kg‐1. The Li‐S system proposed thus meets the requirements for large scale energy storage systems and is expected to be environmentally friendly and have a low cost when compared to commercial Li‐ion battery thanks to the removal of both cobalt and fluorine from the overall formulation.

    更新日期:2018-06-08
  • 更新日期:2018-06-07
  • In situ Biofilm Quantification in Bioelectrochemical Systems by using Optical Coherence Tomography
    ChemSusChem (IF 7.226) Pub Date : 2018-04-25
    Sam D. Molenaar; Tom Sleutels; Joao Pereira; Matteo Iorio; Casper Borsje; Julian A. Zamudio; Francisco Fabregat‐Santiago; Cees J. N. Buisman; Annemiek ter Heijne
    更新日期:2018-06-07
  • Dual Rh‐Ru catalysts for reductive hydroformylations of olefins to alcohols
    ChemSusChem (IF 7.226) Pub Date : 2018-06-06
    Fabio Rodrigues; Peter Kucmierczyk; Marta Pineiro; Ralf Jackstell; Robert Franke; Mariette Pereira; Matthias Beller

    An active and selective dual catalytic systems to promote domino hydroformylation/reduction reactions are described. Apart from terminal, di‐ and tri‐substituted olefins for the first time also less active internal C‐C double bond of tetra‐substituted alkenes can be utilized. As an example, 2,3‐dimethylbut‐2‐ene is converted to the corresponding n‐alcohol with high yield (90%) as well as regio‐ and chemoselectivity (>97%). Key for this development is the use of a combination of Rh complexes with bulky monophosphites and the Ru‐based Shvo's‐complex. A variety of aromatic and aliphatic alkenes can be directly used to obtain mainly linear alcohols.

    更新日期:2018-06-07
  • Deactivation and Regeneration of Sulfonated Carbon Catalysts in Hydrothermal Reaction Environments
    ChemSusChem (IF 7.226) Pub Date : 2018-05-07
    David Scholz; Oliver Kröcher; Frédéric Vogel
    更新日期:2018-06-06
  • Quasi‐solid state electrolytes for low‐grade thermal energy harvesting using a cobalt redox couple
    ChemSusChem (IF 7.226) Pub Date : 2018-06-06
    Abuzar Taheri; Douglas MacFarlane; Cristina Pozo-Gonzalo; Jennifer M. Pringle

    Thermoelectrochemical cells, also known as thermocells, are electrochemical devices for the conversion of thermal energy directly to electricity. They are a promising method for harvesting low‐grade waste heat from a variety of different natural and man‐made sources. The development of solid or quasi‐solid state electrolytes for thermocells could address the possible leakage problems of liquid electrolytes and make this technology more applicable for wearable devices. Here we report the gelation of an organic solvent‐based electrolyte system containing a redox couple, for application in thermocell technologies. The effect of gelation of the liquid electrolyte, comprising a cobalt bipyridyl redox couple dissolved in 3‐methoxypropionitrile (MPN), on the performance of thermocells was investigated. Polyvinylidene difluoride (PVDF) and poly(vinylidene fluoride‐co‐hexafluoropropene) (PVDF‐HFP) were used for gelation of the electrolyte, and the influence of the different polymers on the mechanical properties was studied. The Seebeck coefficient and diffusivity of the cobalt redox couple were measured in both liquid and gelled electrolytes and the effect of gelation on the thermocell performance is reported. Finally, the cell performance was further improved by optimising the redox couple concentration and the separation between the hot and cold electrode, and the stability of the device over 25 hours of operation is demonstrated.

    更新日期:2018-06-06
  • Highly selective synthesis of acrylic acid from lactide in liquid phase
    ChemSusChem (IF 7.226) Pub Date : 2018-06-06
    Jens Nagengast; Simon Hahn; Nicola Taccardi; Matthias Kehrer; Julian Kadar; Dimitris Collias; Peter Dziezok; Peter Wasserscheid; Jakob Albert

    A novel reaction system for the highly selective, hydrobromic acid catalysed conversion of lactide into acrylic acid under mild conditions is reported. The applied liquid reaction system consists of a temperature‐stable bromide‐containing ionic liquid and 2‐bromopropionic acid as source of dry HBr, with no volatile organic solvent being used. This allows for the in situ removal of the formed acrylic acid leading to an unmatched acrylic acid selectivity of over 72% at full lactide conversion. Accounting for leftover reaction intermediates on the way to acrylic acid that could be recycled in an elaborate continuous process, the proposed reaction system shows potential for acrylic acid yields well above 85% in liquid phase. This opens new avenues for the effective conversion of biogenic lactic acid (e.g. obtained by fermentation from starch) to acrylic acid. The resulting bio‐acrylic acid is a highly attractive product for, e.g. the diaper industry, where we expect consumers to be especially sensitive to aspects of sustainability.

    更新日期:2018-06-06
  • Iridium‐coordinated Histidyl Bolaamphiphile Self‐assemblies as Heterogeneous Catalysts for Water Oxidation
    ChemSusChem (IF 7.226) Pub Date : 2018-06-06
    Changjoon Keum; Sang-Yup Lee

    Catalysts promoting oxygen evolution from water are necessary for green energy production. In this study, colloidal heterogeneous catalysts for oxygen evolution were prepared by coordination of Ir species to self‐assemblies of histidyl bolaamphiphiles. When dissolved in water, the histidyl bolaamphiphiles self‐assembled to form particulate structures with exposure of densely packed histidine imidazoles on their surface. Subsequent coordination of Ir species to the bolaamphiphile assembly exhibited catalytic activity toward the oxygen evolution reaction. The oxygen evolution was examined using the catalytic assemblies in the presence of a sacrificial oxidant, cerium ammonium nitrate. The Ir‐coordinated assemblies showed a turnover frequency of 13 min−1, which was comparable to those previously reported for molecular water oxidation catalysts. The catalytic activity increased with the histidine imidazole to Ir molar ratio, thereby suggesting that multiple coordination of Ir to imidazoles facilitates the formation of active Ir intermediates. This study demonstrated the feasibility of colloidal bolaamphiphile assemblies with biochemical ligands to construct catalytically active interfaces.

    更新日期:2018-06-06
  • Ruthenium Supported on High‐Surface‐Area Zirconia as an Efficient Catalyst for the Base‐Free Oxidation of 5‐Hydroxymethylfurfural to 2,5‐Furandicarboxylic Acid
    ChemSusChem (IF 7.226) Pub Date : 2018-05-15
    Christian M. Pichler; Mohammad G. Al‐Shaal; Dong Gu; Hrishikesh Joshi; Wirawan Ciptonugroho; Ferdi Schüth
    更新日期:2018-06-05
  • Synthesis of Grain‐like MoS2 for High‐Performance Sodium‐Ion Batteries
    ChemSusChem (IF 7.226) Pub Date : 2018-05-05
    Kai Yao; Zhanwei Xu; Zhi Li; Xinyue Liu; Xuetao Shen; Liyun Cao; Jianfeng Huang
    更新日期:2018-06-05
  • Construction of Bifunctional Co/H‐ZSM‐5 Catalysts for the Hydrodeoxygenation of Stearic Acid to Diesel‐Range Alkanes
    ChemSusChem (IF 7.226) Pub Date : 2018-04-27
    Guangjun Wu; Nan Zhang; Weili Dai; Naijia Guan; Landong Li
    更新日期:2018-06-05
  • Fe‐catalyzed graphitic carbon materials from biomass resources as anodes for lithium ion batteries
    ChemSusChem (IF 7.226) Pub Date : 2018-06-05
    Aurora Gomez-Martin; Julian Martinez-Fernandez; Mirco Ruttert; Andreas Heckmann; Martin Winter; Tobias Placke; Joaquin Ramirez-Rico

    Graphitized carbon materials from biomass resources were successfully synthesized by means of an iron catalyst, and their electrochemical performance as anode materials for lithium‐ion batteries (LIBs) was investigated. Peak pyrolysis temperatures between 850 °C and 2000 ºC were covered to study the effect of crystallinity and microstructural parameters on the anodic behaviour, focusing on the first‐cycle Coulombic efficiency, reversible specific capacity and rate performance. In terms of capacity, results at the highest temperatures are comparable to those of commercially used synthetic graphite derived from a petroleum coke precursor at higher temperatures, and up to two times than non‐catalyzed biomass‐derived carbons. The opportunity to graphitize low‐cost biomass resources at moderate temperatures through this one‐step environmental friendly process and the positive effects on the specific capacity, make it interesting to develop more sustainable graphite‐based anodes for LIBs.

    更新日期:2018-06-05
  • Dual modification of BiVO4 photoanode by constructing heterojunction with NiMoO4 and depositing CoPi co‐catalyst for enhanced photoelectrochemical performance
    ChemSusChem (IF 7.226) Pub Date : 2018-06-04
    Lili Gao; Feng Li; Haiguo Hu; Xuefeng Long; Na Xu; Yiping Hu; Shenqi Wei; Chenglong Wang; Jiantai Ma; Jun Jin

    Bismuth vanadate (BiVO4) has triggered extensive interests in photoelectrochemical (PEC) water splitting owing to its narrow bandgap and sufficiently positive valence band. However, some defects still exist to block the solar utilization efficiency and hydrogen evolution kinetics. In this work, we bring NiMoO4 semiconductor to the fields of BiVO4 photoanode designation for the first time and achieve excellent PEC performance on the basis of the heterojunction formation as well as favorable conductivity of NiMoO4. In addition, it has been demonstrated that NiMoO4 works for promotion of light absorption ability, charge separation efficiency (ηsep), and surface charge transfer efficiency (ηtrans) comprehensively. To further improve its photo conversion efficiency, we deposited cobalt phosphate (CoPi) as an oxygen evolution reaction (OER) co‐catalyst on the above electrode and achieved much more enhanced utilization efficiency of 1.18% with the photocurrent density of 5.3 mA cm‐2 at 1.23 V vs. reversible hydrogen electrode (RHE), exceeding most researches as far as we know. This rational and unique photoanode construction provides a new thread for the photoelectrode designation.

    更新日期:2018-06-05
  • Revealing the relationship between the photocatalytic property and structure characteristic of reduced TiO2 by hydrogen and carbon monoxide treatment
    ChemSusChem (IF 7.226) Pub Date : 2018-06-04
    Yunpeng Liu; Yuhang Li; Siyuan Yang; Yuan Lin; Jianliang Zuo; Hong Liang; Feng Peng

    The hydrogenation (reduction) has been considered as an effective method to improve the photocatalytic activity of TiO2, however, the underlying relationship between structure and photocatalytic performance has still not been adequately unveiled so far. Herein, to obtain insight into the effect of structure on photocatalytic activity, two types of reduced TiO2 were prepared by CO (CO‐TiO2) and H2 (H‐TiO2), respectively. For H‐TiO2, Ti‐H bonds and oxygen vacancies are formed on the surface of H‐TiO2, resulting in a more disorder surface lattice. However, for CO‐TiO2, the more Ti‐OH bonds are formed on the surface and the more bulk oxygen vacancies are introduced, the disorder layer of CO‐TiO2 is relatively thin owing to the most of surface vacancies repaired by Ti‐OH bonds. Under the simulated solar irradiation, the photocatalytic H2 evolution rate of CO‐TiO2 reaches 7.17 mmol g‐1 h‐1, which is 4.14 and 1.50 times those of TiO2 and H‐TiO2, respectively. The photocatalytic degradation rate constant of methyl orange on CO‐TiO2 is 2.45 and 6.39 times those on H‐TiO2 and TiO2. The superior photocatalytic activity of CO‐TiO2 is attributed to the effective separation and transfer of the photo‐generated electron‐hole pairs, due to the synergistic effects of oxygen vacancies and surface Ti‐OH bonds. This study reveals the relation between the photocatalytic property and structure, and provides a new method to prepare highly active TiO2 for H2 production and environmental treatment.

    更新日期:2018-06-05
  • Pt Nanostructures/N‐Doped Carbon hybrid, an Efficient Catalyst for Hydrogen Evolution/Oxidation Reactions: Enhancing its Base Media Activity through Bifunctionality of the Catalyst
    ChemSusChem (IF 7.226) Pub Date : 2018-06-04
    Sudip Barman; Manas Kundu; Tanmay Bhowmik; Ranjit Mishra

    Design and synthesis of active catalyst for HER/HOR are important for the development of hydrogen based renewable technologies. We report synthesis of Pt nanostructures‐N‐doped carbon hybrid (Pt‐(PtO2)‐NSs/C) for HER/HOR applications. The HER activity of this Pt‐(PtOx)‐NSs/C catalyst is 4 and 6.5 times better than commercial Pt/C in acid and base. The catalyst exhibits a current density of 10 mA/cm2 at overpotentials of 5 and 51 mV with tafel slopes of 29 and 64mV/dec in in 0.5 M H2SO4 and 0.5 M KOH. This catalyst also showed superior HOR activity at all pH values. The HER/HOR activity of Pt‐(PtOx)‐NSs/C and PtOx‐free Pt‐Nanostructures/C (PtNSs/C) catalysts are comparable in acid. The presence of PtOx in Pt‐(PtOx)‐NSs/C makes this Pt‐catalyst more HER/HOR active in base media. The activity of Pt‐(PtOx)NSs/C catalyst is 5 fold higher than that of PtNSs/C catalyst in basic medium although their activity is comparable in acid. Hydrogen binding energy and oxophilicity are the two equivalent descriptors for HER/HOR in basic media. We propose a bi‐functional mechanism for the enhanced alkaline HER/HOR activity of Pt(PtOx)‐NSs/C catalyst. In bi‐functional Pt‐(PtOx)‐NSs/C catalyst, PtOx provide an active site for OH‐ adsorption to form OHads which reacts with hydrogen intermediate (Hads), present at neighbouring Pt sites to form H2O leading to enhancement of HOR activity in basic medium This work may provide opportunity to develop catalysts for various renewable energy technologies.

    更新日期:2018-06-04
  • "Clicking" biobased polyphenols: A sustainable platform for aromatic polymeric materials
    ChemSusChem (IF 7.226) Pub Date : 2018-06-03
    Pietro Buono; Luc Averous; Antoine Duval; Youssef Habibi

    Lignin, tannins and cashew nut shell liquid are considered the main sources of aromatic based macromolecules. They represent an abundant alternative feedstock for the elaboration of aromatic chemicals and polymers, in view to replace some fossil‐based fractions. Located in different tissues of plants, these compounds with a large diversity and structural complexity are until now considered as by‐products derived from fractionation‐separation industrial processes with low added values. In the last decade, the use of the so‐called "click chemistry" as a tool for the synthesis of controlled macromolecular architectures has seen a large development in fundamental and applied research for a wide range of applications. It could represent a valid solution to overcome the main limitations encountered in the chemical modification of natural source of chemicals, with an environmentally friendly approach to create new substrates for the development of innovative polymers and materials. After a quick description of the main aromatic biopolymers, including the main extraction techniques along with their structure and their properties, this review article describes the chemical modifications which have been mainly focused on natural polyphenols aiming to the introduction of "clickable" groups, and its further use for the synthesis of bio‐based materials and additives. Special stress will be laid on several still unexplored chemical features which could contribute to further fundamental and applied materials science research.

    更新日期:2018-06-04
  • 更新日期:2018-06-03
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.
化学 • 材料 期刊列表