Co2FeO4@rGO composite: Towards trifunctional water splitting in alkaline media

Development of efficient, low cost and multifunctional electrocatalysts for water splitting to harvest hydrogen fuels is a challenging task, but the combination of carbon materials with transition metal-based compounds is providing a unique and attractive strategy. Herein, composite systems based on cobalt ferrite oxide-reduced graphene oxide (Co₂FeO₄) @(rGO) using simultaneous hydrothermal and chemical reduction methods have been prepared. The proposed study eliminates one step associated with the conversion of GO into rGO as it uses direct GO during the synthesis of cobalt ferrite oxide, consequently rGO based hybrid system is achieved in-situ significantly, the optimized Co₂FeO₄@rGO composite has revealed an outstanding multifunctional applications related to both oxygen evolution reaction (OER) and hydrogen counterpart (HER). Various metal oxidation states and oxygen vacancies at the surface of Co₂FeO₄@rGO composites guided the multifunctional surface properties. The optimized Co₂FeO₄@rGO composite presents excellent multifunctional properties with onset potential of 0.60 V for ORR, an overpotential of 240 mV at a 20 mAcm^?2 for OER and 320 mV at a 10 mAcm^?2 for HER respectively. Results revealed that these multifunctional properties of the optimized Co₂FeO₄@ rGO composite are associated with high electrical conductivity, high density of active sites, crystal defects, oxygen vacancies, and favorable electronic structure arisinng from the substitution of Fe for Co atoms in binary spinel oxide phase. These surface features synergistically uplifted the electrocatalytic properties of Co₂FeO₄@rGO composites. The multifunctional properties of the Co₂FeO₄@ rGO composite could be of high interest for its use in a wide range of applications in sustainable and renewable energy fields.     

氮杂冠醚合成中的双功能基试剂

综述了氮杂冠醚合成中的双功能基试剂的进展。着重讨论了典型的双功能基试剂,如取代多甘醇、二胺、氨基二醇、二卤代物、二醛和二酮以及3-烷氧丙烯醛等的制备方法。     

Synthesis of p‐aminophenol from the hydrogenation of nitrobenzene over metal–solid acid bifunctional catalyst

BACKGROUND: A single‐step conversion of nitrobenzene (NB) to p‐aminophenol (PAP) through catalytic hydrogenation is a widely used synthesis route for PAP. The main shortcoming of this route is the use of sulfuric acid for rearrangement of the phenylhydroxylamine (PHA) intermediate. In this paper, S₂O₈^2?/ZrO₂ (PSZ) solid acid and Pt‐S₂O₈^2?/ZrO₂ (Pt‐PSZ) bifunctional catalysts were prepared for the synthesis of PAP in non‐acid medium. RESULTS: Calcination temperature has a substantial effect on the acidity, structure and activity for PHA rearrangement of PSZ. The highest PAP yield was 33.8% over PSZ calcined at 823 K when the reaction was carried out in water at 423 K. A high PAP yield of 23.9% was achieved by a single‐step reaction of nitrobenzene over Pt‐PSZ bifunctional catalysts. CONCLUSION: PSZ solid acid exhibits high activity for PHA rearrangement. Perfect tetragonal ZrO₂ and much stronger acid sites play important roles in catalytic activity. Inhibiting the hydrogenation activity by reducing the amount of Pt loading on Pt‐PSZ can improve the competition of PHA rearrangement on acid sites with hydrogenation of PHA on metal active sites, resulting in better selectivity to PAP. Copyright © 2008 Society of Chemical Industry     

H2-O2气氛中丙烯环氧化反应研究进展

对H2-O2气氛中丙烯环氧化反应所采用的催化剂、反应器及操作方式进行了评述.综合分析了所使用的钯(金或银)/钛硅分子筛(或氧化钛)双功能催化剂的各项性能指标以及所采用的反应器型式.结合H2-O2直接合成H2O2所用催化剂,对原位氧化丙烯反应过程进行了系统描述.指出进一步的研究方向是借助反应或分离耦合技术,创造有利于原位生成的H2O2及时进行环氧化而避免分解的操作环境,包括催化剂表面状态、反应器型式、溶剂体系和操作方式,并提出以丙烷路线经脱氢、环氧化是制取环氧丙烷的最佳组合.     

双活性基活性染料真丝绸染色工艺研究

双活性基活性染料用于真丝绸染色有诸多影响因素：缚酸剂用碳酸氢钠比碳酸钠的固色率高用量在2％～4％，pH为8～9时最为合适：染色温度从60℃升到85℃时固色率提高3％～8％，超过85℃时易造成“灰伤”．当元明粉的用量从30g／l升到60g／l时上染率和固色率提高10％。随着浴比的增加，其固色率会有不同程度的降低，在实验条件下，浴比为1：40最好。通过上染曲线，讨论了染色过程的控制。     

Enhancement of the electrooxidation of ethanol on a Pt–PEM electrode modified by tin. Part I: Half cell study

The direct platinisation of a solid polymer electrolyte (Nafion^® membrane) was realized by chemical reduction of a platinum salt. The Pt–PEM electrodes thus obtained were modified by tin to improve the electrocatalytic activity towards the electrooxidation of ethanol. The Pt–PEM and Pt–Sn–PEM electrodes were characterized by TEM, EDX and XRD analysis, cyclic voltammetry, and their polarisation curves for the electrooxidation of ethanol were determined under quasisteady state conditions.     

A study of PtRuO2 catalysts thermally formed on titanium mesh for methanol oxidation

Platinum-based catalysts, for the electro-oxidation of methanol, have been made by thermal decomposition of chloride precursors onto titanium mesh. The catalysed electrodes were successfully operated in acidic methanol electrolytes. Electrochemical characterisation has been carried out using cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic polarisations. A complete analysis of the electrochemical results showed that the preliminary performance of the catalysed titanium mesh was comparable to that achieved with carbon-supported PtRu catalysts. The catalysts formed on titanium mesh by thermal decomposition also exhibited dimensional stability. Catalysed titanium mesh therefore appears to be a promising alternative to carbon-supported catalysts for certain fuel cell applications.     

低CO2选择性的合成气制轻烯烃双功能催化剂

为开发高活性、高收率的合成气制低碳烯烃（STO）双功能催化剂，通过共沉淀法制备非化学计量尖晶石Zn-Cr-Al氧化物，对其织构性质、晶体结构、形貌特征以及表面电荷性质等进行研究。结果表明添加过量锌能够促进晶体粒径减小，表面氧空位增多。其中Zn/(Cr+Al)摩尔比为1.25时锌含量较为适宜，将其与SAPO-34沸石分子筛结合为双功能催化剂用于STO性能研究。在进气n(H2):n(CO)=2:1，3000 mL/(gcat·h)，3.2 MPa，400 ℃反应条件下，实现46.9% CO转化率，C2-4烯烃收率高达15.9%，高于大部分已有文献报道（8~14%），特别是副产物CO2选择性仅29.2%，低于普遍报道的40~50% CO2选择性。并且催化剂运行100 h后活性良好，稳定的催化性能使其具有工业应用价值。     

Roles of interaction between components in CZZA/HZSM-5 catalyst for dimethyl ether synthesis via CO2 hydrogenation

The roles of interaction between two catalyst components in CuO–ZnO–ZrO₂–Al₂O₃ (CZZA)/HZSM-5 bifunctional catalyst for dimethyl ether (DME) synthesis via carbon dioxide hydrogenation were investigated. It was found that CZZA catalyst showed excellent stability during methanol (MeOH) synthesis for 100 h, while there was a severe loss of catalytic activity in the bifunctional catalyst for DME synthesis. Hence, the effects of different degrees of intimacy of two catalyst components were studied for DME synthesis, including mixed and separated modes. For the mixed mode, the particle size of catalysts and the amount of reaction intermediates were proven to influence the catalyst deactivation. For the separated mode, the catalysts showed rapid deactivation within a short time. Various characterizations indicated that the remarkable deactivation of separated mode was mainly caused by the decrease of copper active centers (e.g., sintering and oxidation) and blockage of acid sites via increased coke deposition on HZSM-5.