铜纳米颗粒催化剂的重构及其合成碳酸二甲酯性能研究  

Reconstruction of copper nanoparticles catalysts and its catalytic performance for synthesis of dimethyl carbonate

作　　者：裴永丽 权燕红[2,3,4] 任军 PEI Yongli;QUAN Yanhong;REN Jun(Department of Energy Chemistry and Materials Engineering,Shanxi Institute of Energy,Jinzhong 030600,China;State Key Laboratory of Clean and Efficient Coal Utilization,Taiyuan University of Technology,Taiyuan 030024,China;College of Chemical Engineering and Technology(Taiyuan University of Technology),Taiyuan 030024,China;Shanxi Research Institute for Clean Energy Tsinghua University,Taiyuan 030024,China)

机构地区：[1]山西能源学院能源化学与材料工程系,山西晋中030600 [2]太原理工大学省部共建煤基能源清洁高效利用国家重点实验室,山西太原030024 [3]太原理工大学化学工程与技术学院,山西太原030024 [4]清华大学山西清洁能源研究院,山西太原030024

出　　处：《燃料化学学报（中英文）》2024年第3期335-342,共8页Journal of Fuel Chemistry and Technology

基　　金：山西省基础研究计划(202203021222330)资助。

摘　　要：甲醇氧化羰基化合成碳酸二甲酯(DMC)是中国重点开发的现代煤化工路线,其关键在于高性能催化剂的设计研发。本研究采用液相重构法,通过调变溶剂种类、气氛和压力制得高效铜团簇催化剂,在DMC合成反应中时空收率(STY_(DMC))高达3520 mg/(g·h),经过10次循环,STY_(DMC)下降21.8%。N2吸附-脱附、XRD、TEM、STEM等表征手段表明,强还原性的CO不但可使铜纳米颗粒(~9.7 nm)部分重构为亚纳米团簇(~1.34 nm),同时有效维持了Cu^(0)物种的存在,从而提升了催化活性和稳定性。进一步研究表明,铜重构的发生取决于气氛-金属-载体三者的相互作用,且随氧化、还原性气氛的变化呈可逆状态。Dimethyl carbonate(DMC)is an important and environmentally friendly chemical intermediate to meet the growing demand for a clean and sustainable energy supply.Among several routes for DMC synthesis,the oxidative carbonylation of methanol has attracted much attention with the advantages of a high utilization rate of carbon source,moderate operating conditions and environmental benefits.More importantly,the oxidative carbonylation of methanol is an important development route of modern coal chemical industry in China,and the key lies in the design of highly efficient catalysts.Copper-based catalysts have been used extensively in this reaction.Problems,such as reactor corrosion and catalyst deactivation,occur with chlorine-containing catalysts.The development of chlorine-free catalysts is the focus of current research.Recently,Cu-based catalysts supported on carbon materials have been used extensively in DMC synthesis because of its high activity,high selectivity and facile preparation process.However,the carbon-supported Cu catalysts suffer from the leaching and aggregation of Cu nanoparticles(NPs)in the harsh reaction conditions of high temperature,high pressure as well as severe stirring,leading to the deactivation.It has become a key scienctific problem that needs to be addressed urgently.In our previous studies,several strategies have been attempted to solve the deactivation problem caused by these reasons.For instance,encapsulating Cu NPs with hollow porous carbon spheres or mesoporous carbon materials.Besides,the introduction of N species in the carbon framework or sulfonic acid groups and oxygen-containing groups on the surface of carbon materials leads to an anchoring effect on Cu NPs.Great progress has been made via these methods,yet still unsatisfactory.Supported metal clusters have adjacent metal sites,countable numbers of atoms in each clusters,and limited size range(normally smaller than 2 nm).Benefiting from these distinct geometric and electronic structures,supported metal clusters can trigger synerg

关 键 词：碳酸二甲酯 铜团簇 液相重构 高活性和稳定性 

分 类 号：O643[理学—物理化学]