金属氧化物担载双金属催化剂的制备、结构及其对乙醇重整的性能研究

Steam reforming of bioethanol to produce hydrogen for fuel cell is an important way in energy framework, which has several advantages, such as environmental friend, high efficiency and can avoid separating water from the bioethanol. The critical technique of steam reforming of bioethanol is to develop durable and active catalyst. For developing catalyst, the key challenge is the deactivation of the catalysts due to carbon deposition and sintering of the active components. We proposed in this application a new scheme to overcome the problem of the deactivation. Two kinds of new catalysts were designed based on the following considerations:.(1)Perovskite-type oxide (PTO) and the solid solution of ceria-based oxide can form oxygen vacancies on their surface and in their bulk, which faviours the elimination of the deposited carbon; both of the two type oxides tend to interact with the metal species supported on them, which is beneficial for anti-sintering of the supported metal species; bimetal nano particles can eliminate the deposited carbon via synergy of them and can improve its anti-sintering ability by tailoring its structure and the interaction with its support..(2)Most of metal ions can be served as the crystalline ions of PTO, which means that most of metal ions can be dispersed in PTO lattice or on PTO suface evenly at atomic level. The so evenly mixed metal ions can be readly reduced to metal alloy, and the structure of the metal alloy can be adjusted by adjusting the reduction conditions..Thus, in this proposal, the study will concentrate on the catalysts of bimetal/PTO and bimetal/ceria-based oxide for ethanol steam reforming, in which the bimetal will be derived from conditioned reduction of PTO. Study on tailoring the structure of the bimetal with catalyst preparing and reduction, study on the relation between the structure of the bimetal nano particles and the catalytic performance, emphasized on anti-carbon deposition and anti-sintering..This is a novel method with potentially extensive application areas for the preparation of bimetal nano particles supported on metal oxide materials..Rare earth is a characteristic resource of Inner Mongolia, this project study rare earth catlyst oriented to the resource of Inner Mongolia.

生物乙醇重整制氢供给燃料电池，具有环境友好、效率高、避免醇水分离等优点，其中制氢的技术核心是催化剂，催化剂面临的核心问题是积碳和烧结失活。本项目对此问题提出了新的解决对策，学术思想：（1）钙钛矿型稀土复合氧化物（PTO）和铈基氧化物均易形成氧空位，这利于消积碳；这两种复合氧化物均易与金属组分形成相互作用，可抗烧结；双金属组分既可通过协同作用改善消积碳，又可能通过对其结构和与载体相互作用的调节改善其抗烧结性能。（2）大部分金属离子可以进入PTO晶格形成复合氧化物，这意味着大部分金属离子可以原子水平地均匀分散于PTO晶格中或高分散于PTO表面，这样高度均匀混合的金属离子被还原后容易形成合金，而且合金的结构可以通过还原过程的控制来调控。本项目拟研究双金属/PTO和双金属/铈基氧化物催化剂，用于乙醇重整，其中双金属从PTO还原得到。学术角度，这是纳米双金属/氧化物体系的一种新型制备方法，拓展面很宽

积碳和烧结失活是碳氢化合物转化催化剂共同面临的一个关键问题，本项目针对此问题提出了新的解决思想：（1）钙钛矿型稀土复合氧化物（PTO）和铈基氧化物均易形成氧空位，这利于消积碳；这两种复合氧化物均易与金属组分形成相互作用，可抗烧结；双金属组分既可通过协同作用改善消积碳，又可能通过对其结构和与载体相互作用的调节改善其抗烧结性能。（2）大部分金属离子可以进入PTO晶格形成复合氧化物，这意味着大部分金属离子可以原子水平地均匀分散于PTO晶格中或高分散于PTO表面，这样高度均匀混合的金属离子被还原后容易形成合金，而且合金的结构可以通过还原过程的控制来调控。基于此思路研究了以PTO为前驱体制备纳米双金属催化剂以及铈基氧化物担载的纳米金属催化剂，用于乙醇重整以及合成气制低碳醇等反应。所研究催化剂的活性组分包括Cu-Co、Cu-Ni或Ni-Co，以及核壳结构双金属Cu@Co和Co@Cu等，载体有LaFeO3、ZrO2、Al2O3、SiO2、La2O3、CeO2等，提出了一种制备纳米双金属的新方法，研发出了有应用潜力的新型催化剂。发表标注本基金资助的SCI收录论文12篇，申请专利2项。