期刊
ACS CATALYSIS
卷 10, 期 16, 页码 9098-9108出版社
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.0c02320
关键词
monoclinic ZrO2; tetragonal ZrO2; metal-support interface; fatty acid hydrogenation; methanol reforming; carrier crystal
资金
- National Natural Science Foundation of China [21978259, 21706228]
- Zhejiang Provincial Natural Science Foundation of China [LR17B060002]
- Fundamental Research Funds for the Central Universities
The catalytic transformation of renewable fatty acids into value-added fatty alcohols without the use of gaseous hydrogen is a versatile technique for the utilization of microalgae and waste cooking oil, where Cu-based catalysts are considered to be the most suitable candidate. However, the interpretation of the structure-reactivity relationship caused by different crystal types of carriers and the metal-support interface is not well understood. Herein we synthesized ZrO2 -supported Cu nanoparticle catalysts via different preparation methods and reduction temperatures under similarly exposed surface facets and Cu valency but different polymorphic phases of ZrO2 (monoclinic ZrO2: m-ZrO2; tetragonal ZrO2: t-ZrO2) and the metal-support interface. Interestingly, the as-synthesized Cu/t-ZrO2 catalysts showed remarkably better catalytic performance than Cu/m-ZrO2 for the in situ hydrogenation of lauric acid in the methanol-water system. Combined experimental and density functional theory (DFT) calculation results ascribed the lower efficiency of m-ZrO2 as a carrier to weakly adsorbed reactant and intermediate molecules as well as the absence of an oxygen vacancy in the crystal phase. The interface-rich Cu/t-ZrO2 catalysts displayed higher activity normalized to the surface-exposed Cu sites toward lauryl alcohol production than the interface-deficient counterparts. DFT calculation results further revealed that this metal-support interface plays an important role in promoting the C-O bond or H-H bond cleavage in two possible reaction routes, thus reducing the activation barrier of the overall reaction.
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