429897 First-Principles Study of Hydrogen Production on ZnO Supported Single-Atom Catalysts

Thursday, November 12, 2015: 2:10 PM
355C (Salt Palace Convention Center)
Xiang-Kui Gu1, Botao Qiao1, Jingyue Liu2 and Wei-Xue Li1, (1)State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China, (2)Department of Physics, Arizona State University, Tempe, AZ

Single-atom catalysts have attracted considerable interests in heterogeneous catalysis recently. These single atoms generally stabilized by lattice oxygen of oxide supports or alkali metals with the benefits of highest atomic efficiency and structural simplicity. Moreover, their promising catalytic activity has been reported for CO oxidation and water gas shift reaction (WGSR). However, it is still an open question that how to rational design single-atom catalyst for a certain catalytic reaction. Here we report that design of ZnO supported single atoms for hydrogen production from methanol steam reforming (MSR) and WGSR via density functional theory (DFT) calculations combined with experimental study. We found that the single Pt1 and Au1 atoms stabilized by lattice oxygen of ZnO surface have significantly higher activity for MSR. It is revealed that the catalysis of these single precious metal atoms together with coordinated lattice oxygen stems from its stronger binding towards the intermediates, lower reaction barriers, changing on the reaction pathway. The measured turn-over-frequency of single Pt1 sites was more than 1000 times higher than the pristine ZnO. For WGSR on ZnO supported single transition metal atoms, we found that the activity of WGSR via favorable associative mechanism can be tuned by changing single atom. Based on microkinetic modeling analysis, a volcano-like relationship between calculated rates and binding energies of COOH intermediate was found. Among single transition metal atoms considered here, Ni1/ZnO has the highest activity of WGSR. These results provide valuable insights into the catalysis of the atomically dispersed metals on oxide supports.


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