Facilitating Hydrogen Dissociation over Dilute Nanoporous Ti–Cu Catalysts

Lee, Jennifer D.; Qi, Zhen; Foucher, Alexandre C.; Ngan, Hio Tong; Dennis, Kevin; Cui, Jun; Sadykov, Ilia I.; Crumlin, Ethan J.; Sautet, Philippe; Stach, Eric A.; Friend, Cynthia M.; Madix, Robert J.; Biener, Juergen

doi:10.1021/jacs.2c00830

Facilitating Hydrogen Dissociation over Dilute Nanoporous Ti–Cu Catalysts

Journal Article · Fri Sep 02 00:00:00 EDT 2022 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.2c00830· OSTI ID:1903746

^[1]; ^[2]; ^[3]; Ngan, Hio Tong ^[4]; Dennis, Kevin ^[5]; Cui, Jun ^[5]; ^[6]; ^[7]; ^[4]; ^[3]; ^[8]; ^[8]; ^[2]

Harvard Univ., Cambridge, MA (United States); Harvard
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Univ. of Pennsylvania, Philadelphia, PA (United States)
Univ. of California, Los Angeles, CA (United States)
Ames Lab., Ames, IA (United States)
Paul Scherrer Inst. (PSI), Villigen (Switzerland)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Harvard Univ., Cambridge, MA (United States)

The dissociation of H₂ is an essential elementary step in many industrial chemical transformations, typically requiring precious metals. Here, we report a hierarchical nanoporous Cu catalyst doped with small amounts of Ti (npTiCu) that increases the rate of H₂–D₂ exchange by approximately one order of magnitude compared to the undoped nanoporous Cu (npCu) catalyst. The promotional effect of Ti was measured via steady-state H₂–D₂ exchange reaction experiments under atmospheric pressure flow conditions in the temperature range of 300–573 K. Pretreatment with flowing H₂ is required for stable catalytic performance, and two temperatures, 523 and 673 K, were investigated. The experimentally determined H₂–D₂ exchange rate is 5–7 times greater for npTiCu vs the undoped Cu material under optimized pretreatment and reaction temperatures. The H₂ pretreatment leads to full reduction of Cu oxide and partial reduction of surface Ti oxide species present in the as-prepared catalyst as demonstrated using in situ ambient pressure X-ray photoelectron spectroscopy and X-ray absorption spectroscopy. The apparent activation energies and pre-exponential factors measured for H₂–D₂ exchange are substantially different for Ti-doped vs undoped npCu catalysts. Density functional theory calculations suggest that isolated, metallic Ti atoms on the surface of the Cu host can act as the active surface sites for hydrogen recombination. Furthermore, the increase in the rate of exchange above that of pure Cu is caused primarily by a shift in the rate-determining step from dissociative adsorption on Cu to H/D atom recombination on Ti-doped Cu, with the corresponding decrease in activation entropy that it produces.

View Accepted Manuscript (DOE)

Research Organization:: Harvard Univ., Cambridge, MA (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231; AC52-07NA27344; SC0012573

OSTI ID:: 1903746

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 37 Vol. 144; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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