Hydrogen Spillover Is Regulating Minority Rh1 Active Sites on TiO2 in Room-Temperature Ethylene Hydrogenation

Chen, Linxiao; Meira, Debora; Kovarik, Libor; Szanyi, János

doi:10.1021/acscatal.4c00482

Title: Hydrogen Spillover Is Regulating Minority Rh₁ Active Sites on TiO₂ in Room-Temperature Ethylene Hydrogenation

Journal Article · 26 April 2024 · ACS Catalysis

DOI: https://doi.org/10.1021/acscatal.4c00482 · OSTI ID:2446688

^[1];

^[2]; Kovarik, Libor ^[3];

^[3]

Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Univ. of Akron, OH (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Univ. of Saskatchewan, Saskatoon, SK (Canada). Canadian Light Source, Inc.
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Institute for Integrated Catalysis

The complicated dynamics of active sites on single-atom catalysts under reducing conditions limits their applications in hydrogenation reactions and mechanistic understanding. Herein, we report that on Rh₁/TiO₂, *H spillover during room-temperature ethylene hydrogenation hydroxylates and reduces TiO₂, enhancing the intrinsic activity of Rh₁ by 9-fold. Spectroscopic and kinetic evidence suggests that the spillover of *H is suppressed by their facile reaction with C₂H₄, most of the spilled *H are nonreactive spectators, and >99% turnovers occur on a small subset (<20%) of exposed “active Rh₁”. Steady-state kinetics indicates competitive adsorption between H and C₂H₄, H₂ dissociation is the rate-determining step, and the apparent activation barrier (E_a,app) of the reaction is ~48 kJ/mol. The evolution of Rh₁ under H₂ was further tracked by spectroscopic and microscopic techniques at elevated temperatures. At 200 °C, more Rh₁ are exposed, but these Rh₁ are at least 5-fold less active than that of the “active Rh₁”. At 300 °C, Rh clusters derived from Rh₁ become the main active sites, shifting E_a,app to 62 kJ/mol, characteristic of Rh nanoparticles. At ≥400 °C, larger and more active Rh particles in the strong metal–support interaction state are created. In conclusion, this work revealed the unexpected regulation effects of *H spillover on M₁ active sites under ambient conditions, differentiated the minority active M₁ sites, and demonstrated how the stability of M₁ under reducing atmospheres affects hydrogenation catalysis.

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC05-76RL01830; AC02-06CH11357

OSTI ID:: 2446688

Report Number(s):: PNNL-SA--191971

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 10 Vol. 14; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
hydrogen spillover
hydrogenation
rhodium
single-atom catalysis
titania

Title: Hydrogen Spillover Is Regulating Minority Rh1 Active Sites on TiO2 in Room-Temperature Ethylene Hydrogenation

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Title: Hydrogen Spillover Is Regulating Minority Rh₁ Active Sites on TiO₂ in Room-Temperature Ethylene Hydrogenation