Significant Roles of Surface Hydrides in Enhancing the Performance of Cu/BaTiO 2.8 H 0.2 Catalyst for CO 2 Hydrogenation to Methanol

He, Yang; Li, Yuanyuan; Lei, Ming; Polo‐Garzon, Felipe; Perez‐Aguilar, Jorge; Bare, Simon R.; Formo, Eric; Kim, Hwangsun; Daemen, Luke; Cheng, Yongqiang; Hong, Kunlun; Chi, Miaofang; Jiang, De‐en; Wu, Zili

doi:10.1002/ange.202313389

Title: Significant Roles of Surface Hydrides in Enhancing the Performance of Cu/BaTiO _2.8 H _0.2 Catalyst for CO ₂ Hydrogenation to Methanol

Journal Article · 12 November 2023 · Angewandte Chemie

DOI: https://doi.org/10.1002/ange.202313389 · OSTI ID:2274848

He, Yang ^[1]; Li, Yuanyuan ^[1]; Lei, Ming ^[2]; Polo‐Garzon, Felipe ^[1]; Perez‐Aguilar, Jorge ^[3]; Bare, Simon R. ^[3]; Formo, Eric ^[4]; Kim, Hwangsun ^[5]; Daemen, Luke ^[6]; Cheng, Yongqiang ^[6]; Hong, Kunlun ^[5]; Chi, Miaofang ^[5]; Jiang, De‐en ^[2];

^[1]

Chemical Sciences Division and Center for Nanophase Materials Sciences Oak Ridge National Laboratory Oak Ridge TN-37831 USA
Department of Chemical and Biomolecular Engineering Vanderbilt University Nashville TN-37235 USA
Stanford Synchrotron Radiation Lightsource SLAC National Accelerator Laboratory 2575 Sand Hill Road Menlo Park CA-94025 USA
Georgia Electron Microscopy University of Georgia Athens GA-30602 USA
Center for Nanophase Materials Sciences Oak Ridge National Laboratory Oak Ridge TN-37831 USA
Neutron Scattering Division Oak Ridge National Laboratory Oak Ridge TN-37831 USA

Abstract Tuning the anionic site of catalyst supports can impact reaction pathways by creating active sites on the support or influencing metal‐support interactions when using supported metal nanoparticles. This study focuses on CO ₂ hydrogenation over supported Cu nanoparticles, revealing a 3‐fold increase in methanol yield when replacing oxygen anions with hydrides in the perovskite support (Cu/BaTiO _2.8 H _0.2 yields ~146 mg/h/gCu vs. Cu/BaTiO ₃ yields ~50 mg/h/gCu). The contrast suggests that significant roles are played by the support hydrides in the reaction. Temperature programmed reaction and isotopic labelling studies indicate that BaTiO _2.8 H _0.2 surface hydride species follow a Mars van Krevelen mechanism in CO ₂ hydrogenation, promoting methanol production. High‐pressure steady‐state isotopic transient kinetic analysis (SSITKA) studies suggest that Cu/BaTiO _2.8 H _0.2 possesses both a higher density and more active and selective sites for methanol production compared to Cu/BaTiO ₃ . An operando high‐pressure diffuse reflectance infrared spectroscopy (DRIFTS)‐SSITKA study shows that formate species are the major surface intermediates over both catalysts, and the subsequent hydrogenation steps of formate are likely rate‐limiting. However, the catalytic reactivity of Cu/BaTiO _2.8 H _0.2 towards the formate species is much higher than Cu/BaTiO ₃ , likely due to the altered electronic structure of interface Cu sites by the hydrides in the support as validated by density functional theory (DFT) calculations.

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Sponsoring Organization:: USDOE

OSTI ID:: 2274848

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 1 Vol. 136; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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Title: Significant Roles of Surface Hydrides in Enhancing the Performance of Cu/BaTiO _2.8 H _0.2 Catalyst for CO ₂ Hydrogenation to Methanol