Engineering nanoscale H supply chain to accelerate methanol synthesis on ZnZrOx

Kyungho Lee; Paulo C D Mendes; Hyungmin Jeon; Yizhen Song; Maxim Park Dickieson; Uzma Anjum; Luwei Chen; Tsung-Cheng Yang; Chia-Min Yang; Minkee Choi; Sergey M Kozlov; Ning Yan

doi:10.1038/s41467-023-36407-1

Engineering nanoscale H supply chain to accelerate methanol synthesis on ZnZrO_x

Nat Commun. 2023 Feb 13;14(1):819. doi: 10.1038/s41467-023-36407-1.

Authors

Affiliations

¹ Department of Chemical and Biomolecular Engineering, National University of Singapore, 4 Engineering Drive 4, Singapore, 117585, Singapore.
² Department of Chemical and Biomolecular Engineering, KAIST, Daejeon, 34141, Republic of Korea.
³ Institute of Sustainability for Chemical, Energy and Environment, Agency for Science, Technology and Research (A*STAR), Singapore, 627833, Singapore.
⁴ Department of Chemistry, National Tsing Hua University, Hsinchu, 300044, Taiwan.
⁵ Frontier Research Center on Fundamental and Applied Sciences of Matters, National Tsing Hua University, Hsinchu, 300044, Taiwan.
⁶ Department of Chemical and Biomolecular Engineering, National University of Singapore, 4 Engineering Drive 4, Singapore, 117585, Singapore. cheserg@nus.edu.sg.
⁷ Department of Chemical and Biomolecular Engineering, National University of Singapore, 4 Engineering Drive 4, Singapore, 117585, Singapore. ning.yan@nus.edu.sg.

Abstract

Metal promotion is the most widely adopted strategy for enhancing the hydrogenation functionality of an oxide catalyst. Typically, metal nanoparticles or dopants are located directly on the catalyst surface to create interfacial synergy with active sites on the oxide, but the enhancement effect may be compromised by insufficient hydrogen delivery to these sites. Here, we introduce a strategy to promote a ZnZrO_x methanol synthesis catalyst by incorporating hydrogen activation and delivery functions through optimized integration of ZnZrO_x and Pd supported on carbon nanotube (Pd/CNT). The CNT in the Pd/CNT + ZnZrO_x system delivers hydrogen activated on Pd to a broad area on the ZnZrO_x surface, with an enhancement factor of 10 compared to the conventional Pd-promoted ZnZrO_x catalyst, which only transfers hydrogen to Pd-adjacent sites. In CO₂ hydrogenation to methanol, Pd/CNT + ZnZrO_x exhibits drastically boosted activity-the highest among reported ZnZrO_x-based catalysts-and excellent stability over 600 h on stream test, showing potential for practical implementation.