Strain-Induced Self-Assembly at Interface of Two-Dimensional Heterostructures Boosts CO2 Reduction to Methanol by H2O

Ming Cheng; Ning Cao; Zhi Wang; Ke Wang; Tiancheng Pu; Yukun Li; Tulai Sun; Xuanyu Yue; Wenkang Ni; Wenxin Dai; Yi He; Yao Shi; Peng Zhang; Yihan Zhu; Pengfei Xie

doi:10.1021/acsnano.4c00350

Strain-Induced Self-Assembly at Interface of Two-Dimensional Heterostructures Boosts CO₂ Reduction to Methanol by H₂O

ACS Nano. 2024 Apr 16;18(15):10582-10595. doi: 10.1021/acsnano.4c00350. Epub 2024 Apr 2.

Authors

Ming Cheng¹, Ning Cao¹, Zhi Wang², Ke Wang^{1

3}, Tiancheng Pu¹, Yukun Li⁴, Tulai Sun², Xuanyu Yue⁵, Wenkang Ni⁵, Wenxin Dai⁵, Yi He¹, Yao Shi¹, Peng Zhang⁴, Yihan Zhu², Pengfei Xie^{1

3

6}

Affiliations

¹ College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310058, China.
² Center for Electron Microscopy, Institute for Frontier and Interdisciplinary Sciences, State Key Laboratory Breeding Base of Green Chemistry Synthesis Technology and College of Chemical Engineering, Zhejiang University of Technology, Hangzhou, Zhejiang 310014, China.
³ Institute of Zhejiang University-Quzhou, Quzhou 324000, China.
⁴ State Center for International Cooperation on Designer Low-Carbon and Environmental Materials School of Materials, School of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450001, China.
⁵ Research Institute of Photocatalysis, State Key Laboratory of Photocatalysis on Energy and Environment, Fuzhou University, Fuzhou 350002, China.
⁶ State Key Laboratory of Baiyunobo Rare Earth Resource Researches and Comprehensive Utilization, Baotou Research Institute of Rare Earths, Baotou 014030, China.

PMID: 38564712
DOI: 10.1021/acsnano.4c00350

Abstract

CO₂ conversion with pure H₂O into CH₃OH and O₂ driven by solar energy can supply fuels and life-essential substances for extraterrestrial exploration. However, the effective production of CH₃OH is significantly challenging. Here we report an organozinc complex/MoS₂ heterostructure linked by well-defined zinc-sulfur covalent bonds derived by the structural deformation and intensive coupling of d_{x² - y²}(Zn)-p(S) orbitals at the interface, resulting in distinctive charge transfer behaviors and excellent redox capabilities as revealed by experimental characterizations and first-principle calculations. The synthesis strategy is further generalized to more organometallic compounds, achieving various heterostructures for CO₂ photoreduction. The optimal catalyst delivers a promising CH₃OH yield of 2.57 mmol g_cat^-1 h^-1 and selectivity of more than 99.5%. The reverse water gas shift mechanism is identified for methanol formation. Meanwhile, energy-unfavorable adsorption of methanol on MoS₂, where the photogenerated holes accumulate, ensures the selective oxidation of water over methanol.

Keywords: CO2 photoreduction; extraterrestrial synthesis; methanol; strong metal−support interactions; two-dimensional heterostructures.