Catalytic Hydrogenation of CO2 to Methanol: Low Temperature and High Efficiency

Sulfur-deficient MoS₂ enables efficient CO₂-to-methanol conversion at low temperatures.

Efficient conversion of CO₂ is strategically significant for alleviating the energy crisis and achieving the goal of carbon neutrality. One promising conversion route is the hydrogenation of CO₂ to methanol using a renewable energy-based “green hydrogen” source.

Challenges with Traditional Catalysts

Traditional metal oxide catalysts for this reaction typically require a high temperature (>300 ^oC or 570 ^oF), which tends to promote undesired reverse water-gas shift (RWGS) side reactions, thus producing a large amount of CO as the by-product.

Introduction of transition metal components onto metal oxides can promote the activation of H₂, thereby reducing the reaction temperature, but this also facilitates excessive hydrogenation of CO₂ to CH₄, leading to lowered methanol selectivity. Further improvement of the performance of conventional metal/metal oxide catalysts for low-temperature CO₂ hydrogenation to methanol is severely restricted by the tradeoff between their activity and selectivity.

Recently, a group led by Prof. DENG Dehui from the Dalian Institute of Chemical Physics (DICP) of the Chinese Academy of Sciences (CAS), in collaboration with Prof. WANG Ye from Xiamen University, achieved for the first time low-temperature high-efficiency hydrogenation of CO₂ to methanol, with a long working life over sulfur vacancy-rich few-layered MoS₂, as well as remarkably higher activity and selectivity than those of the commercial Cu/ZnO/Al₂O₃ catalyst.

Their work which was published in Nature Catalysis, opens up a new way for the conversion of CO₂ with low energy consumption and high efficiency.

Superior Catalytic Performance and Stability

They found that the sulfur vacancy-rich few-layered MoS₂ could simultaneously activate and dissociate CO₂ and H₂ at low temperatures and even at room temperature, thereby facilitating the low-temperature hydrogenation of CO₂ to methanol with high activity and selectivity.

In addition, they found that the RWGS reaction and excessive hydrogenation of methanol to CH₄ were effectively suppressed. At 180 ^oC (450 ^oF), 94.3% methanol selectivity for a CO₂ conversion of 12.5% was achieved over the catalyst; this result was better than that obtained with the commercial Cu/ZnO/Al₂O₃ catalyst and previously reported catalysts.

The activity and selectivity were steadily maintained for over 3000 hours over the MoS₂ catalyst, rendering it a promising candidate for industrial applications. In situ characterizations combined with theoretical calculations demonstrated that the in-plane sulfur vacancies on MoS₂ were the active centers for catalyzing the highly selective hydrogenation of CO₂ to methanol.

“This work reveals the potential of in-plane vacancies in two-dimensional materials for catalysis and provides a novel strategy for the development of new catalysts to be used in CO₂ hydrogenation,” said Prof. DENG.

Reference: “Sulfur vacancy-rich MoS₂ as a catalyst for the hydrogenation of CO₂ to methanol” by Jingting Hu, Liang Yu, Jiao Deng, Yong Wang, Kang Cheng, Chao Ma, Qinghong Zhang, Wu Wen, Shengsheng Yu, Yang Pan, Jiuzhong Yang, Hao Ma, Fei Qi, Yongke Wang, Yanping Zheng, Mingshu Chen, Rui Huang, Shuhong Zhang, Zhenchao Zhao, Jun Mao, Xiangyu Meng, Qinqin Ji, Guangjin Hou, Xiuwen Han, Xinhe Bao, Ye Wang & Dehui Deng, 22 March 2021, Nature Catalysis.
DOI: 10.1038/s41929-021-00584-3

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