Synthesis of a Triangle-Fused Six-Pointed Star and Its Electrocatalytic CO2 Reduction Activity

Guotao Wang; Zi-Xi Zhang; Hao Chen; Yingxue Fu; Kaisong Xiang; Ermeng Han; Tun Wu; Qixia Bai; Pei-Yang Su; Zhujiang Wang; Die Liu; Fenghua Shen; Hui Liu; Zhilong Jiang; Jie Yuan; Yiming Li; Pingshan Wang

doi:10.1021/acs.inorgchem.4c00550

Synthesis of a Triangle-Fused Six-Pointed Star and Its Electrocatalytic CO₂ Reduction Activity

Inorg Chem. 2024 Apr 22;63(16):7442-7454. doi: 10.1021/acs.inorgchem.4c00550. Epub 2024 Apr 12.

Authors

Guotao Wang^{1

2

3}, Zi-Xi Zhang⁴, Hao Chen^{1

2

3}, Yingxue Fu^{1

2

3}, Kaisong Xiang^{1

2

3}, Ermeng Han⁴, Tun Wu⁵, Qixia Bai⁵, Pei-Yang Su⁵, Zhujiang Wang^{1

2

3}, Die Liu⁴, Fenghua Shen^{1

2

3}, Hui Liu^{1

2

3}, Zhilong Jiang⁵, Jie Yuan⁶, Yiming Li⁴, Pingshan Wang^{4

5

3}

Affiliations

¹ School of Metallurgy and Environment, Central South University, Changsha, Hunan 410083, China.
² Chinese National Engineering Research Center for Control & Treatment of Heavy Metal Pollution, Changsha, Hunan 410083, China.
³ State Key Laboratory of Advanced Metallurgy for Non-ferrous Metals, Changsha, Hunan 410083, China.
⁴ Department of Organic and Polymer Chemistry and Hunan Key Laboratory of Micro & Nano Materials Interface Science, College of Chemistry and Chemical Engineering, Central South University, Changsha, Hunan 410083, China.
⁵ Institute of Environmental Research at Greater Bay Area, Key Laboratory for Water Quality and Conservation of the Pearl River Delta, Ministry of Education, Guangzhou Key Laboratory for Clean Energy and Materials, Guangzhou University, Guangzhou 510006, China.
⁶ School of Chemistry and Chemical Engineering, Henan Normal University Xinxiang, Xinxiang, Henan 453007, China.

PMID: 38606439
DOI: 10.1021/acs.inorgchem.4c00550

Abstract

As electrocatalysts, molecular catalysts with large aromatic systems (such as terpyridine, porphyrin, or phthalocyanine) have been widely applied in the CO₂ reduction reaction (CO₂RR). However, these monomeric catalysts tend to aggregate due to strong π-π interactions, resulting in limited accessibility of the active site. In light of these challenges, we present a novel strategy of active site isolation for enhancing the CO₂RR. Six Ru(Tpy)₂ were integrated into the skeleton of a metallo-organic supramolecule by stepwise self-assembly in order to form a rhombus-fused six-pointed star R1 with active site isolation. The turnover frequency (TOF) of R1 was as high as 10.73 s^-1 at -0.6 V versus reversible hydrogen electrode (vs RHE), which is the best reported value so far at the same potential to our knowledge. Furthermore, by increasing the connector density on R1's skeleton, a more stable triangle-fused six-pointed star T1 was successfully synthesized. T1 exhibits exceptional stability up to 126 h at -0.4 V vs RHE and excellent TOF values of CO. The strategy of active site isolation and connector density increment significantly enhanced the catalytic activity by increasing the exposure of the active site. This work provides a starting point for the design of molecular catalysts and facilitates the development of a new generation of catalysts with a high catalytic performance.