MOF-Templated Sulfurization of Atomically Dispersed Manganese Catalysts Facilitating Electroreduction of CO2 to CO

Hui-Ying Tan; Sheng-Chih Lin; Jiali Wang; Chia-Jui Chang; Shu-Chih Haw; Kuo-Hsin Lin; Li Duan Tsai; Hsiao-Chien Chen; Hao Ming Chen

doi:10.1021/acsami.1c10059

MOF-Templated Sulfurization of Atomically Dispersed Manganese Catalysts Facilitating Electroreduction of CO₂ to CO

ACS Appl Mater Interfaces. 2021 Nov 10;13(44):52134-52143. doi: 10.1021/acsami.1c10059. Epub 2021 Jul 14.

Authors

Hui-Ying Tan¹, Sheng-Chih Lin¹, Jiali Wang¹, Chia-Jui Chang¹, Shu-Chih Haw², Kuo-Hsin Lin³, Li Duan Tsai³, Hsiao-Chien Chen^{4

5}, Hao Ming Chen^{1

2}

Affiliations

¹ Department of Chemistry, National Taiwan University, Taipei 10617, Taiwan.
² National Synchrotron Radiation Research Center, Hsinchu 30076, Taiwan.
³ Material and Chemical Research Laboratories, Industrial Technology Research Institute, Chutung, Hsinchu 31040, Taiwan.
⁴ Center for Reliability Sciences and Technologies, Chang Gung University, Taoyuan 333, Taiwan.
⁵ Kidney Research Center, Department of Nephrology, Linkou Chang Gung Memorial Hospital, Taoyuan 333, Taiwan.

PMID: 34258990
DOI: 10.1021/acsami.1c10059

Abstract

To reach a carbon-neutral future, electrochemical CO₂ reduction reaction (eCO₂RR) has proven to be a strong candidate for the next-generation energy system. Among potential materials, single-atom catalysts (SACs) serve as a model to study the mechanism behind the reduction of CO₂ to CO, given their well-defined active metal centers and structural simplicity. Moreover, using metal-organic frameworks (MOFs) as supports to anchor and stabilize central metal atoms, the common concern, metal aggregation, for SACs can be addressed well. Furthermore, with their turnability and designability, MOF-derived SACs can also extend the scope of research on SACs for the eCO₂RR. Herein, we synthesize sulfurized MOF-derived Mn SACs to study effects of the S dopant on the eCO₂RR. Using complementary characterization techniques, the metal moiety of the sulfurized MOF-derived Mn SACs (Mn_SA/SNC) is identified as MnN₃S₁. Compared with its non-sulfur-modified counterpart (Mn_SA/NC), the Mn_SA/SNC provides uniformly superior activity to produce CO. Specifically, a nearly 30% enhancement of Faradaic efficiency (F.E.) in CO production is observed, and the highest F.E. of approximately 70% is identified at -0.45 V. Through operando spectroscopic characterization, the probing results reveal that the overall enhancement of CO production on the Mn_SA/SNC is possibly caused by the S atom in the local MnN₃S₁ moiety, as the sulfur atom may induce the formation of S-O bonding to stabilize the critical intermediate, *COOH, for CO₂-to-CO. Our results provide novel design insights into the field of SACs for the eCO₂RR.

Keywords: XAS; eCO2RR; metal−organic framework; operando spectroscopy; single-atom catalysts; sulfurization.

Publication types

Review