MOF-Templated Sulfurization of Atomically Dispersed Manganese Catalysts Facilitating Electroreduction of CO2to CO
Journal
ACS Applied Materials and Interfaces
Journal Volume
13
Journal Issue
44
Pages
52134-52143
Date Issued
2021
Author(s)
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 (MnSA/SNC) is identified as MnN3S1. Compared with its non-sulfur-modified counterpart (MnSA/NC), the MnSA/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 MnSA/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. ? 2021 American Chemical Society.
Subjects
eCO2RR
metal-organic framework
operando spectroscopy
single-atom catalysts
sulfurization
XAS
Atoms
Carbon dioxide
Catalysts
Electrolytic reduction
Manganese
Metal-Organic Frameworks
Organometallics
Sulfur
Central metals
Characterization techniques
Electroreduction of CO2
Energy systems
Faradaic efficiencies
Metalorganic frameworks (MOFs)
Potential materials
Spectroscopic characterization
Manganese compounds
Type
journal article