Single‐Atom Electrocatalysts from Multivariate Metal–Organic Frameworks for Highly Selective Reduction of CO₂ at Low Pressures

Abstract

Single-atom catalysts (SACs) are of great interest because of their ultrahigh activity and selectivity.However,itis difficult to construct model SACs according to ag eneral synthetic method, and therefore,d iscerning differences in activity of diverse single-atom catalysts is not straightforward. Herein, ag eneral strategy for synthesis of single-atom metals implanted in N-doped carbon (M 1-N-C;M= Fe,C o, Ni and Cu) has been developed starting from multivariate metalorganic frameworks (MOFs). The M 1-N-C catalysts,featuring identical chemical environments and supports,p rovided an ideal platform for differentiating the activity of single-atom metal species.W hen employed in electrocatalytic CO 2 reduction, Ni 1-N-C exhibited av ery high CO Faradaic efficiency (FE) up to 96.8 %t hat far surpassed Fe 1-, Co 1-a nd Cu 1-N-C. Remarkably,t he best-performer,N i 1-N-C,e ven demonstrated excellent CO FE at low CO 2 pressures,t herebyr epresenting ap romising opportunity for the direct use of dilute CO 2 feedstock.

Regulating the Electron Localization of Metallic Bismuth for Boosting CO2 Electroreduction

“…This is in good agreement with the experimental results that more positive onset potential is needed for Bi-B. Furthermore, the thermodynamic limiting potential difference between CO 2 RR and HER (U L (CO 2 )-U L (H 2 )) is a descriptor for CO 2 RR selectivity [55,56]. As shown in Fig.…”

Metal–Organic Framework-Derived CuS Nanocages for Selective CO 2 Electroreduction to Formate

“…It has been widely recognized that metal-organic frameworks are one kind of promising precursor for constructing functional nanomaterials with well-defined composition, morphology, and microstructure. 47,48 To better understand the effects of S-doping on the formate selectivity of Cu(S), density functional theory (DFT) calculations were performed to study reaction thermodynamics of E-CO 2 R and competitive hydrogen evolution reaction (HER) on Cu, Cu 0.96 S 0.04 , and Cu 0.87 S 0.13 . The Cu 0.87 S 0.13 model slab was chosen due to its similar composition to that of CuS-HP-derived Cu(S).…”

Support-based modulation strategies in single-atom catalysts for electrochemical CO2 reduction: graphene and conjugated macrocyclic complexes

“…39 Thus, it is necessary to introduce heteroatoms to provide the coordination environment for metal centers to form strong metal–substrate interactions. In general, N-doped Gr substrates are widely used to anchor single atoms, 40 and various SACs with the structure of MN x ( x = 1–4) have been successfully prepared by many synthesis methods, 41–43 including metal–organic framework (MOF) derived materials and conjugated macrocycle derived materials . 44,45 Moreover, advanced characterization techniques such as extended X-ray absorption fine structure (EXAFS), X-ray absorption near-edge structure (XANES), etc.…”