Divergent Paths, Same Goal: A Pair‐Electrosynthesis Tactic for Cost‐Efficient and Exclusive Formate Production by Metal–Organic‐Framework‐Derived 2D Electrocatalysts

Abstract

Electrosynthesis of formic acid/formate is a promising alternative protocol to industrial processes. Herein, a pioneering pair‐electrosynthesis tactic is reported for exclusively producing formate via coupling selectively electrocatalytic methanol oxidation reaction (MOR) and CO2 reduction reaction (CO2RR), in which the electrode derived from Ni‐based metal–organic framework (Ni‐MOF) nanosheet arrays (Ni‐NF‐Af), as well as the Bi‐MOF‐derived ultrathin bismuthenes (Bi‐enes), both obtained through an in situ electrochemical conversion process, are used as efficient anodic and cathodic electrocatalysts, respectively, achieving concurrent yielding of the same high‐value product at both electrodes with greatly reduced energy input. The as‐prepared Ni‐NF‐Af only needs quite low potentials to reach large current densities (e.g., 100 mA cm−2@1.345 V) with ≈100% selectivity for anodic methanol‐to‐formate conversion. Meanwhile, for CO2RR in the cathode, the as‐prepared Bi‐enes can simultaneously exhibit near‐unity selectivity, large current densities, and good stability in a wide potential window toward formate production. Consequently, the coupled MOR//CO2RR system based on the distinctive MOF‐derived catalysts displays excellent performance for pair‐electrosynthesis of formate, delivering high current densities and nearly 100% selectivity for formate production in both the anode and the cathode. This work provides a novel way to design advanced MOF‐derived electrocatalysts and innovative electrolytic systems for electrochemical production of value‐added feedstocks.

Efficient Electroconversion of Carbon Dioxide to Formate by a Reconstructed Amino‐Functionalized Indium–Organic Framework Electrocatalyst

“…[4][5][6] To date, technicaleconomic analysis indicates that formate is one of the most economically promising options in CO 2 electrocatalytic conversion. [7,8] Among many catalysts, indium (In)-based catalysts manifest extremely high selectivity to formate product, and they are considered as the potential catalysts for CO 2 reduction to produce formate due to their low toxicity and environmental friendliness. [9][10][11] Nevertheless, the lower intrinsic activity and poor stability limit their further application in CO 2 reduction.…”

Toward High‐Performance CO2‐to‐C2 Electroreduction via Linker Tuning on MOF‐Derived Catalysts

“…[4] As a kind of porous material, metal-organic frameworks (MOFs) have been extensively explored in eCO 2 RR due to their ordered structure, [5,6] high porosity, [7,8] adjustable chemical functionality, [9][10][11] and flexibility in the structure design. [10,12] Additionally, the structures of MOF catalysts are easy to be in situ reconstructed under electrochemical conditions to be derive to new structures, [2,13] which are commonly referred to as MOF-derived catalyst. Due to the diverse structural regulation released Cu + ions slowly, and the Cu + ions were further oxidized by O 2 in the solution to form a 2D framework.…”

Single-phase proton- and electron-conducting Ag-organic coordination polymers for efficient CO2electroreduction

“…30 More MOCPs are used as the precursors to prepare doped carbon materials, nanosheet and single-atom catalysts, etc. 31–34 However, the mentioned method is not conducive to the study of the intrinsic structure–property relationship of MOCPs. Therefore, there is still a need for developing new MOCPs as CO 2 RR electrocatalysts.…”