Screening of Transition Metal Supported on Black Phosphorus as Electrocatalysts for CO₂ Reduction

Abstract

The electrocatalytic CO 2 reduction (CO 2 RR) is an effective and economical strategy to eliminate CO 2 through conversion into value-added chemicals and fuels. However, exploring and screening suitable 2D material-based single-atom catalysts (SACs) for CO 2 reduction are still a great challenge. In this study, 27 (3d, 4d, and 5d, except Tc and Hg) transition metal (TM) atom-doped black phosphorus (TM@BP) electrocatalysts were systematically investigated for CO 2 RR by density functional theory calculations. According to the stability of SACs and their effectiveness in activating the CO 2 molecule, three promising catalysts, Zr@BP, Nb@BP, and Ru@BP, were successfully screened out, exhibiting outstanding catalytic activity for the production of carbon monoxide (CO), methyl alcohol (CH 3 OH), and methane (CH 4 ) with limiting potentials of −0.79, −0.49, and −0.60 V, respectively. A catalytic relationship between the d-band centers of SACs and the limiting potential of CO 2 RR was used to estimate the catalytic activity of catalysts. Furthermore, Nb@BP has high selectivity for CO 2 RR to CH 3 OH compared to H 2 formation, while the hydrogen evolution reaction significantly impacts the synthesis of CO and CH 4 on Zr@BP and Ru@BP. Nitrogen atom doping in BP is beneficial for enhancing the selectivity of CO 2 RR, but it is detrimental to the activity of CO 2 RR. This study offers theoretical guidance for synthesizing highly efficient CO 2 RR electrocatalysts and further enhances structural modulation methods for layered 2D materials.

Selectivity-Enhanced Electroreduction of CO2 to CO at Novel Ru-Linked-GO Nanohybrids: the Role of Nanoarchitecture

“…The formation of CO from the electroreduction of CO 2 is more favorable, either electrochemically, thermodynamically, and in certain circumstances also kinetically than other two-electron reduction products. , Single electron (e̅) reduction of CO 2 to CO 2 •– is an energetically demanding approach (−2.17 V vs Ag/AgCl), while multiple-e̅ reduction routes are accessible at substantially lower overpotentials. ,− Therefore, the design of new electrocatalysts to facilitate the multiple-e̅ reduction of CO 2 to CO at lower overpotential could be helpful to overcome low rates. − To date, a great number of homogeneous and heterogeneous electrocatalysts have been developed for CO 2 RR. The typical homogeneous catalysts include metal–organic frameworks, transition-metal complexes, carbon-doped and decorated materials, two-dimensional materials, MXene-based single-atom catalysts, and so on. − In recent decades, noble metal coordination complexes have enticed significant consideration in CO 2 reduction according to their potential to create efficient functional and structural models due to the availability of multiple-oxidation states based on both metal and ligands. ,,, Ruthenium as a classical noble metal catalyst was widely studied, and it also presented outstanding electrocatalytic performance. At present, great advances have also been achieved in the development of Ru-based electrocatalysts through alloying, heteroatom doping, nanocompositing, carrier-optimizing, etc.…”

Constructing a Stable Built-In Electric Field in Bi/Bi2Te3 Nanowires for Electrochemical CO2 Reduction Reaction

“…Converting CO 2 into value-added chemicals or fuels is an appealing method for reducing CO 2 emissions and thereby achieving carbon neutrality. − Nevertheless, the inertness and thermodynamic stability of CO 2 severely constrain its conversion efficiency. Electroreduction CO 2 (CO 2 RR) has attracted substantial attention from researchers due to its high conversion efficiency, mild reaction conditions, and elevated energy efficiency. − The specific products formed depend on the number of protons, electrons, and reduction pathways involved, as the CO 2 RR is a multiproton-coupled and multielectron-transfer processes. , By altering the catalytic conditions or reduction pathways, different surface-bound species can generate corresponding reaction intermediates, leading to the formation of different carbon-containing products such as carbon monoxide (CO), formic acid (HCOOH), methane (CH 4 ), and so on. − HCOOH, revered as a high-value CO 2 electroreduction product, is an important raw material in the pharmaceutical and chemical industries, making it one of the most economically viable products in the CO 2 RR process. − In the electrochemical reaction mechanism, HCOOH requires minimal electron transfer during the electroreduction process, which not only simplifies the reduction of CO 2 to HCOOH but also allows for its subsequent conversion into other raw materials such as hydrogen (H 2 ), CO, and methanol (CH 3 OH) through simple catalytic reactions to meet various industrial production needs. − Therefore, the rational design of catalysts and reduction pathways is crucial to the selectivity and yield of the products.…”