Computational Screening of Transition Metal /p-block Hybrid Electrocatalysts for CO2 Reduction

Reduction Reaction ◽

Intermediate Species ◽

Computational Screening ◽

Reduction Of Co2 ◽

Future Work

Among all the pollutants in the atmosphere, CO2 has the highest impact on global warming and with the rising levels of this pollutant, studies on developing various technologies to convert CO2 into carbon neutral fuels and chemicals have become more valuable. In this work, we present a detailed computational study of electrochemical reduction of CO2 reduction (CO2RR) to methane and methanol over different transition metal-p block catalysts using Density Functional Theory calculations. In addition to the catalyst structure, we studied reaction mechanisms using free energy diagrams that explain the product selectivity with respect to the competing hydrogen evolution reaction. Furthermore, we developed scaling relations between all the active C bound intermediate species with ΔG (CO*) and O bound species with ΔG (OH*). The limiting potential lines with ΔG(OH*) as descriptor are much less negative compared to UL lines with ΔG(CO*) as descriptor indicating that catalyst materials following pathways via OH- bound intermediate species require more negative potentials than CO*HCO* and CO2 COOH* steps to convert into products. We developed thermodynamic volcano plots with two descriptors; CO* and OH* binding free energies and determined the best catalyst material among the initially investigated catalyst materials expecting this plot will provide guidance to the future work on improving the activity of transition metal-p block catalysts for this important reduction reaction.<br>

A computational study of hydrogen doping induced metal-to-insulator transition in CaFeO3, SrFeO3, BaFeO3 and SmMnO3

Physical Chemistry Chemical Physics ◽

10.1039/c9cp04669k ◽

2019 ◽

Vol 21 (45) ◽

pp. 25397-25405

Author(s):

Shukai Yao ◽

Pilsun Yoo ◽

Peilin Liao

Keyword(s):

Transition Metal ◽

First Principles ◽

Density Functional ◽

Computational Study ◽

Functional Theory ◽

Hydrogen Doping ◽

Gap Opening ◽

Metal To Insulator Transition

First principles density functional theory calculations were performed to identify transition metal perovskites CaFeO3, SrFeO3, BaFeO3 and SmMnO3 as promising candidates with large band gap opening upon hydrogen doping.

Graphene Supported Tungsten Carbide as Catalyst for Electrochemical Reduction of CO2

Catalysts ◽

10.3390/catal9070604 ◽

2019 ◽

Vol 9 (7) ◽

pp. 604

Author(s):

Sahithi Ananthaneni ◽

Zachery Smith ◽

Rees B. Rankin

Keyword(s):

Tungsten Carbide ◽

Electrochemical Reduction ◽

Density Functional ◽

Low Cost ◽

Co2 Reduction ◽

Platinum Group Metal ◽

Reduction Reaction ◽

Depth Study ◽

Reduction Of Co2 ◽

Co2 Reduction Reaction

Electrochemical reduction of CO2 to useful chemical and fuels in an energy efficient way is currently an expensive and inefficient process. Recently, low-cost transition metal-carbides (TMCs) have been proven to exhibit similar electronic structure similarities to Platinum-Group-Metal (PGM) catalysts and hence, can be good substitutes for some important reduction reactions. In this work, we test graphene-supported WC (Tungsten Carbide) nanoclusters as an electrocatalyst for the CO2 reduction reaction. Specifically, we perform density functional theory (DFT) studies to understand various possible reaction mechanisms and determine the lowest thermodynamic energy landscape of CO2 reduction to various products, such as CO, HCOOH, CH3OH, and CH4. This in-depth study of reaction energetics could lead to improvements and development of more efficient electrocatalysts for CO2 reduction.

A computational study of the competing reaction mechanisms of the photo-catalytic reduction of CO2 on anatase(101)

Physical Chemistry Chemical Physics ◽

10.1039/c6cp02642g ◽

2016 ◽

Vol 18 (36) ◽

pp. 25010-25021 ◽

Cited By ~ 11

Author(s):

Chung Man Ip ◽

Alessandro Troisi

Keyword(s):

Carbon Dioxide ◽

Reaction Mechanisms ◽

Density Functional ◽

Catalytic Reduction ◽

Computational Study ◽

Reaction Pathways ◽

Functional Theory ◽

Reduction Of Co2

Three reaction pathways for the photocatalytic reduction of carbon dioxide to methane are investigated with density functional theory calculations.

Gold-like activity copper-like selectivity of heteroatomic transition metal carbides for electrocatalytic carbon dioxide reduction reaction

Nature Communications ◽

10.1038/s41467-021-25295-y ◽

2021 ◽

Vol 12 (1) ◽

Author(s):

Mohammadreza Esmaeilirad ◽

Artem Baskin ◽

Alireza Kondori ◽

Ana Sanz-Matias ◽

Jin Qian ◽

...

Keyword(s):

Carbon Dioxide ◽

Transition Metal ◽

Density Functional ◽

Choline Chloride ◽

Fuel Efficiency ◽

Photovoltaic Cell ◽

Carbon Dioxide Reduction ◽

Reduction Reaction ◽

Transition Metal Carbide

AbstractAn overarching challenge of the electrochemical carbon dioxide reduction reaction (eCO2RR) is finding an earth-abundant, highly active catalyst that selectively produces hydrocarbons at relatively low overpotentials. Here, we report the eCO2RR performance of two-dimensional transition metal carbide class of materials. Our results indicate a maximum methane (CH4) current density of −421.63 mA/cm2 and a CH4 faradic efficiency of 82.7% ± 2% for di-tungsten carbide (W2C) nanoflakes in a hybrid electrolyte of 3 M potassium hydroxide and 2 M choline-chloride. Powered by a triple junction photovoltaic cell, we demonstrate a flow electrolyzer that uses humidified CO2 to produce CH4 in a 700-h process under one sun illumination with a CO2RR energy efficiency of about 62.3% and a solar-to-fuel efficiency of 20.7%. Density functional theory calculations reveal that dissociation of water, chemisorption of CO2 and cleavage of the C-O bond—the most energy consuming elementary steps in other catalysts such as copper—become nearly spontaneous at the W2C surface. This results in instantaneous formation of adsorbed CO—an important reaction intermediate—and an unlimited source of protons near the tungsten surface sites that are the main reasons for the observed superior activity, selectivity, and small potential.

Transition-metal-atom-pairs deposited on g-CN monolayer for nitrogen reduction reaction: Density functional theory calculations

Chinese Journal of Catalysis ◽

10.1016/s1872-2067(20)63745-7 ◽

2021 ◽

Vol 42 (7) ◽

pp. 1160-1167

Author(s):

Bin Huang ◽

Yifan Wu ◽

Bibo Chen ◽

Yong Qian ◽

Naigen Zhou ◽

...

Keyword(s):

Transition Metal ◽

Metal Atom ◽

Density Functional ◽

Reduction Reaction ◽

Transition Metal Atom ◽

Functional Theory ◽

Nitrogen Reduction ◽

Atom Pairs

Graphene Supported Tungsten Carbide as Catalyst for Electrochemical Reduction of CO2

10.26434/chemrxiv.8280986 ◽

2019 ◽

Author(s):

Sahithi Ananthaneni ◽

Rees Rankin

Keyword(s):

Tungsten Carbide ◽

Electrochemical Reduction ◽

Low Cost ◽

Co2 Reduction ◽

Platinum Group Metal ◽

Reduction Reaction ◽

Metal Carbides ◽

Depth Study ◽

Reduction Of Co2 ◽

Co2 Reduction Reaction

<div>Electrochemical reduction of CO2 to useful chemical and fuels in an energy efficient way is currently an expensive and inefficient process. Recently, low-cost transition metal-carbides (TMCs) are proven to exhibit similar electronic structure similarities to Platinum-Group-Metal (PGM) catalysts and hence can be good substitutes for some important reduction reactions. In this work, we test graphenesupported WC (Tungsten Carbide) nanocluster as an electrocatalyst for the CO2 reduction reaction. Specifically, we perform DFT studies to understand various possible reaction mechanisms and determine the lowest thermodynamic energy landscape of CO2 reduction to various products such as CO, HCOOH, CH3OH, and CH4. This in-depth study of reaction energetics could lead to improvements and develop more efficient electrocatalysts for CO2 reduction.<br></div>

Three-dimensional porous copper-decorated bismuth-based nanofoam for boosting electrochemical reduction of CO2 to formate

Inorganic Chemistry Frontiers ◽

10.1039/d1qi00065a ◽

2021 ◽

Author(s):

Yingchun Zhang ◽

Changsheng Cao ◽

Xintao Wu ◽

Qi-Long Zhu

Keyword(s):

Current Density ◽

High Current Density ◽

Three Dimensional ◽

Co2 Reduction ◽

Reduction Reaction ◽

High Current ◽

Porous Copper ◽

Reduction Of Co2 ◽

Co2 Reduction Reaction ◽

Wide Potential

Bismuth (Bi)-based nanomaterials are considered as the promising electrocatalysts for electrocatalytic CO2 reduction reaction (CO2RR), but it is challenging to achieve high current density and selectivity in a wide potential...

Probing the activity of transition metal M and heteroatom N4 co-doped in vacancy fullerene (M–N4–C64, M = Fe, Co, and Ni) towards the oxygen reduction reaction by density functional theory

RSC Advances ◽

10.1039/d0ra08652e ◽

2021 ◽

Vol 11 (5) ◽

pp. 3174-3182

Author(s):

Siwei Yang ◽

Chaoyu Zhao ◽

Ruxin Qu ◽

Yaxuan Cheng ◽

Huiling Liu ◽

...

Keyword(s):

Transition Metal ◽

Oxygen Reduction Reaction ◽

Oxygen Reduction ◽

Density Functional ◽

Reduction Reaction ◽

Functional Theory ◽

Co Doped

In this study, a novel type oxygen reduction reaction (ORR) electrocatalyst is explored using density functional theory (DFT); the catalyst consists of transition metal M and heteroatom N4 co-doped in vacancy fullerene (M–N4–C64, M = Fe, Co, and Ni).