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

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 ◽  
Density Functional Theory Calculations ◽  
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.

scholarly journals Gold-Like Activity, Copper-Like Selectivity of Heteroatomic Transition Metal Carbides (M2C) for Electrocatalytic Carbon Dioxide Reduction Reaction

2021 ◽  
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 ◽  
Highly Active

Abstract An 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 have studied the two-dimensional transition metal carbide (TMC) class of materials and found that di-tungsten carbide (W2C) nanoflakes exhibit maximum methane (CH4) current density of -421.63 mA/cm2 and a CH4 faradic efficiency of 82.7%±2% in a hybrid electrolyte of 3 M potassium hydroxide (KOH) and 2 M choline-chloride (CC). Powered by a triple junction photovoltaic cell, we have demonstrated a flow electrolyzer that uses humidified CO2 to produce CH4 in a 700-hours 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 (DFT) 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.

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

2019 ◽  
Author(s):  
Sahithi Ananthaneni ◽  
Rees Rankin
Keyword(s):  
Transition Metal ◽  
Density Functional ◽  
Computational Study ◽  
Co2 Reduction ◽  
Density Functional Theory Calculations ◽  
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>

scholarly journals Transition metal-nitrogen sites for electrochemical carbon dioxide reduction reaction

2019 ◽  
Vol 40 (1) ◽  
pp. 23-37 ◽  
Author(s):  
Chengcheng Yan ◽  
Long Lin ◽  
Guoxiong Wang ◽  
Xinhe Bao
Keyword(s):  
Carbon Dioxide ◽  
Transition Metal ◽  
Carbon Dioxide Reduction ◽  
Reduction Reaction

scholarly journals Electronic structure of porphyrin-based metal–organic frameworks and their suitability for solar fuel production photocatalysis

2015 ◽  
Vol 3 (46) ◽  
pp. 23458-23465 ◽  
Author(s):  
Said Hamad ◽  
Norge C. Hernandez ◽  
Alex Aziz ◽  
A. Rabdel Ruiz-Salvador ◽  
Sofia Calero ◽  
...  
Keyword(s):  
Carbon Dioxide ◽  
Density Functional Theory ◽  
Electronic Structure ◽  
Density Functional ◽  
Metal Organic Frameworks ◽  
Density Functional Theory Calculations ◽  
Carbon Dioxide Reduction ◽  
Fuel Production ◽  
Functional Theory ◽  
Metal Organic

Density functional theory calculations reveal that the electronic structure of a family of porphyrin-based metal–organic frameworks is suitable for the photocatalysis of water splitting and carbon dioxide reduction reactions.

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

2019 ◽  
Author(s):  
Sahithi Ananthaneni ◽  
Rees Rankin
Keyword(s):  
Transition Metal ◽  
Density Functional ◽  
Computational Study ◽  
Co2 Reduction ◽  
Density Functional Theory Calculations ◽  
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>

scholarly journals 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 ◽  
2021 ◽  
Vol 11 (5) ◽  
pp. 3174-3182
Author(s):  
Siwei Yang ◽  
Chaoyu Zhao ◽  
Ruxin Qu ◽  
Yaxuan Cheng ◽  
Huiling Liu ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
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).

scholarly journals Selective capture of carbon dioxide from hydrocarbons using a metal-organic framework

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Omid T. Qazvini ◽  
Ravichandar Babarao ◽  
Shane G. Telfer
Keyword(s):  
Carbon Dioxide ◽  
Density Functional ◽  
Metal Organic Framework ◽  
Density Functional Theory Calculations ◽  
Time Lags ◽  
X Ray Crystallography ◽  
Metal Organic ◽  
Adsorption Of Co ◽  
Short Time ◽  
Organic Framework

AbstractEfficient and sustainable methods for carbon dioxide capture are highly sought after. Mature technologies involve chemical reactions that absorb CO2, but they have many drawbacks. Energy-efficient alternatives may be realised by porous physisorbents with void spaces that are complementary in size and electrostatic potential to molecular CO2. Here, we present a robust, recyclable and inexpensive adsorbent termed MUF-16. This metal-organic framework captures CO2 with a high affinity in its one-dimensional channels, as determined by adsorption isotherms, X-ray crystallography and density-functional theory calculations. Its low affinity for other competing gases delivers high selectivity for the adsorption of CO2 over methane, acetylene, ethylene, ethane, propylene and propane. For equimolar mixtures of CO2/CH4 and CO2/C2H2, the selectivity is 6690 and 510, respectively. Breakthrough gas separations under dynamic conditions benefit from short time lags in the elution of the weakly-adsorbed component to deliver high-purity hydrocarbon products, including pure methane and acetylene.

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