Photoelectrocatalytic Carbon Dioxide Reduction to Value-Added Products

Kalra, Paras; Suresh, Cini M.; Rashid, Awais; Ingole, Pravin P.

doi:10.1201/9781003211761-5

Cited by 3 publications

(2 citation statements)

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“…The absence of nitrogen in our electrocatalyst, unlike nitrides or phthalocyanines, eliminates the possibility of false-positive results via nonelectrocatalytic reactions in aqueous electrolytes. Further, to gain more insights into the catalytic activity of BSTO, the turnover frequency (TOF) was calculated for BSTO using eq and was compared with the previously reported catalyst (Figure f). TOF = n t × n ′ …”

Section: Resultsmentioning

confidence: 99%

Engineered Electron-Deficient Sites at Boron-Doped Strontium Titanate/Electrolyte Interfaces Accelerate the Electrocatalytic Reduction of N₂ to NH₃: A Combined DFT and Experimental Electrocatalysis Study

Kalra,

Samolia,

Bashir

et al. 2024

ACS Appl. Mater. Interfaces

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The development of an efficient, selective, and durable catalysis system for the electrocatalytic N 2 reduction reaction (ENRR) is a promising strategy for the sustainable production of ammonia. The highperformance ENRR is limited by two major challenges: poor adsorption of N 2 over the catalyst surface and abysmal N 2 solubility in aqueous electrolytes. Herein, with the help of our combined density functional theory (DFT) calculations and experimental electrocatalysis study, we demonstrate that concurrently induced electron-deficient Lewis acid sites in an electrocatalyst and in an electrolyte medium can significantly boost the ENRR performance. The DFT calculations, ex situ X-ray photoelectron and FTIR spectroscopy, electrochemical measurements, and N 2 -TPD (temperature-programmed desorption) over boron-doped strontium titanate (BSTO) samples reveal that the Lewis acid−base interactions of N 2 synergistically enhance the adsorption and activation of N 2 . Besides, the B-dopant induces the defect sites (oxygen vacancies and Ti 3+ ) that assist in enhanced N 2 adsorption and results in suppressed hydrogen evolution due to B-induced electron-deficient sites for H + adsorption. The insights from the DFT study evince that B prefers the Sr top position (on top of Sr) where N 2 adsorbs in an end-on configuration, which favors the associative alternating pathway and suppresses the competitive hydrogen evolution. Thus, our combined experimental and DFT study demonstrates an insight toward enhancing the ENRR performance along with the suppressed hydrogen evolution via concurrently engineered electron-deficient sites at electrode and electrolyte interfaces.

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Section: Resultsmentioning

confidence: 99%

Engineered Electron-Deficient Sites at Boron-Doped Strontium Titanate/Electrolyte Interfaces Accelerate the Electrocatalytic Reduction of N₂ to NH₃: A Combined DFT and Experimental Electrocatalysis Study

Kalra,

Samolia,

Bashir

et al. 2024

ACS Appl. Mater. Interfaces

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“…The electrochemical CO 2 reduction reaction (ECO 2 RR) into value-added products is a promising way to address the formidable task of CO 2 mitigation due to its zero pollution causing feature. As carbon monoxide (CO) is one of the most important raw chemicals for the industrial processes including methanol production, Fischer–Tropsch synthesis, and pharmaceuticals, the ECO 2 RR to CO conversion is a crucial process − However, due to the high thermodynamic stability of CO 2 , the ECO 2 RR demands high overpotential to make this process economically viable. This bottleneck can be overcome by the rational design of a low-cost, highly active, and robust electrocatalyst.…”

Section: Introductionmentioning

confidence: 99%

Favoring Product Desorption by a Tailored Electronic Environment of Oxygen Vacancies in SrTiO₃ via Cr Doping for Enhanced and Selective Electrocatalytic CO₂ to CO Conversion

Kalra

Ghosh

Ingole

2023

ACS Appl. Mater. Interfaces

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The electrochemical CO2 reduction reaction (ECO2RR) into value-added products is crucial to address the herculean task of CO2 mitigation. Several efforts are being made to develop active ECO2RR catalysts, targeting enhanced CO2 adsorption and activation. A rational design of ECO2RR catalysts with a facile product desorption step is seldom reported. Herein, ensuing the Sabatier principle, we report a strategy for an enhanced ECO2RR with a faradaic efficiency of 85% for CO production by targeting the product desorption step. The energy barrier for product desorption was lowered via a tailored electronic environment of oxygen vacancies (Ovac) in Cr-doped SrTiO3. The substitutional doping of Cr3+ for Ti4+ into the SrTiO3 lattice favors the generation of more Ovac and modifies the local electronic environment. Density functional theory analysis evinces the spontaneous dissociation of COOH# intermediates over Ovac and lower CO intermediate binding on Ovac reducing the energy demand for CO release due to Cr doping.

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Tuning the Selectivity of Electrocatalytic CO₂ Reduction Reaction via Anion-driven Nanostructuring of Copper Electrodeposits

Suresh,

Mudgil,

Choudhari

et al. 2023

ECS Adv.

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Electrochemical CO2 reduction (ECR) to value-added products is one of the potential ways to utilise CO2 as a feedstock, thereby decreasing its level in the atmosphere as it has harmful repercussions on planet earth. Copper (Cu)-nanostructures have demonstrated a great potential to convert CO2 into valuable higher-end hydrocarbons electrochemically, but with poor selectivity. Therefore, novel strategies to tune Cu-based electrocatalysts' activity and selectivity toward multi-carbon products, particularly at low overpotential, are highly desirable. In the present work, we report an atom-economic strategy to tune the physicochemical properties and the electrocatalytic activity of Cu-nanostructures towards ECR. The Cu-nanostructures synthesized via pulse electrodeposition from an electrolyte bath containing Cu-precursor salts with varying anions (viz. acetates, nitrates, sulphates, and chlorides) are investigated for their effect on the physicochemical properties and the ECR performance. The Cu-electrodeposits having cubic morphology, exposed Cu(100) facets, higher Cu+ content and enhanced electrochemical active surface area demonstrated the best ECR performance depicting good selectivity for ethylene formation.

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Photoelectrocatalytic Carbon Dioxide Reduction to Value-Added Products

Cited by 3 publications

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Engineered Electron-Deficient Sites at Boron-Doped Strontium Titanate/Electrolyte Interfaces Accelerate the Electrocatalytic Reduction of N₂ to NH₃: A Combined DFT and Experimental Electrocatalysis Study

Engineered Electron-Deficient Sites at Boron-Doped Strontium Titanate/Electrolyte Interfaces Accelerate the Electrocatalytic Reduction of N₂ to NH₃: A Combined DFT and Experimental Electrocatalysis Study

Favoring Product Desorption by a Tailored Electronic Environment of Oxygen Vacancies in SrTiO₃ via Cr Doping for Enhanced and Selective Electrocatalytic CO₂ to CO Conversion

Tuning the Selectivity of Electrocatalytic CO₂ Reduction Reaction via Anion-driven Nanostructuring of Copper Electrodeposits

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Photoelectrocatalytic Carbon Dioxide Reduction to Value-Added Products

Cited by 3 publications

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Engineered Electron-Deficient Sites at Boron-Doped Strontium Titanate/Electrolyte Interfaces Accelerate the Electrocatalytic Reduction of N2 to NH3: A Combined DFT and Experimental Electrocatalysis Study

Engineered Electron-Deficient Sites at Boron-Doped Strontium Titanate/Electrolyte Interfaces Accelerate the Electrocatalytic Reduction of N2 to NH3: A Combined DFT and Experimental Electrocatalysis Study

Favoring Product Desorption by a Tailored Electronic Environment of Oxygen Vacancies in SrTiO3 via Cr Doping for Enhanced and Selective Electrocatalytic CO2 to CO Conversion

Tuning the Selectivity of Electrocatalytic CO2 Reduction Reaction via Anion-driven Nanostructuring of Copper Electrodeposits

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Engineered Electron-Deficient Sites at Boron-Doped Strontium Titanate/Electrolyte Interfaces Accelerate the Electrocatalytic Reduction of N₂ to NH₃: A Combined DFT and Experimental Electrocatalysis Study

Engineered Electron-Deficient Sites at Boron-Doped Strontium Titanate/Electrolyte Interfaces Accelerate the Electrocatalytic Reduction of N₂ to NH₃: A Combined DFT and Experimental Electrocatalysis Study

Favoring Product Desorption by a Tailored Electronic Environment of Oxygen Vacancies in SrTiO₃ via Cr Doping for Enhanced and Selective Electrocatalytic CO₂ to CO Conversion

Tuning the Selectivity of Electrocatalytic CO₂ Reduction Reaction via Anion-driven Nanostructuring of Copper Electrodeposits