Active Surface Structure of SnO<sub>2</sub> Catalysts for CO<sub>2</sub> Reduction Revealed by Ab Initio Simulations

Salvini, Clara; Fiorentin, Michele Re; Risplendi, Francesca; Raffone, Federico; Cicero, Giancarlo

doi:10.1021/acs.jpcc.2c02583

Cited by 19 publications

(20 citation statements)

References 51 publications

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“…SnO 2 @C GDE to dry under air, in situ reduction of SnO 2 to metallic Sn 0 under the harsh cathodic operating conditions and subsequent re-oxidation in air appear to be the main cause of the temporary loss of selectivity. [28] To confirm our hypothesis, additional ex situ physicochemical characterization for both electrocatalysts was performed on both pristine pray coated GDEs and used electrodes. Firstly, ex situ XRD (Figure 6), after 24 h of electrolysis, clearly indicates a change in the oxidation state of the pomegranate SnO 2 nanocomposites when comparing the Pom.…”

Section: Physicochemical Characterizationmentioning

confidence: 75%

“…In literature currently no definitive consensus has been reached concerning the active site and selective species for the eCO 2 RR towards formate on Sn‐based electrocatalysts [25–28] . Nevertheless, the importance of Sn oxide species, present in our pomegranate‐structured electrocatalysts, has been highlighted for the selective eCO 2 RR towards formate [29–35] .…”

Section: Resultsmentioning

confidence: 98%

“…[23,24] In literature currently no definitive consensus has been reached concerning the active site and selective species for the eCO 2 RR towards formate on Sn-based electrocatalysts. [25][26][27][28] Nevertheless, the importance of Sn oxide species, present in our pomegranate-structured electrocatalysts, has been highlighted for the selective eCO 2 RR towards formate. [29][30][31][32][33][34][35] For example, density functional theory (DFT) calculations by An et al [36] found that a suitable ratio of Sn 0 /Sn 2 + /Sn 4 + results in a synergistic effect.…”

Section: Physicochemical Characterizationmentioning

confidence: 94%

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Enhanced Pomegranate‐Structured SnO₂ Electrocatalysts for the Electrochemical CO₂ Reduction to Formate

et al. 2023

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Although most state‐of‐the‐art Sn‐based electrocatalysts yield promising results in terms of selectivity and catalyst activity, their stability remains insufficient to date. Here, we demonstrate the successful application of the recently developed pomegranate‐structured SnO2 (Pom. SnO2) and SnO2@C (Pom. SnO2@C) nanocomposite electrocatalysts for the efficient electrochemical conversion of CO2 to formate. With an initial selectivity of 83 and 86 % towards formate and an operating potential of −0.72 V and −0.64 V vs. RHE, respectively, these pomegranate SnO2 electrocatalysts are able to compete with most of the current state‐of‐the‐art Sn‐based electrocatalysts in terms of activity and selectivity. Given the importance of electrocatalyst stability, long‐term experiments (24 h) were performed and a temporary loss in selectivity for the Pom. SnO2@C electrocatalyst was largely restored to its initial selectivity upon drying and exposure to air. Of all the used (24 h) electrocatalysts, the pomegranate SnO2@C had the highest selectivity over a time period of one hour, reaching an average recovered Faradaic efficiency (FE) of 85 %, while the commercial SnO2 and bare pomegranate SnO2 electrocatalysts reached an average of 79 and 80 % FE towards formate, respectively. Furthermore, the pomegranate structure of Pom. SnO2@C was largely preserved due to the presence of the heterogeneous carbon shell, which acts as a protective layer, physically inhibiting particle segregation/pulverisation and agglomeration.

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Section: Physicochemical Characterizationmentioning

confidence: 75%

Section: Resultsmentioning

confidence: 98%

Section: Physicochemical Characterizationmentioning

confidence: 94%

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Enhanced Pomegranate‐Structured SnO₂ Electrocatalysts for the Electrochemical CO₂ Reduction to Formate

et al. 2023

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“…Several remarkable works have successfully exploited the ab initio DFT and ab initio MD to analyze the experimental results. [ 186–188 ] For instance, Ge et al. successfully employed ab initio DFT to screen out a series of transition metal (TM) atoms supported on MoS 2 nanosheets (TM@MoS 2 ).…”

Section: Discussionmentioning

confidence: 99%

“…Several remarkable works have successfully exploited the ab initio DFT and ab initio MD to analyze the experimental results. [186][187][188] For instance, Ge et al successfully employed ab initio DFT to screen out a series of transition metal (TM) atoms supported on MoS 2 nanosheets (TM@MoS 2 ). The ab initio MD was further performed to demonstrate the high thermodynamic stability and excellent electrical conductivity of Re@MoS 2 , which are consistent with the DFT results.…”

Section: Coupling Of Multiscale Theoretical Calculations and Simulationsmentioning

confidence: 99%

Advancing the Electrochemistry of Gas‐Involved Reactions through Theoretical Calculations and Simulations from Microscopic to Macroscopic

Liu

Wang

et al. 2022

Adv Funct Materials

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Nowadays, gas‐involved electrochemical reactions, such as carbon dioxide reduction reaction (CO2RR), nitrogen reduction reaction (NRR), and hydrogen evolution reaction (HER), have gradually become viable solutions to the global environmental pollution and energy crisis. However, their further development is inseparable from the in‐depth understanding of reaction mechanisms, which are incredibly complicated and cannot be satisfied by experiments alone. In this context, theoretical calculations and simulations are of great significance in establishing composition–structure–activity relationships, providing priceless mechanistic discernment and predicting prospective electrocatalysts and systems. Among them, density functional theory (DFT), molecular dynamics (MD) simulations, and finite element simulation (FES) are emerging as three mature theoretical tools. This paper presents a review of the basic principles and research progress of DFT, MD, and FES to deepen the understanding of CO2RR, NRR, and HER. Some remarkable work around theoretical calculations and simulations are highlighted, including the utilization of DFT to investigate the intrinsic properties of catalysts and MD or FES to restore the whole reaction systems from different temporal and spatial scales. Eventually, to sum up, forward‐looking insights and perspectives on the future optimizations and application modes of the three computational techniques to compensate for their shortcomings and limitations are presented.

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Theoretically Designed Cu₁₀Sn₃‐Cu‐SnO_x as Three‐Component Electrocatalyst for Efficient and Tunable CO₂ Reduction to Syngas

Woldu,

Harrath,

Huang

et al. 2023

Small

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Electrocatalytic transformation of CO2 to various syngas compositions is an exceedingly attractive approach to carbon‐neutral recycling. Meanwhile, the achievement of selectivity, stability, and tunability of product ratios using single‐component electrocatalysts is challenging. Herein, the theoretically‐assisted design of the triple‐component nanocomposite electrocatalyst Cu10Sn3‐Cu‐SnOx that addresses this challenge is presented. It is shown that Cu10Sn3 is a valuable electrocatalyst for suitable CO2 reduction to CO, SnO2 for CO2 reduction to formate at large overpotentials, and that the Cu–SnO2 interface facilitates H2 evolution. Accordingly, the interaction between the three functional components affords tunable CO/H2 ratios, from 1:2 to 2:1, of the produced syngas by controlling the applied potentials and relative contents of functional components. The syngas generation is selective (Faradaic efficiency, FE = 100%) at relatively lower cathodic potentials, whereas formate is the only liquid product detected at relatively higher cathodic potentials. The theoretically guided design approach therefore provides a new opportunity to boost the selectivity and stability of CO2 reduction to tunable syngas.

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Active Surface Structure of SnO₂ Catalysts for CO₂ Reduction Revealed by Ab Initio Simulations

Cited by 19 publications

References 51 publications

Enhanced Pomegranate‐Structured SnO₂ Electrocatalysts for the Electrochemical CO₂ Reduction to Formate

Enhanced Pomegranate‐Structured SnO₂ Electrocatalysts for the Electrochemical CO₂ Reduction to Formate

Advancing the Electrochemistry of Gas‐Involved Reactions through Theoretical Calculations and Simulations from Microscopic to Macroscopic

Theoretically Designed Cu₁₀Sn₃‐Cu‐SnO_x as Three‐Component Electrocatalyst for Efficient and Tunable CO₂ Reduction to Syngas

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Active Surface Structure of SnO2 Catalysts for CO2 Reduction Revealed by Ab Initio Simulations

Cited by 19 publications

References 51 publications

Enhanced Pomegranate‐Structured SnO2 Electrocatalysts for the Electrochemical CO2 Reduction to Formate

Enhanced Pomegranate‐Structured SnO2 Electrocatalysts for the Electrochemical CO2 Reduction to Formate

Advancing the Electrochemistry of Gas‐Involved Reactions through Theoretical Calculations and Simulations from Microscopic to Macroscopic

Theoretically Designed Cu10Sn3‐Cu‐SnOx as Three‐Component Electrocatalyst for Efficient and Tunable CO2 Reduction to Syngas

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Product

Resources

About

Active Surface Structure of SnO₂ Catalysts for CO₂ Reduction Revealed by Ab Initio Simulations

Enhanced Pomegranate‐Structured SnO₂ Electrocatalysts for the Electrochemical CO₂ Reduction to Formate

Enhanced Pomegranate‐Structured SnO₂ Electrocatalysts for the Electrochemical CO₂ Reduction to Formate

Theoretically Designed Cu₁₀Sn₃‐Cu‐SnO_x as Three‐Component Electrocatalyst for Efficient and Tunable CO₂ Reduction to Syngas