Chlorine in NiO promotes electroreduction of CO2 to formate

Rodriguez-Olguin, M.A.; Flox, Cristina; Ponce‐Pérez, R.; Lipin, Raju; Ruiz‐Zepeda, Francisco; Winczewski, J.P.; Kallio, Tanja; Vandichel, Matthias; Guerrero-Sánchez, J.; Gardeniers, Han; Takeuchi, Noboru; Susarrey-Arce, Arturo

doi:10.1016/j.apmt.2022.101528

Cited by 8 publications

(5 citation statements)

References 76 publications

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“…The TOF is separately calculated as 7.84 s −1 (i cat /i p = 6.3) in CO 2 -saturated 0.1 M n Bu 4 NPF 6 /DMF solution with 0.0175 M CH 3 COOH at −1.99 V, which is comparable to those reported nickel-based homogeneous catalysts (Table S4) [76][77][78][79][80][81]. However, due to the process being controlled by diffusion, for most molecular catalysts, the product of the electrocatalytic CO 2 is carbon monoxide, which is very different from other heterogeneous catalysts for producing formic acid and formate with Ni-based anodes [82][83][84][85]. Then, the rinse test was conducted on the FTO glass electrode after electrocatalysis, and no obvious current density was observed, which was similar to the blank solution before catalysis (navy blue line), ensuring that complex 1 is a stable homogeneous catalyst.…”

Section: Electrocatalytic Co 2 Reductionsupporting

confidence: 73%

Electrochemical Water Oxidation and CO2 Reduction with a Nickel Molecular Catalyst

Jian,

Lu,

Zheng

et al. 2024

Molecules

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Mimicking the photosynthesis of green plants to combine water oxidation with CO2 reduction is of great significance for solving energy and environmental crises. In this context, a trinuclear nickel complex, [NiII3(paoH)6(PhPO3)2]·2ClO4 (1), with a novel structure has been constructed with PhPO32− (phenylphosphonate) and paoH (2-pyridine formaldehyde oxime) ligands and possesses a reflection symmetry with a mirror plane revealed by single-crystal X-ray diffraction. Bulk electrocatalysis demonstrates that complex 1 can homogeneously catalyze water oxidation and CO2 reduction simultaneously. It can catalyze water oxidation at a near-neutral condition of pH = 7.45 with a high TOF of 12.2 s−1, and the Faraday efficiency is as high as 95%. Meanwhile, it also exhibits high electrocatalytic activity for CO2 reduction towards CO with a TOF of 7.84 s−1 in DMF solution. The excellent electrocatalytic performance of the water oxidation and CO2 reduction of complex 1 could be attributed to the two unique µ3-PhPO32− bridges as the crucial factor for stabilizing the trinuclear molecule as well as the proton transformation during the catalytic process, while the oxime groups modulate the electronic structure of the metal centers via π back-bonding. Therefore, apart from the cooperation effect of the three Ni centers for catalysis, simultaneously, the two kinds of ligands in complex 1 can also synergistically coordinate the central metal, thereby significantly promoting its catalytic performance. Complex 1 represents the first nickel molecular electrocatalyst for both water oxidation and CO2 reduction. The findings in this work open an avenue for designing efficient molecular electrocatalysts with peculiar ligands.

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Section: Electrocatalytic Co 2 Reductionsupporting

confidence: 73%

Electrochemical Water Oxidation and CO2 Reduction with a Nickel Molecular Catalyst

Jian,

Lu,

Zheng

et al. 2024

Molecules

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“…This may result from the improved accessibility between In sites and CO 2 as demonstrated above. Moreover, the CO 2 RR performances of as-designed In 1 /NC-3D outperform most of the recently reported catalysts (Figure g and Table S2) in terms of high FE formate at a large current density. ,,,− Such a strategy of constructing 3D porous In SACs is demonstrated to attain high formate selectivity at high current density, circumventing the present limitation of In-based SACs.…”

Section: Resultsmentioning

confidence: 75%

Three-Dimensional Porous Indium Single-Atom Catalysts with Improved Accessibility for CO₂ Reduction to Formate

Zhu,

Xu,

Ran

et al. 2024

Inorg. Chem.

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Single-atom catalysts (SACs) present substantial potential in electrocatalytic CO 2 reduction reactions; however, inferior accessibility of single-atom sites to CO 2 limits the overall CO 2 RR performances. Herein, we propose to improve the accessibility between In sites and CO 2 through the construction of a three-dimensional (3D) porous indium single-atom catalyst (In 1 / NC-3D). The NaCl template-mediated synthesis strategy generates the unique 3D porous nanostructure of In 1 /NC-3D. Multiple characterizations validate that In 1 /NC-3D exhibits increased exposure of active sites and enhanced CO 2 transport/adsorption capacity compared to the bulk In 1 /NC, thus improving accessibility of active sites to CO 2 . As a result, the In 1 /NC-3D presents superior CO 2 RR performance to the bulk In 1 /NC, with a partial current density of formate of 67.24 mA cm −2 at −1.41 V, relative to a reversible hydrogen electrode (vs RHE). The CO 2 RR performances with high formate selectivity at a large current density also outperform most reported In-based SACs. Importantly, the In 1 /NC-3D is demonstrated to maintain an FE formate of >82% at −66.83 mA•cm −2 over 21 h. This work highlights the design of a 3D porous single-atom catalyst for efficient CO 2 RR, promoting the development of advanced catalysts toward advanced energy conversion.

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“…It is important to note that, in this analysis, we did not include the effect of pH since the study primarily focuses on ORR reaction mechanisms. The pH effect can be analyzed through surface Pourbaix diagrams obtained from the thermodynamically stable hydrogenation steps . Such analysis is beyond the scope of this work.…”

Section: Methodsmentioning

confidence: 99%

“…The pH effect can be analyzed through surface Pourbaix diagrams obtained from the thermodynamically stable hydrogenation steps. 40 Such analysis is beyond the scope of this work. However, this aspect may be an avenue for future investigations to comprehensively understand the role of pH in these reactions.…”

Section: Oxygen Reduction Reaction Analysesmentioning

confidence: 99%

Density Functional Theory Study of Single-Atom Transition Metal Catalysts Supported on Pyridine-Substituted Graphene Nanosheets for Oxygen Reduction Reaction

Alvarado-Leal,

Fernández-Escamilla,

Paez-Ornelas

et al. 2023

ACS Appl. Nano Mater.

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The oxygen reduction reaction (ORR) is of great importance due to its applications for alternative energies and environmental remediation. Therefore, controlling the selectivity toward the four-electrons pathway is of current interest. In this work, using density functional theory calculations, we give a detailed explanation of the role that transition metal centers play as single-atom catalysts to generate either the four or the two-electron pathway. The model system is the TM−N 4 V 2 graphene monolayer (TM = Cr, Mn, Fe, Co, Ni, Cu), where N stands for pyridinic nitrogen species and V for vacancies. Our results show that the magnetic moment present in the Cr, Mn, and Fe results in a strong O 2 * chemisorption. This favors the O 2 * bond breaking after the first hydrogenation, resulting in O* and OH* (dissociative mechanism, which could lead toward the four-electrons pathway). In the case of Co, with its lower magnetic moment, a chemisorbed O 2 * molecule is also obtained, but the reaction follows an associative mechanism, since after the first hydrogenation, an OOH* is formed. Afterward, the reaction also proceeds toward the four-electron pathway. According to our free energy analyses (ΔG), the monolayers with Fe and Mn have the smallest overpotentials, making them the best choices as catalysts for the four electrons ORR. The nonmagnetic Ni or the low magnetic moment Cu atoms only interact weakly with O 2 in a physisorption-type mechanism, leading to the two-electron pathway. The results presented here shed light on the parameters�as the magnetic moment�that help control the selectivity toward the four-electron reaction and they will certainly contribute to the design of electrocatalytic materials, depending on the required application.

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Chlorine in NiO promotes electroreduction of CO2 to formate

Cited by 8 publications

References 76 publications

Electrochemical Water Oxidation and CO2 Reduction with a Nickel Molecular Catalyst

Electrochemical Water Oxidation and CO2 Reduction with a Nickel Molecular Catalyst

Three-Dimensional Porous Indium Single-Atom Catalysts with Improved Accessibility for CO₂ Reduction to Formate

Density Functional Theory Study of Single-Atom Transition Metal Catalysts Supported on Pyridine-Substituted Graphene Nanosheets for Oxygen Reduction Reaction

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Chlorine in NiO promotes electroreduction of CO2 to formate

Cited by 8 publications

References 76 publications

Electrochemical Water Oxidation and CO2 Reduction with a Nickel Molecular Catalyst

Electrochemical Water Oxidation and CO2 Reduction with a Nickel Molecular Catalyst

Three-Dimensional Porous Indium Single-Atom Catalysts with Improved Accessibility for CO2 Reduction to Formate

Density Functional Theory Study of Single-Atom Transition Metal Catalysts Supported on Pyridine-Substituted Graphene Nanosheets for Oxygen Reduction Reaction

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Three-Dimensional Porous Indium Single-Atom Catalysts with Improved Accessibility for CO₂ Reduction to Formate