Tuning the C1/C2 Selectivity of Electrochemical CO2 Reduction on Cu–CeO2 Nanorods by Oxidation State Control (Adv. Mater. 8/2023)

Hong, Seungwon; Abbas, Hafiz Ghulam; Jang, Kyuseon; Patra, Kshirodra Kumar; Kim, Beom-Il; Choi, Byeong‐Uk; Song, Hakhyeon; Lee, Kug‐Seung; Choi, Pyuck‐Pa; Ringe, Stefan; Oh, Jihun

doi:10.1002/adma.202370051

Cited by 6 publications

(6 citation statements)

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“…It can be considered that the synergy between Cu + and Cu 0 in the hydrogenation reaction should be derived from the rate matching of reactant adsorption/activation on Cu + and *H formation/transference from Cu 0 . This is why the number of the Cu 0 −Cu + interfacial site is vital in hydrogenation reaction, 33,44 regardless of the presence or absence of O V sites. Combined with the above analysis, we proposed a sitesynergistic mechanism for DMO hydrogenation over Cu-based catalysts.…”

Section: ■ Introductionmentioning

confidence: 99%

Understanding the Synergistic Catalysis in Hydrogenation of Carbonyl Groups on Cu-Based Catalysts

Wang,

Duan,

Feng

et al. 2024

ACS Catal.

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Understanding the synergy of Cu0 and Cu+ in hydrogenation reactions is indispensable for reasonably modulating the product distributions and improving the catalyst design. Herein, we investigated the hydrogenation of dimethyl oxalate on CeZrO x -supported Cu with varying molar ratios of n Cu +/n Cu 0. A volcano-type correlation of structure and activity indicates that the selectivity of ethylene glycol is strongly dependent on the n Cu +/n Cu 0 ratio, arising from the matching of rates for the activation of carbonyl group-included reactants and H2 on Cu+ and Cu0, respectively. The maximal selectivity toward ethylene glycol is achieved at a ratio of 0.15; deviating from this value leads to the favorable formation of methyl glycolate, a primary product. Results obtained from temperature-programmed surface reactions indicate that the presence of Cu+ and oxygen vacancies (OV) reduces the reaction temperature for the hydrogenation of carbonyl groups. Theoretical data show that the OV located at the copper–ceria interface induces a downward-directed adsorption configuration of the reaction intermediate adsorbed at the Cu+ site, compared to the presence of an upward-directed counterpart at the Cu0–Cu+ center. This change leads to a reduction in the kinetic barrier for the subsequent hydrogenation step, which consumes active *H species transferred from adjacent Cu0 via a hydrogen spillover process. Manipulating the Cu valence state and oxygen vacancies via interfacial engineering offers a viable strategy for governing product distributions, serving as an inspiration for the design of selective hydrogenation catalysts.

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Section: ■ Introductionmentioning

confidence: 99%

Understanding the Synergistic Catalysis in Hydrogenation of Carbonyl Groups on Cu-Based Catalysts

Wang,

Duan,

Feng

et al. 2024

ACS Catal.

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“…generated products are diverse and selective, [12][13][14][15][16][17][18][19][20] including CO, CH 4 , HCOOH or HCOO À (formate), CH 3 OH, C 2 H 4 , CH 3 CH 2 OH and n-C 3 H 7 OH, depending on the electrocatalysts and electrolytes. [21][22][23][24] Based on techno-economic analysis, HCOOH/HCOO À is a typical C 1 molecule that has a high net present value and a large commercial value of up to $0.50/kg, 25 and is widely used in the chemical and pharmaceutical industries in large quantities.…”

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confidence: 99%

Halide precursor reduction strategy to modulate bismuthene with high selectivity and wide potential window for electrochemical CO₂ reduction

Xia,

Xie,

Xie

et al. 2024

AIChE Journal

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Developing high‐performance electrocatalysts for CO2 reduction reaction (CO2RR) is vital in achieving a carbon‐neutral society by converting CO2 into valuable chemicals. CO2RR electrocatalyst with lower overpotential, higher selectivity and wider working potential range is urgently desired, but it is still challenging to realize these factors simultaneously. Here, high‐performance bismuthene‐based electrocatalysts were synthesized by reducing bismuth precursors like BiCl3, BiBr3, and BiI3 in liquid phases. Especially, bismuthene‐I derived from BiI3 showed a nanosheet morphology (around four‐layer) with significantly enhanced (110) surfaces. It enabled an ultrawide potential window (0.7 V) for high formate selectivity (>90%) in a H‐type cell and achieved an ultralow potential (−0.46 V vs. reversible hydrogen electrode) to attain a current density of 200 mA cm−2 in a gas‐diffusion flow cell. The prominent long‐term operational capability of bismuthene‐I was demonstrated in both H‐type and gas‐diffusion cells. Density functional theory calculations revealed that bismuthene‐I possessed abundant topological Bi(110) surfaces states that can reduce the CO2RR overpotential, suppress the competitive hydrogen evolution reaction, and facilitate electron donation during CO2 electrocatalysis. The bismuthene‐I realized low overpotential, high selectivity and wide working potential range simultaneously for electrochemical CO2RR. This work unfolds the broader plausibility of facilely reducing precursors for the scalable fabrication of high‐performing CO2RR electrocatalysts.

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“…37−40 On the other hand, the strong metal-oxide interaction can induce the partially charged metal surface to enrich active sites and stabilize the key intermediates for CO 2 electroreduction. 39,41 In particular, CeO x possesses unique electronic structures, abundant oxygen vacancies, as well as special redox properties, which can tune the electronic structure of metal nanomaterials through the electronic transfer between metals and CeO x . 42,43 However until now, the electronic structure modulation of metals using this method has mostly been limited to conventional phase metal nanomaterials.…”

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confidence: 99%

“…42,43 However until now, the electronic structure modulation of metals using this method has mostly been limited to conventional phase metal nanomaterials. 36,40,41 It is worth mentioning that recent studies have found that unusual phase metal nanomaterials usually feature unique electronic structures as well as improved intrinsic catalytic activity. 29,30,44,45 Therefore, the electronic structure modulation of unconventional phase metal nanomaterials could provide a feasible and effective strategy to further boost the electrocatalytic CO 2 RR performance toward practical applications.…”

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confidence: 99%

“…Very recently, the electronic structure modulation of metal nanomaterials has emerged as an effective strategy to improve the electrocatalytic CO 2 RR performance. Among different methods, constructing the metal-oxide interface has been developed as a feasible way to tune the electronic structure of metal nanostructures, such as introducing cerium oxide (CeO x ) to metals. , On the one hand, the resultant metal-oxide interface typically features superior active and highly selective sites for the electrocatalytic CO 2 RR. − On the other hand, the strong metal-oxide interaction can induce the partially charged metal surface to enrich active sites and stabilize the key intermediates for CO 2 electroreduction. , In particular, CeO x possesses unique electronic structures, abundant oxygen vacancies, as well as special redox properties, which can tune the electronic structure of metal nanomaterials through the electronic transfer between metals and CeO x . , However until now, the electronic structure modulation of metals using this method has mostly been limited to conventional phase metal nanomaterials. ,, It is worth mentioning that recent studies have found that unusual phase metal nanomaterials usually feature unique electronic structures as well as improved intrinsic catalytic activity. ,,, Therefore, the electronic structure modulation of unconventional phase metal nanomaterials could provide a feasible and effective strategy to further boost the electrocatalytic CO 2 RR performance toward practical applications.…”

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confidence: 99%

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Electronic Structure Modulation of Unconventional Phase Metal Nanomaterials for Highly Selective Carbon Dioxide Electroreduction

Wang,

Tan,

et al. 2023

ACS Materials Lett.

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Tuning the C₁/C₂ Selectivity of Electrochemical CO₂ Reduction on Cu–CeO₂ Nanorods by Oxidation State Control (Adv. Mater. 8/2023)

Cited by 6 publications

References 0 publications

Understanding the Synergistic Catalysis in Hydrogenation of Carbonyl Groups on Cu-Based Catalysts

Understanding the Synergistic Catalysis in Hydrogenation of Carbonyl Groups on Cu-Based Catalysts

Halide precursor reduction strategy to modulate bismuthene with high selectivity and wide potential window for electrochemical CO₂ reduction

Electronic Structure Modulation of Unconventional Phase Metal Nanomaterials for Highly Selective Carbon Dioxide Electroreduction

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Tuning the C1/C2 Selectivity of Electrochemical CO2 Reduction on Cu–CeO2 Nanorods by Oxidation State Control (Adv. Mater. 8/2023)

Cited by 6 publications

References 0 publications

Understanding the Synergistic Catalysis in Hydrogenation of Carbonyl Groups on Cu-Based Catalysts

Understanding the Synergistic Catalysis in Hydrogenation of Carbonyl Groups on Cu-Based Catalysts

Halide precursor reduction strategy to modulate bismuthene with high selectivity and wide potential window for electrochemical CO2 reduction

Electronic Structure Modulation of Unconventional Phase Metal Nanomaterials for Highly Selective Carbon Dioxide Electroreduction

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Tuning the C₁/C₂ Selectivity of Electrochemical CO₂ Reduction on Cu–CeO₂ Nanorods by Oxidation State Control (Adv. Mater. 8/2023)

Halide precursor reduction strategy to modulate bismuthene with high selectivity and wide potential window for electrochemical CO₂ reduction