Facet engineering accelerates spillover hydrogenation on highly diluted metal nanocatalysts

Jiang, Lizhi; Liu, Kunlong; Hung, Sung‐Fu; Zhou, Lingyun; Qin, Ruixuan; Zhang, Qinghua; Liu, Pengxin; Gu, Lin; Chen, Hao Ming; Fu, Gang; Zheng, Nanfeng

doi:10.1038/s41565-020-0746-x

Cited by 246 publications

(196 citation statements)

References 41 publications

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“…Cu(OH) 2 nanosheets without halogen elements were prepared by am odified reported method (Figure S5a). [21] Hydrogen accounted for the major reduction product over the activated Cu(OH) 2 nanosheets in the range of applied potentials (Figure S5b), while the maximum FE of C 2 H 4 products was only 22.7 %atÀ1.00 V RHE (34.2 %for total C 2+ products). Theo ther control sample was obtained by reducing the CuOHFCl nanosheets in H 2 /Ar atmosphere at 350 8 8Cf or 4h (denoted as h-CuOHFCl).…”

Section: Resultsmentioning

confidence: 98%

“…Based on the peak position of Cu LMM spectra at ≈570.1 eV, the predominating copper species on the surface of CuOHFCl‐4 and CuOHFCl‐240 catalysts were Cu + after CO 2 RR test [23] . For comparison, a halogen‐free Cu(OH) 2 nanosheet sample was prepared and tested for CA at the same potentials as CuOHFCl nanosheets [21b] . The Cu LMM spectra of Cu(OH) 2 nanosheets after CA test (denoted as Cu(OH) 2 ‐CA) showed a sharp peak at ≈568.6 eV, indicating the overwhelming metallic Cu 0 sites on the surface of Cu(OH) 2 ‐CA sample.…”

Section: Resultsmentioning

confidence: 99%

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Residual Chlorine Induced Cationic Active Species on a Porous Copper Electrocatalyst for Highly Stable Electrochemical CO₂ Reduction to C₂₊

Lawrence

et al. 2021

Angewandte Chemie

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Electrochemical carbon dioxide (CO 2 )r eduction reaction (CO 2 RR) is an attractive approach to deal with the emission of CO 2 and to produce valuable fuels and chemicals in ac arbon-neutral way.M any efforts have been devoted to boost the activity and selectivity of high-value multicarbon products (C 2+ )o nC u-based electrocatalysts.H owever,C ubased CO 2 RR electrocatalysts suffer from poor catalytic stability mainly due to the structural degradation and loss of active species under CO 2 RR condition. To date,most reported Cu-based electrocatalysts present stabilities over dozenso f hours,w hich limits the advance of Cu-based electrocatalysts for CO 2 RR. Herein, ap orous chlorine-doped Cu electrocatalyst exhibits high C 2+ Faradaic efficiency (FE) of 53.8 %at À1.00 Vv ersus reversible hydrogen electrode (V RHE ). Importantly,the catalyst exhibited an outstanding catalytic stability in long-term electrocatalysis over 240 h. Experimental results show that the chlorine-induced stable cationic Cu 0 /Cu + species and the well-preserved structure with abundant active sites are critical to the high FE of C 2+ in the long-term run of electrochemical CO 2 reduction.

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Section: Resultsmentioning

confidence: 98%

Section: Resultsmentioning

confidence: 99%

Residual Chlorine Induced Cationic Active Species on a Porous Copper Electrocatalyst for Highly Stable Electrochemical CO₂ Reduction to C₂₊

Lawrence

et al. 2021

Angewandte Chemie

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“…Evidences for hydrogen spillover in Pt 2 Ir 1 /CoP. Inspired by the previous recognition that hydrogen spillover was highly relevant to the properties of supports in heterogeneous catalysis 20,64 , it was expected that the hydrogen adsorption and desorption behavior on CoP support in Pt 2 Ir 1 /CoP catalysts should be substantially different if the hydrogen spillover phenomenon indeed exists. In situ monitoring the hydrogen adsorption and desorption behaviors on catalysts can provide strong evidence to verify the occurrence of hydrogen spillover in Pt 2 Ir 1 /CoP catalysts.…”

Section: Resultsmentioning

confidence: 99%

A fundamental viewpoint on the hydrogen spillover phenomenon of electrocatalytic hydrogen evolution

et al. 2021

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Hydrogen spillover phenomenon of metal-supported electrocatalysts can significantly impact their activity in hydrogen evolution reaction (HER). However, design of active electrocatalysts faces grand challenges due to the insufficient understandings on how to overcome this thermodynamically and kinetically adverse process. Here we theoretically profile that the interfacial charge accumulation induces by the large work function difference between metal and support (∆Φ) and sequentially strong interfacial proton adsorption construct a high energy barrier for hydrogen transfer. Theoretical simulations and control experiments rationalize that small ∆Φ induces interfacial charge dilution and relocation, thereby weakening interfacial proton adsorption and enabling efficient hydrogen spillover for HER. Experimentally, a series of Pt alloys-CoP catalysts with tailorable ∆Φ show a strong ∆Φ-dependent HER activity, in which PtIr/CoP with the smallest ∆Φ = 0.02 eV delivers the best HER performance. These findings have conclusively identified ∆Φ as the criterion in guiding the design of hydrogen spillover-based binary HER electrocatalysts.

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“…[25][26][27] Currently, the difficulty in controlling the favorable interactions and synergistic effects in SAAs has limited their applications in electrocatalysis. [28][29][30][31][32][33][34] Intermetallics possess long-range atomic ordering and isolated metallic atoms on the surface, which could serve as a promising matrix to construct SAAs, yet that has not been explored.…”

Section: Introductionmentioning

confidence: 99%

A Tensile‐Strained Pt–Rh Single‐Atom Alloy Remarkably Boosts Ethanol Oxidation

et al. 2021

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which is also considered a biorenew able energy carrier. However, the anodic ethanol oxidation reaction (EOR) is a complicated and kinetically sluggish process, involving the transfer of multiple electrons and various reaction intermediates and products. Typically, the C2-pathway dominates the EOR in both acidic and alkaline electrolytes, resulting in the formation of acetic acid or acetate by delivering four electrons, and acetaldehyde by delivering two electrons, respectively. The C1-pathway, which involves complete oxidation and the transfer of 12 electrons generating CO 2 or carbonate, is preferred to the C2-pathway, aiming for maximum DEFCs efficiency. [1][2][3][4][5] Specially, highly efficient catalysts have been developed by engineering Pt-based nanocrystals, and the C1-pathway selectivity has been promoted by Rh-based catalysts. [6][7][8][9] In designing electrochemical surfaces toward maximum performance, modifying the electronic structure and strain of catalytic surfaces are considered state-of-the-art strategies, which can for instance be achieved by introducing metals with different intrinsic reactivities and constructing core-shell nanostructures, respectively. [10][11][12][13][14][15] Combining these approaches in a rational manner would be a promising way to substantially improve the EOR, yet the underlying knowledge about their contributions is largely lacking. [10][11][12][13][14][15][16][17][18] Therefore, it is highly desirable to employ tailored nanostructures to resolve these important issues and contribute to the practical deployment of DEFCs by identifying versatile EOR electrocatalysts possessing high atom utilization of noble metals, high mass-normalized activity at low overpotentials, high C1-pathway selectivity, long-term durability, and superior anti-poisoning ability. [1] To maximize atom utilization, single-atom catalysts (SACs) have emerged as one of the most promising frontiers in materials chemistry. [19][20][21] Using specific support materials such as reducible metal oxides, activated carbons, and anisotropic materials such as MoS 2 , single atoms of catalytically metals can be stabilized, which exhibit intriguing physicochemical properties compared with their counterpart clusters and nanoparticles. [22][23][24] Typically, high-performance EOR catalysts should facilitate multiple dehydrogenation and oxidation steps as well as CC bond cleavage reactions. All these reactions typically require ensembles of surface metal atoms, implying that thisThe rational design and control of electrocatalysts at single-atomic sites could enable unprecedented atomic utilization and catalytic properties, yet it remains challenging in multimetallic alloys. Herein, the first example of isolated Rh atoms on ordered PtBi nanoplates (PtBi-Rh 1 ) by atomic galvanic replacement, and their subsequent transformation into a tensile-strained Pt-Rh single-atom alloy (PtBi@PtRh 1 ) via electrochemical dealloying are presented. Benefiting from the Rh 1 -tailored Pt (110) surface with tensile strain, the PtBi@...

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Facet engineering accelerates spillover hydrogenation on highly diluted metal nanocatalysts

Cited by 246 publications

References 41 publications

Residual Chlorine Induced Cationic Active Species on a Porous Copper Electrocatalyst for Highly Stable Electrochemical CO₂ Reduction to C₂₊

Residual Chlorine Induced Cationic Active Species on a Porous Copper Electrocatalyst for Highly Stable Electrochemical CO₂ Reduction to C₂₊

A fundamental viewpoint on the hydrogen spillover phenomenon of electrocatalytic hydrogen evolution

A Tensile‐Strained Pt–Rh Single‐Atom Alloy Remarkably Boosts Ethanol Oxidation

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Facet engineering accelerates spillover hydrogenation on highly diluted metal nanocatalysts

Cited by 246 publications

References 41 publications

Residual Chlorine Induced Cationic Active Species on a Porous Copper Electrocatalyst for Highly Stable Electrochemical CO2 Reduction to C2+

Residual Chlorine Induced Cationic Active Species on a Porous Copper Electrocatalyst for Highly Stable Electrochemical CO2 Reduction to C2+

A fundamental viewpoint on the hydrogen spillover phenomenon of electrocatalytic hydrogen evolution

A Tensile‐Strained Pt–Rh Single‐Atom Alloy Remarkably Boosts Ethanol Oxidation

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Product

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Residual Chlorine Induced Cationic Active Species on a Porous Copper Electrocatalyst for Highly Stable Electrochemical CO₂ Reduction to C₂₊

Residual Chlorine Induced Cationic Active Species on a Porous Copper Electrocatalyst for Highly Stable Electrochemical CO₂ Reduction to C₂₊