Surface electron–hydronium ion-pair bound to silver and gold cathodes: A density functional theoretical study of photocatalytic hydrogen evolution reaction

Finding a low-cost and stable electrocatalyst for hydrogen evolution reaction (HER) as a replacement for scarce and expensive precious metal catalysts has attracted significant interest from chemical and materials research communities. Here, we demonstrate an organic catalyst based on 2,2’-dipyridylamine (dpa) molecules adsorbed on carbon surface, which shows remarkable hydrogen evolution activity and performance durability in strongly acidic polymer electrolytes without involving any metal. The HER onset potential at dpa adsorbed on carbon has been found to be less than 50 mV in sulfuric acid and in a Nafion-based membrane electrode assembly (MEA). At the same time, this catalyst has shown no performance loss in a 60-hour durability test. The HER reaction mechanisms and the low onset overpotential in this system are revealed based on electrochemical study. Density functional theory (DFT) calculations suggest that the pyridyl-N functions as the active site for H adsorption with a free energy of -0.13 eV, in agreement with the unusually low onset overpotential for an organic molecular catalyst.<br>

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2,2’-Dipyridylamine as Organic Molecular Electrocatalyst for Hydrogen Evolution Reaction in Acidic Electrolytes

10.26434/chemrxiv.8273627 ◽

2019 ◽

Author(s):

Xi Yin ◽

Ling Lin ◽

Hoon T. Chung ◽

Ulises Martinez ◽

Andrew M. Baker ◽

...

Keyword(s):

Hydrogen Evolution ◽

Hydrogen Evolution Reaction ◽

Density Functional ◽

Low Cost ◽

Membrane Electrode Assembly ◽

Carbon Surface ◽

Membrane Electrode ◽

Durability Test ◽

Onset Potential ◽

Precious Metal Catalysts

Finding a low-cost and stable electrocatalyst for hydrogen evolution reaction (HER) as a replacement for scarce and expensive precious metal catalysts has attracted significant interest from chemical and materials research communities. Here, we demonstrate an organic catalyst based on 2,2’-dipyridylamine (dpa) molecules adsorbed on carbon surface, which shows remarkable hydrogen evolution activity and performance durability in strongly acidic polymer electrolytes without involving any metal. The HER onset potential at dpa adsorbed on carbon has been found to be less than 50 mV in sulfuric acid and in a Nafion-based membrane electrode assembly (MEA). At the same time, this catalyst has shown no performance loss in a 60-hour durability test. The HER reaction mechanisms and the low onset overpotential in this system are revealed based on electrochemical study. Density functional theory (DFT) calculations suggest that the pyridyl-N functions as the active site for H adsorption with a free energy of -0.13 eV, in agreement with the unusually low onset overpotential for an organic molecular catalyst.<br>

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Engineering single-atomic ruthenium catalytic sites on defective nickel-iron layered double hydroxide for overall water splitting

Nature Communications ◽

10.1038/s41467-021-24828-9 ◽

2021 ◽

Vol 12 (1) ◽

Author(s):

Panlong Zhai ◽

Mingyue Xia ◽

Yunzhen Wu ◽

Guanghui Zhang ◽

Junfeng Gao ◽

...

Keyword(s):

Hydrogen Evolution ◽

Water Splitting ◽

Layered Double Hydroxide ◽

Hydrogen Evolution Reaction ◽

Active Sites ◽

Density Functional ◽

Rational Design ◽

Single Atom ◽

Nickel Iron ◽

Double Hydroxide

AbstractRational design of single atom catalyst is critical for efficient sustainable energy conversion. However, the atomic-level control of active sites is essential for electrocatalytic materials in alkaline electrolyte. Moreover, well-defined surface structures lead to in-depth understanding of catalytic mechanisms. Herein, we report a single-atomic-site ruthenium stabilized on defective nickel-iron layered double hydroxide nanosheets (Ru1/D-NiFe LDH). Under precise regulation of local coordination environments of catalytically active sites and the existence of the defects, Ru1/D-NiFe LDH delivers an ultralow overpotential of 18 mV at 10 mA cm−2 for hydrogen evolution reaction, surpassing the commercial Pt/C catalyst. Density functional theory calculations reveal that Ru1/D-NiFe LDH optimizes the adsorption energies of intermediates for hydrogen evolution reaction and promotes the O–O coupling at a Ru–O active site for oxygen evolution reaction. The Ru1/D-NiFe LDH as an ideal model reveals superior water splitting performance with potential for the development of promising water-alkali electrocatalysts.

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Modulating electronic structure of metal-organic frameworks by introducing atomically dispersed Ru for efficient hydrogen evolution

Nature Communications ◽

10.1038/s41467-021-21595-5 ◽

2021 ◽

Vol 12 (1) ◽

Cited By ~ 1

Author(s):

Yamei Sun ◽

Ziqian Xue ◽

Qinglin Liu ◽

Yaling Jia ◽

Yinle Li ◽

...

Keyword(s):

Electronic Structure ◽

Hydrogen Evolution ◽

Hydrogen Evolution Reaction ◽

Density Functional ◽

Metal Organic Frameworks ◽

Catalyst Design ◽

Single Atom ◽

Hydrogen Energy ◽

Structure Of Metal ◽

Metal Organic

AbstractDeveloping high-performance electrocatalysts toward hydrogen evolution reaction is important for clean and sustainable hydrogen energy, yet still challenging. Herein, we report a single-atom strategy to construct excellent metal-organic frameworks (MOFs) hydrogen evolution reaction electrocatalyst (NiRu0.13-BDC) by introducing atomically dispersed Ru. Significantly, the obtained NiRu0.13-BDC exhibits outstanding hydrogen evolution activity in all pH, especially with a low overpotential of 36 mV at a current density of 10 mA cm−2 in 1 M phosphate buffered saline solution, which is comparable to commercial Pt/C. X-ray absorption fine structures and the density functional theory calculations reveal that introducing Ru single-atom can modulate electronic structure of metal center in the MOF, leading to the optimization of binding strength for H2O and H*, and the enhancement of HER performance. This work establishes single-atom strategy as an efficient approach to modulate electronic structure of MOFs for catalyst design.

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Rationally Designed Ta3N5@ReS2 Heterojunctions for Promoted Photocatalytic Hydrogen Production

Journal of Materials Chemistry A ◽

10.1039/d1ta09030e ◽

2021 ◽

Author(s):

Xiaoqiang Zhan ◽

Zhi Fang ◽

Bing Li ◽

Haitao Zhang ◽

Leyao Xu ◽

...

Keyword(s):

Hydrogen Production ◽

Hydrogen Evolution ◽

Hydrogen Evolution Reaction ◽

Photocatalytic Hydrogen Production ◽

Photocatalytic Hydrogen Evolution ◽

Highly Active ◽

Adsorption Processes

Highly-active heterojunctions hold the pivotal function in photocatalytic hydrogen evolution reaction (HER). Herein, Ta3N5@ReS2 photocatalysts are rationally designed via the combination of template-assisted, hydrothermal and solution-adsorption processes, in which few...

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Identifying the catalytically active sites on the layered tri-chalcogenide compounds CoPS3 and NiPS3 for efficient hydrogen evolution reaction

Physical Chemistry Chemical Physics ◽

10.1039/d1cp01539g ◽

2021 ◽

Author(s):

Khorsed Alam ◽

Tisita Das ◽

Sudip Chakraborty ◽

Prasenjit Sen

Keyword(s):

Density Functional Theory ◽

Electronic Structure ◽

Hydrogen Evolution ◽

Hydrogen Evolution Reaction ◽

Active Sites ◽

Density Functional ◽

Electronic Structure Calculations ◽

Functional Theory ◽

Catalytically Active ◽

Structure Calculations

Electronic structure calculations based on density functional theory are used to identify the catalytically active sites for the hydrogen evolution reaction on single layers of the two transition metal tri-chalcogenide...

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First-Principles Mechanistic Insights into the Hydrogen Evolution Reaction on Ni2P Electrocatalyst in Alkaline Medium

Catalysts ◽

10.3390/catal10030307 ◽

2020 ◽

Vol 10 (3) ◽

pp. 307

Author(s):

Russell W. Cross ◽

Nelson Y. Dzade

Keyword(s):

Hydrogen Evolution ◽

Hydrogen Evolution Reaction ◽

Density Functional ◽

Hydrogen Adsorption ◽

Density Functional Theory Calculations ◽

Transition Metal Doping ◽

Experimental Conditions ◽

Functional Theory ◽

Alkaline Conditions ◽

Modification Of The Surface

Nickel phosphide (Ni2P) is a promising material for the electrocatalytic generation of hydrogen from water. Here, we present a chemical picture of the fundamental mechanism of Volmer–Tafel steps in hydrogen evolution reaction (HER) activity under alkaline conditions at the (0001) and (10 1 ¯ 0) surfaces of Ni2P using dispersion-corrected density functional theory calculations. Two terminations of each surface (Ni3P2- and Ni3P-terminated (0001); and Ni2P- and NiP-terminated (10 1 ¯ 0)), which have been shown to coexist in Ni2P samples depending on the experimental conditions, were studied. Water adsorption on the different terminations of the Ni2P (0001) and (10 1 ¯ 0) surfaces is shown to be exothermic (binding energy in the range of 0.33−0.68 eV) and characterized by negligible charge transfer to/from the catalyst surface (0.01−0.04 e−). High activation energy barriers (0.86−1.53 eV) were predicted for the dissociation of water on each termination of the Ni2P (0001) and (10 1 ¯ 0) surfaces, indicating sluggish kinetics for the initial Volmer step in the hydrogen evolution reaction over a Ni2P catalyst. Based on the predicted Gibbs free energy of hydrogen adsorption (ΔGH*) at different surface sites, we found that the presence of Ni3-hollow sites on the (0001) surface and bridge Ni-Ni sites on the (10 1 ¯ 0) surface bind the H atom too strongly. To achieve facile kinetics for both the Volmer and Heyrovsky–Tafel steps, modification of the surface structure and tuning of the electronic properties through transition metal doping is recommended as an important strategy.

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MXenes: Applications in electrocatalytic, photocatalytic hydrogen evolution reaction and CO2 reduction

Molecular Catalysis ◽

10.1016/j.mcat.2020.110850 ◽

2020 ◽

Vol 486 ◽

pp. 110850 ◽

Cited By ~ 11

Author(s):

Thang Phan Nguyen ◽

Dinh Minh Tuan Nguyen ◽

Dai Lam Tran ◽

Hai Khoa Le ◽

Dai-Viet N. Vo ◽

...

Keyword(s):

Hydrogen Evolution ◽

Hydrogen Evolution Reaction ◽

Co2 Reduction ◽

Photocatalytic Hydrogen Evolution

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Two dimensional MoS2 meets porphyrins via intercalation to enhance the electrocatalytic activity toward hydrogen evolution

Nanoscale ◽

10.1039/c8nr10165e ◽

2019 ◽

Vol 11 (9) ◽

pp. 3780-3785 ◽

Cited By ~ 7

Author(s):

Ik Seon Kwon ◽

In Hye Kwak ◽

Hafiz Ghulam Abbas ◽

Hee Won Seo ◽

Jaemin Seo ◽

...

Keyword(s):

Density Functional Theory ◽

Hydrogen Evolution ◽

Hydrogen Evolution Reaction ◽

Electrocatalytic Activity ◽

Density Functional ◽

Density Functional Theory Calculations ◽

Two Dimensional ◽

Functional Theory ◽

Spin Polarized

Mn-Porphyrin-MoS2 exhibits excellent electrocatalytic activity toward the hydrogen evolution reaction, which is supported by spin-polarized density functional theory calculations.

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Optimization of the facet structure of cobalt oxide catalysts for enhanced hydrogen evolution reaction

Catalysis Science & Technology ◽

10.1039/c9cy01900f ◽

2020 ◽

Vol 10 (4) ◽

pp. 1040-1047 ◽

Cited By ~ 4

Author(s):

Minghong Wu ◽

Shuqiang Ke ◽

Wenqian Chen ◽

Shaomei Zhang ◽

Min Zhu ◽

...

Keyword(s):

Cobalt Oxide ◽

Hydrogen Evolution ◽

Hydrogen Evolution Reaction ◽

Oxide Catalysts ◽

Photocatalytic Hydrogen Evolution ◽

Facet Structure

The three different exposed crystal planes of Co3O4 catalysts, in which the {112} and {011} planes with abundant Co3+ sites exhibited photocatalytic hydrogen evolution activity superior to that of the {001} plane.

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