Exceptional hydrogen evolution in acid enabled by a multi-function-site complex oxide via atomic-scale hydrogen spillover

Abstract Improving the catalytic efficiency of platinum (Pt) for hydrogen evolution reaction (HER) is crucial for water splitting technologies, and hydrogen spillover has emerged as a new frontier in designing the binary-component Pt/support HER electrocatalysts. However, such binary catalysts always suffer from long reaction pathway, undesirable interfacial barrier, and complicated synthesis processes. Here we report a single-phase complex oxide La2Sr2PtO7+δ as a high-performance HER electrocatalysts in acidic media via a unique atomic-scale hydrogen spillover effect between multifunctional catalytic sites. With insights from theoretical calculations, a possible synergistic mechanism involving the hydrogen spillover channel from OLa site→La-Pt bridge site→Pt site is proposed; namely, the OLa site enriches proton, the La-Pt bridge site with thermo-neutral H* adsorption facilitates the hydrogen spillover and H2 generation, and Pt site favors the final H2 desorption. Benefiting from such unusual phenomenon, the resulting La2Sr2PtO7+δ exhibits an exceptional HER electrode activity with low overpotential of 13 mV at 10 mA cm− 2 and small Tafel slope of 22 mV dec− 1, and significantly enhanced intrinsic activity and durability than commercial Pt black catalyst.

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Platinum–copper single atom alloy catalysts with high performance towards glycerol hydrogenolysis

Nature Communications ◽

10.1038/s41467-019-13685-2 ◽

2019 ◽

Vol 10 (1) ◽

Cited By ~ 33

Author(s):

Xi Zhang ◽

Guoqing Cui ◽

Haisong Feng ◽

Lifang Chen ◽

Hui Wang ◽

...

Keyword(s):

Active Sites ◽

High Performance ◽

Reaction Pathway ◽

Theoretical Calculations ◽

Experimental Studies ◽

Value Added ◽

Catalytic Performance ◽

Single Atom ◽

Glycerol Hydrogenolysis ◽

Single Atom Alloy

AbstractSelective hydrogenolysis of biomass-derived glycerol to propanediol is an important reaction to produce high value-added chemicals but remains a big challenge. Herein we report a PtCu single atom alloy (SAA) catalyst with single Pt atom dispersed on Cu nanoclusters, which exhibits dramatically boosted catalytic performance (yield: 98.8%) towards glycerol hydrogenolysis to 1,2-propanediol. Remarkably, the turnover frequency reaches up to 2.6 × 103 molglycerol·molPtCu–SAA−1·h−1, which is to our knowledge the largest value among reported heterogeneous metal catalysts. Both in situ experimental studies and theoretical calculations verify interface sites of PtCu–SAA serve as intrinsic active sites, in which the single Pt atom facilitates the breakage of central C–H bond whilst the terminal C–O bond undergoes dissociation adsorption on adjacent Cu atom. This interfacial synergistic catalysis based on PtCu–SAA changes the reaction pathway with a decreased activation energy, which can be extended to other noble metal alloy systems.

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Dynamic oxygen adsorption on single-atomic Ruthenium catalyst with high performance for acidic oxygen evolution reaction

Nature Communications ◽

10.1038/s41467-019-12886-z ◽

2019 ◽

Vol 10 (1) ◽

Cited By ~ 52

Author(s):

Linlin Cao ◽

Qiquan Luo ◽

Jiajia Chen ◽

Lan Wang ◽

Yue Lin ◽

...

Keyword(s):

Oxygen Evolution ◽

Oxygen Evolution Reaction ◽

High Performance ◽

Theoretical Calculations ◽

Cost Effective ◽

Carbon Support ◽

Oxygen Adsorption ◽

Single Atom ◽

Intrinsic Activity ◽

Acid Media

Abstract Achieving active and stable oxygen evolution reaction (OER) in acid media based on single-atom catalysts is highly promising for cost-effective and sustainable energy supply in proton electrolyte membrane electrolyzers. Here, we report an atomically dispersed Ru1-N4 site anchored on nitrogen-carbon support (Ru-N-C) as an efficient and durable electrocatalyst for acidic OER. The single-atom Ru-N-C catalyst delivers an exceptionally intrinsic activity, reaching a mass activity as high as 3571 A gmetal−1 and turnover frequency of 3348 O2 h−1 with a low overpotential of 267 mV at a current density of 10 mA cm−2. The catalyst shows no evident deactivation or decomposition after 30-hour operation in acidic environment. Operando synchrotron radiation X-ray absorption spectroscopy and infrared spectroscopy identify the dynamic adsorption of single oxygen atom on Ru site under working potentials, and theoretical calculations demonstrate that the O-Ru1-N4 site is responsible for the high OER activity and stability.

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Electrocatalytic glycerol oxidation with concurrent hydrogen evolution utilizing an efficient MoOx/Pt catalyst

10.21203/rs.3.rs-113878/v1 ◽

2020 ◽

Author(s):

Mats Johnsson ◽

Xiaowen Yu ◽

Egon Campos dos Santos ◽

Jai White ◽

German Salazar-Alvarez ◽

...

Keyword(s):

Hydrogen Evolution ◽

High Performance ◽

Theoretical Calculations ◽

Value Added ◽

Pt Nanoparticles ◽

Cell Voltage ◽

Water Electrolysis ◽

Pt Catalyst ◽

Electronic Interaction ◽

Glycerol Oxidation

Abstract Glycerol electrolysis affords a green and energetically favorable route for the production of value-added chemicals at the anode and H2 production in parallel at the cathode. Here, we report a novel and facile method for trapping Pt nanoparticles at oxygen vacancies of molybdenum oxide (MoOx) nanosheets, yielding a high-performance MoOx/Pt composite electrocatalyst for both the glycerol oxidation reaction (GOR) and the hydrogen evolution reaction (HER) in alkaline electrolytes. Combined electrochemical experiments and theoretical calculations revealed the important role of MoOx nanosheets for the adsorption of glycerol molecules in GOR and the dissociation of water molecules in HER, as well as the strong electronic interaction with Pt. With MoOx/Pt electrodes serving as both cathode and anode, we achieve two-electrode glycerol electrolysis at a cell voltage of 0.70 V to reach a current density of 10 mA cm− 2, which is 0.90 V less than that required for water electrolysis.

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Phase reconfiguration of multivalent nickel sulfides in hydrogen evolution

10.21203/rs.3.rs-167398/v1 ◽

2021 ◽

Author(s):

Yu Sun ◽

Jing Wu ◽

Zheng Zhang ◽

Qingliang Liao ◽

Suicai Zhang ◽

...

Keyword(s):

Hydrogen Evolution ◽

Theoretical Calculations ◽

Catalyst Design ◽

Transition Metal Catalysts ◽

Operating Conditions ◽

Atomic Scale ◽

Dynamic Evolution ◽

Dynamic Reconstruction ◽

Time Dynamic ◽

Valence States

Abstract Deciphering the dynamic evolution of catalysts’ atomic and electronic structure in operating conditions is pivotal for unraveling the activity origin and improving catalyst design. Earth-abundant transition metal catalysts have shown efficient catalytic efficiency and are attractive due to sustainable and economic considerations. However, the dynamic evolution process during their whole service time remains elusive, which is greatly complicated by the multiple component and valence states as well as the structural complexity of materials. Here in this work, we investigated the atomic-scale evolution of multivalent nickel-based sulfides (from NiS2 to α-NiS, β-NiS and Ni3S4) as model catalysts for hydrogen evolution reaction (HER), via operando Raman and X-ray absorption spectroscopies corroborated by theoretical calculations. Dynamic reconstruction propagating from surface to bulk, mediated by sulphur vacancy, has been demonstrated for these materials, all with the terminated Ni3S2 phase on catalyst surface being responsible for subsequent catalysis. Partial Fe substitution prompts such reconfiguration process and hence improves HER performance, which establishes the dynamic working mechanism of widely-adopted doping strategy. We unprecedentedly reveal the dynamic reconstruction with lower valence state tendency of transition metals in the catalytically terminated phase during HER, and the life-time dynamic correlation between structure and activity, providing insights into future catalyst design.

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A CoMoO4–Co2Mo3O8 heterostructure with valence-rich molybdenum for a high-performance hydrogen evolution reaction in alkaline solution

Journal of Materials Chemistry A ◽

10.1039/c9ta04180j ◽

2019 ◽

Vol 7 (28) ◽

pp. 16761-16769 ◽

Cited By ~ 9

Author(s):

Zheng Liu ◽

Changhong Zhan ◽

Linkai Peng ◽

Yang Cao ◽

Yong Chen ◽

...

Keyword(s):

Hydrothermal Synthesis ◽

Hydrogen Evolution ◽

Hydrogen Evolution Reaction ◽

Alkaline Solution ◽

High Performance ◽

Hydrogen Reduction ◽

Intrinsic Activity ◽

Step Method ◽

Hierarchical Nanostructures ◽

Reduction Treatment

The heterostructure CoMoO4–Co2Mo3O8 was prepared by a two-step method, including hydrothermal synthesis of CoMoO4 nanowire and subsequent hydrogen reduction treatment of CoMoO4. Due to hierarchical nanostructures of CoMoO4–Co2Mo3O8 facilitated intrinsic activity and conductivity, the outstanding performance for HER, surpassing most cobalt–molybdenum bimetal oxide.

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Evoking ordered vacancies in metallic nanostructures toward a vacated Barlow packing for high-performance hydrogen evolution

Science Advances ◽

10.1126/sciadv.abd6647 ◽

2021 ◽

Vol 7 (13) ◽

pp. eabd6647

Author(s):

Zhicheng Zhang ◽

Guigao Liu ◽

Xiaoya Cui ◽

Yue Gong ◽

Ding Yi ◽

...

Keyword(s):

Hydrogen Evolution ◽

High Performance ◽

Theoretical Calculations ◽

Metallic Nanostructures ◽

Alkaline Media ◽

Hexagonal Close Packed ◽

Close Packed Structure ◽

Hexagonal Close Packed Structure ◽

Packed Structure ◽

Structural Aspects

Metallic nanostructures are commonly densely packed into a few packing variants with slightly different atomic packing factors. The structural aspects and physicochemical properties related with the vacancies in such nanostructures are rarely explored because of lack of an effective way to control the introduction of vacancy sites. Highly voided metallic nanostructures with ordered vacancies are however energetically high lying and very difficult to synthesize. Here, we report a chemical method for synthesis of hierarchical Rh nanostructures (Rh NSs) composed of ultrathin nanosheets, composed of hexagonal close-packed structure embedded with nanodomains that adopt a vacated Barlow packing with ordered vacancies. The obtained Rh NSs exhibit remarkably enhanced electrocatalytic activity and stability toward the hydrogen evolution reaction (HER) in alkaline media. Theoretical calculations reveal that the exceptional electrocatalytic performance of Rh NSs originates from their unique vacancy structures, which facilitate the adsorption and dissociation of H2O in the HER.

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Rugae-like FeP nanocrystal assembly on a carbon cloth: an exceptionally efficient and stable cathode for hydrogen evolution

Nanoscale ◽

10.1039/c5nr02375k ◽

2015 ◽

Vol 7 (25) ◽

pp. 10974-10981 ◽

Cited By ~ 95

Author(s):

Xiulin Yang ◽

Ang-Yu Lu ◽

Yihan Zhu ◽

Shixiong Min ◽

Mohamed Nejib Hedhili ◽

...

Keyword(s):

Gas Phase ◽

Surface Area ◽

Hydrogen Evolution ◽

Hydrogen Generation ◽

High Surface ◽

High Surface Area ◽

Catalytic Efficiency ◽

Carbon Cloth ◽

Nanocrystal Assembly

High surface area FeP nanosheets on a carbon cloth were prepared by gas phase phosphidation of electroplated FeOOH, which exhibit exceptionally high catalytic efficiency and stability for hydrogen generation.

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Synthesis of hierarchical MoSe2 nanolayers on sodium sulfide crystals for electrocatalytic hydrogen evolution

CrystEngComm ◽

10.1039/d1ce00831e ◽

2021 ◽

Author(s):

Xiaoshuang Chen ◽

Meina Ju ◽

Kun Song ◽

Guoli Chen ◽

Rui Yang ◽

...

Keyword(s):

Catalytic Activity ◽

Hydrogen Evolution ◽

High Performance ◽

Sodium Sulfide ◽

Hydrogen Generation ◽

Clean Energy

Hydrogen generation via water electroreduction is a pivotal portion of exploiting clean-energy skills. Nevertheless, developing a low price and high-performance catalytic activity substance to take the place of expensively precious...

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