Lattice Strain and Schottky Junction Dual Regulation Boosts Ultrafine Ruthenium Nanoparticles Anchored on a N-Modified Carbon Catalyst for H₂ Production

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(42), P. 19619 - 19626

Published: Oct. 12, 2022

Ruthenium-based materials are considered great promising candidates to replace Pt-based catalysts for hydrogen production in alkaline conditions. Herein, we adopt a facile method rationally design neoteric Schottky catalyst which uniform ultrafine ruthenium nanoparticles featuring lattice compressive stress supported on nitrogen-modified carbon nanosheets (Ru NPs/NC) efficient evolution reaction (HER). Lattice strain and junction dual regulation ensures that the Ru NPs/NC with an appropriate nitrogen content displays superb H2 media. Particularly, NPs/NC-900 1.3% attractive activity durability HER low overpotential of 19 mV at 10 mA cm-2 1.0 M KOH electrolyte. The situ X-ray absorption fine structure measurements indicate low-valence nanoparticle shrinking Ru-Ru bond acts as catalytic active site during process. Furthermore, multiple spectroscopy analysis density functional theory calculations demonstrate tunes electron adsorption center, thus enhancing activity. This strategy provides novel concept advanced electrocatalysts production.

Language: Английский

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Arming Ru with Oxygen‐Vacancy‐Enriched RuO₂ Sub‐Nanometer Skin Activates Superior Bifunctionality for pH‐Universal Overall Water Splitting

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(24)

Published: Jan. 7, 2023

Water electrolysis has been expected to assimilate the renewable yet intermediate energy-derived electricity for green H2 production. However, current benchmark anodic catalysts of Ir/Ru-based compounds suffer severely from poor dissolution resistance. Herein, an effective modification strategy is proposed by arming a sub-nanometer RuO2 skin with abundant oxygen vacancies interconnected Ru clusters/carbon hybrid microsheet (denoted as Ru@V-RuO2 /C HMS), which can not only inherit high hydrogen evolution reaction (HER) activity Ru, but more importantly, activate superior toward (OER) in both acid and alkaline conditions. Outstandingly, it achieve ultralow overpotential 176/201 mV OER 46/6 HER reach 10 mA cm-2 acidic solution, respectively. Inspiringly, overall water splitting be driven ultrasmall cell voltage 1.467/1.437 V 0.5 m SO4 /1.0 KOH, Density functional theory calculations reveal that armoring oxygen-vacancy-enriched exoskeleton cooperatively alter interfacial electronic structure make adsorption behavior intermediates much close ideal level, thus simultaneously speeding up kinetics decreasing energy barrier release.

Language: Английский

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Competitive Adsorption: Reducing the Poisoning Effect of Adsorbed Hydroxyl on Ru Single‐Atom Site with SnO₂for Efficient Hydrogen Evolution

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(39)

Published: July 21, 2022

Ruthenium (Ru) has been theoretically considered a viable alkaline hydrogen evolution reaction electrocatalyst due to its fast water dissociation kinetics. However, strong affinity the adsorbed hydroxyl (OH

Language: Английский

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Ir Nanoparticles Anchored on Metal‐Organic Frameworks for Efficient Overall Water Splitting under pH‐Universal Conditions

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(17)

Published: March 2, 2023

The construction of high-activity and low-cost electrocatalysts is critical for efficient hydrogen production by water electrolysis. Herein, we developed an advanced electrocatalyst anchoring well-dispersed Ir nanoparticles on nickel metal-organic framework (MOF) Ni-NDC (NDC: 2,6-naphthalenedicarboxylic) nanosheets. Benefiting from the strong synergy between MOF through interfacial Ni-O-Ir bonds, synthesized Ir@Ni-NDC showed exceptional electrocatalytic performance evolution reaction (HER), oxygen (OER) overall splitting in a wide pH range, superior to commercial benchmarks most reported electrocatalysts. Theoretical calculations revealed that charge redistribution bridge induced optimization H2 O, OH* H* adsorption, thus leading accelerated electrochemical kinetics HER OER. This work provides new clue exploit bifunctional pH-universal splitting.

Language: Английский

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Co-catalytic metal–support interactions in single-atom electrocatalysts

Nature Reviews Materials, Journal Year: 2024, Volume and Issue: 9(3), P. 173 - 189

Published: Jan. 10, 2024

Language: Английский

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Stabilizing Low‐Valence Single Atoms by Constructing Metalloid Tungsten Carbide Supports for Efficient Hydrogen Oxidation and Evolution

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(42)

Published: Sept. 2, 2023

Abstract Designing novel single‐atom catalysts (SACs) supports to modulate the electronic structure is crucial optimize catalytic activity, but rather challenging. Herein, a general strategy proposed utilize metalloid properties of trap and stabilize single‐atoms with low‐valence states. A series supported on surface tungsten carbide (M‐WC x , M=Ru, Ir, Pd) are rationally developed through facile pyrolysis method. Benefiting from WC exhibit weak coordination W C atoms, resulting in formation active centers similar metals. The unique metal‐metal interaction effectively stabilizes single atoms improves orbital energy level distribution sites. As expected, representative Ru‐WC exhibits superior mass activities 7.84 62.52 mg Ru −1 for hydrogen oxidation evolution reactions (HOR/HER), respectively. In‐depth mechanistic analysis demonstrates that an ideal dual‐sites cooperative mechanism achieves suitable adsorption balance H ad OH energetically favorable Volmer step. This work offers new guidance precise construction highly SACs.

Language: Английский

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Advanced electrocatalysts with unusual active sites for electrochemical water splitting

InfoMat, Journal Year: 2023, Volume and Issue: 6(1)

Published: Nov. 27, 2023

Abstract Electrochemical water splitting represents a promising technology for green hydrogen production. To design advanced electrocatalysts, it is crucial to identify their active sites and interpret the relationship between structures performance. Materials extensively studied as electrocatalysts include noble‐metal‐based (e.g., Ru, Ir, Pt) non‐noble‐metal‐based 3d transition metals) compounds. Recently, advancements in characterization techniques theoretical calculations have revealed novel unusual sites. The present review highlights latest achievements discovery identification of various unconventional electrochemical splitting, with focus on state‐of‐the‐art strategies determining true establishing structure–activity relationships. Furthermore, we discuss remaining challenges future perspectives development next‐generation By presenting fresh perspective reaction involved this aims provide valuable guidance study industrial applications. image

Language: Английский

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Ru–Cu Nanoheterostructures for Efficient Hydrogen Evolution Reaction in Alkaline Water Electrolyzers

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(39), P. 21419 - 21431

Published: Sept. 25, 2023

Combining multiple species working in tandem for different hydrogen evolution reaction (HER) steps is an effective strategy to design HER electrocatalysts. Here, we engineered a hierarchical electrode the composed of amorphous-TiO2/Cu nanorods (NRs) decorated with cost-effective Ru-Cu nanoheterostructures (Ru mass loading = 52 μg/cm2). Such exhibits stable, over 250 h, low overpotential 74 mV at -200 mA/cm2 1 M NaOH. The high activity attributed, by structural analysis, operando X-ray absorption spectroscopy, and first-principles simulations, synergistic functionalities: (1) mechanically robust, vertically aligned Cu NRs electrical conductivity porosity provide fast charge gas transfer channels; (2) Ru electronic structure, regulated size clusters surface, facilitates water dissociation (Volmer step); (3) grown atop exhibit close-to-zero Gibbs free energy adsorption, promoting Heyrovsky/Tafel steps. An alkaline electrolyzer (AEL) coupling proposed cathode stainless-steel anode can stably operate both continuous (1 A/cm2 200 h) intermittent modes (accelerated stress tests). A techno-economic analysis predicts minimal overall production cost US$2.12/kg MW AEL plant 30 year lifetime based on our single cell, hitting worldwide targets (US$2-2.5/kgH2).

Language: Английский

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Why do Single‐Atom Alloys Catalysts Outperform both Single‐Atom Catalysts and Nanocatalysts on MXene?

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(4)

Published: Dec. 1, 2023

Abstract Single‐atom alloys (SAAs), combining the advantages of single‐atom and nanoparticles (NPs), play an extremely significant role in field heterogeneous catalysis. Nevertheless, understanding catalytic mechanism SAAs catalysis reactions remains a challenge compared with single atoms NPs. Herein, ruthenium‐nickel (RuNi ) synthesized by embedding atomically dispersed Ru Ni NPs are anchored on two‐dimensional Ti 3 C 2 T x MXene. The RuNi SAA‐3 −Ti catalysts exhibit unprecedented activity for hydrogen evolution from ammonia borane (AB, NH BH hydrolysis mass‐specific (r mass value 333 L min −1 g . Theoretical calculations reveal that anchoring optimizes dissociation AB H O as well binding ability H* intermediates during due to d‐band structural modulation caused alloying effect metal‐supports interactions (MSI) This work provides useful design principles developing optimizing efficient hydrogen‐related demonstrates over energy

Language: Английский

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Cooperative Ni(Co)‐Ru‐P Sites Activate Dehydrogenation for Hydrazine Oxidation Assisting Self‐powered H₂ Production

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(35)

Published: July 10, 2023

Water electrolysis for H2 production is restricted by the sluggish oxygen evolution reaction (OER). Using thermodynamically more favorable hydrazine oxidation (HzOR) to replace OER has attracted ever-growing attention. Herein, we report a twisted NiCoP nanowire array immobilized with Ru single atoms (Ru1 -NiCoP) as superior bifunctional electrocatalyst toward both HzOR and hydrogen (HER), realizing an ultralow working potential of -60 mV overpotential 32 current density 10 mA cm-2 , respectively. Inspiringly, two-electrode electrolyzer based on overall splitting (OHzS) demonstrates outstanding activity record-high 522 at cell voltage 0.3 V. DFT calculations elucidate cooperative Ni(Co)-Ru-P sites in Ru1 -NiCoP optimize H* adsorption, enhance adsorption *N2 significantly lower energy barrier dehydrogenation. Moreover, self-powered system utilizing OHzS device driven direct fuel (DHzFC) achieve satisfactory rate 24.0 mol h-1 m-2 .

Language: Английский

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