Tailoring Competitive Adsorption Sites by Oxygen‐Vacancy on Cobalt Oxides to Enhance the Electrooxidation of Biomass

Advanced Materials, Journal Year: 2021, Volume and Issue: 34(2)

Published: Oct. 17, 2021

The electrooxidation of 5-hydroxymethylfurfural (HMF) offers a promising green route to attain high-value chemicals from biomass. HMF reaction (HMFOR) is complicated process involving the combined adsorption and coupling organic molecules OH- on electrode surface. An in-depth understanding these sites processes electrocatalysts fundamentally important. Herein, behavior , role oxygen vacancy Co3 O4 are initially unraveled. Correspondingly, instead competitive metal sites, it observed that can fill into (Vo) prior couple with through lattice oxidation process, which could accelerate rate-determining step dehydrogenation 5-hydroxymethyl-2-furancarboxylic acid (HMFCA) intermediates. With modulated as-designed Vo-Co3 shows excellent activity for HMFOR earlier potential 90 120 mV at 10 mA cm-2 in 1 m KOH PBS solution. This work sheds insight catalytic mechanism vacancy, benefits designing novel modulate multi-molecules behaviors.

Language: Английский

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Platinum Modulates Redox Properties and 5‐Hydroxymethylfurfural Adsorption Kinetics of Ni(OH)₂ for Biomass Upgrading

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(42), P. 22908 - 22914

Published: Aug. 18, 2021

Abstract Nickel hydroxide (Ni(OH) 2 ) is a promising electrocatalyst for the 5‐hydroxymethylfurfural oxidation reaction (HMFOR) and dehydronated intermediates Ni(OH)O species are proved to be active sites HMFOR. In this study, Ni(OH) modified by platinum adjust electronic structure current density of HMFOR improves 8.2 times at Pt/Ni(OH) electrode compared with that on electrode. Operando methods reveal introduction Pt optimized redox property accelerate formation during catalytic process. Theoretical studies demonstrate enhanced kinetics originates from reduced dehydrogenation energy . The product analysis transition state simulation prove also reduces adsorption HMF behavior as can act site HMF. Overall, work here provides strategy design an efficient universal nickel‐based catalyst electro‐oxidation, which extended other Ni‐based catalysts such Ni(HCO 3 NiO.

Language: Английский

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Formation and Stabilization of NiOOH by Introducing α‐FeOOH in LDH: Composite Electrocatalyst for Oxygen Evolution and Urea Oxidation Reactions

Advanced Materials, Journal Year: 2022, Volume and Issue: 35(7)

Published: Nov. 19, 2022

NiOOH is considered as the most active intermediate during electrochemical oxidation reaction, however, it hard to directly synthesize due high energy. Herein, theoretical calculations predict that α-FeOOH enables a decline in formation energy and an improvement stabilization of NiFe-based layered double hydroxide (LDH). Inspiringly, composite composed LDH well-designed successfully fabricated hydrothermal treatment by adding extra Fe3+ resource, stable obtained following electro-oxidation method. Benefiting from strong electron-capturing capability α-FeOOH, efficiently promotes charge redistribution around Ni/Fe sites activates Ni atoms LDH, verified X-ray photoelectron spectra (XPS) absorption (XAS). The d-band center optimized balances desorption energy, thus Gibbs free barrier lowered dramatically toward oxygen evolution reaction (OER) urea (UOR), finally showing outstanding overpotential 195 mV potential 1.35 V at 10 mA cm-2 , respectively. This study provides novel strategy construct highly efficient catalysts via introduction new phase for complex multiple-electron reactions.

Language: Английский

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Bifunctional Electrocatalysts for Overall and Hybrid Water Splitting

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(7), P. 3694 - 3812

Published: March 22, 2024

Electrocatalytic water splitting driven by renewable electricity has been recognized as a promising approach for green hydrogen production. Different from conventional strategies in developing electrocatalysts the two half-reactions of (e.g., and oxygen evolution reactions, HER OER) separately, there growing interest designing bifunctional electrocatalysts, which are able to catalyze both OER. In addition, considering high overpotentials required OER while limited value produced oxygen, is another rapidly exploring alternative oxidation reactions replace hybrid toward energy-efficient generation. This Review begins with an introduction on fundamental aspects splitting, followed thorough discussion various physicochemical characterization techniques that frequently employed probing active sites, emphasis reconstruction during redox electrolysis. The design, synthesis, performance diverse based noble metals, nonprecious metal-free nanocarbons, overall acidic alkaline electrolytes, thoroughly summarized compared. Next, their application also presented, wherein anodic include sacrificing agents oxidation, pollutants oxidative degradation, organics upgrading. Finally, concise statement current challenges future opportunities presented hope guiding endeavors quest sustainable

Language: Английский

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Progress in Hydrogen Production Coupled with Electrochemical Oxidation of Small Molecules

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(51)

Published: Oct. 6, 2022

Abstract The electrochemical oxidation of small molecules to generate value‐added products has gained enormous interest in recent years because the advantages benign operation conditions, high conversion efficiency and selectivity, absence external oxidizing agents, eco‐friendliness. Coupling replace oxygen evolution reaction (OER) at anode hydrogen (HER) cathode an electrolyzer would simultaneously realize generation high‐value chemicals or pollutant degradation highly efficient production hydrogen. This Minireview presents introduction on small‐molecule choice design strategies electrocatalysts as well breakthroughs achieved Finally, challenges future orientations are highlighted.

Language: Английский

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Surface Activation and Ni‐S Stabilization in NiO/NiS₂for Efficient Oxygen Evolution Reaction

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(35)

Published: June 22, 2022

Manipulating the active species and improving structural stabilization of sulfur-containing catalysts during OER process remain a tremendous challenge. Herein, we constructed NiO/NiS2 Fe-NiO/NiS2 as catalyst models to study effect Fe doping. As expected, exhibits low overpotential 270 mV at 10 mA cm-2 . The accumulation hydroxyl groups on surface materials after doping can promote formation highly NiOOH lower potential. Moreover, investigated level corrosion M-S bonds compared stability variation with different locations. Interestingly, bonded S in bulk sacrificial agent alleviate oxidation partial Ni-S thus endow long-term durability. This work could motivate community focus more resolving materials.

Language: Английский

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A review of Ni based powder catalyst for urea oxidation in assisting water splitting reaction

Advanced Powder Materials, Journal Year: 2022, Volume and Issue: 1(3), P. 100030 - 100030

Published: Jan. 10, 2022

Water splitting has been regarded as a sustainable and environmentally-friendly technique to realize green hydrogen generation, while more energy is consumed due the high overpotentials required for anode oxygen evolution reaction. Urea electrooxidation, an ideal substitute, thus received increasing attention in assisting water-splitting reactions. Note that highly efficient catalysts are still drive urea oxidation, facile generation of valence state species significant reaction based on electrochemical-chemical mechanisms. The cost rareness make noble metal impossible further consideration large-scale application. Ni-based very promising their cheap price, structure tuning, good compatibility, easy active phase formation. In light advances made recently, herein, we reviewed recent powder oxidation fundamental firstly presented clarify mechanism urea-assisted water splitting, then prevailing evaluation indicators briefly expressed electrochemical measurements. catalyst design principle including synergistic effect, electronic defect construction surface reconstruction well main fabrication approaches various assisted summarized discussed. problems challenges also concluded fabrication, performance evaluation, Considering key influencing factors catalytic process application, should be given structure−property relationship deciphering, novel development real device; specifically, effort directed with multi-functions simultaneously promote steps anti-corrosion ability by revealing local integration practical We believe current summarization will instructive helpful understanding action via technique.

Language: Английский

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Dual‐Atom Support Boosts Nickel‐Catalyzed Urea Electrooxidation

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(22)

Published: March 24, 2023

Nickel-based catalysts have been regarded as one of the most promising electrocatalysts for urea oxidation reaction (UOR), however, their activity is largely limited by inevitable self-oxidation Ni species (NSOR) during UOR. Here, we proposed an interface chemistry modulation strategy to trigger occurrence UOR before NSOR via constructing a 2D/2D heterostructure that consists ultrathin NiO anchored Ru-Co dual-atom support (Ru-Co DAS/NiO). Operando spectroscopic characterizations confirm this unique triggering mechanism on surface DAS/NiO. Consequently, fabricated catalyst exhibits outstanding with low potential 1.288 V at 10 mA cm-2 and remarkable long-term durability more than 330 h operation. DFT calculations demonstrate favorable electronic structure induced heterointerface endows energetically NSOR.

Language: Английский

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Coordination environment tuning of nickel sites by oxyanions to optimize methanol electro-oxidation activity

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: May 25, 2022

To achieve zero-carbon economy, advanced anode catalysts are desirable for hydrogen production and biomass upgrading powered by renewable energy. Ni-based non-precious electrocatalysts considered as potential candidates because of intrinsic redox attributes, but in-depth understanding rational design Ni site coordination still remain challenging. Here, we perform anodic electrochemical oxidation Ni-metalloids (NiPx, NiSx, NiSex) to in-situ construct different oxyanion-coordinated amorphous nickel oxyhydroxides (NiOOH-TOx), among which NiOOH-POx shows optimal local environment boosts electrocatalytic activity sites towards selective methanol formate. Experiments theoretical results demonstrate that possesses improved adsorption OH* methanol, favors the formation CH3O* intermediates. The coordinated phosphate oxyanions effectively tailor d band center increases Ni-O covalency, promoting catalytic activity. This study provides additional insights into modulation active-center via organic molecules transformation.

Language: Английский

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Recent Advances on Electrolysis for Simultaneous Generation of Valuable Chemicals at both Anode and Cathode

Advanced Energy Materials, Journal Year: 2021, Volume and Issue: 11(46)

Published: Nov. 6, 2021

Abstract To make efficient use of electrical energy in the whole electrocatalysis conversion process, integrating anode and cathode reactions plays a vital role. The combination electrocatalytic anodic oxidation with cathodic reduction can not only maximize return investment, but also produces value‐added materials on both sides. Herein, this review, recent advances co‐electrolysis processes for valuable chemical production are systematically summarized. be more specific, popular hydrogen evolution reaction, carbon dioxide nitrogen reaction as well nitrate integrated to products, respectively comprehensively reviewed, then other paired electrolysis systems (especially biomass‐based compounds) toward high‐value‐added generation discussed detail. This review sheds light integration reductions develop high‐value substances. benefit researchers facilitate progress field, challenges future prospects these proposed.

Language: Английский

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