Descriptors for the Evaluation of Electrocatalytic Reactions: d‐Band Theory and Beyond

Advanced Functional Materials, Journal Year: 2021, Volume and Issue: 32(4)

Published: Oct. 13, 2021

Abstract Closing the carbon‐, hydrogen‐, and nitrogen cycle with renewable electricity holds promises for mitigation of facing environment energy crisis, along continuing prosperity human society. Descriptors bridge gap between physicochemical factors electrocatalysts their boosted activity serve as guiding principles during rational design electrocatalysts. The optimal adsorption strength key intermediates is potentially accessed under tendentious guidelines proposed by indicators, such d‐band center, Δ G H , E O* coordination number (CN), bond length, etc. Here, in this review, a comprehensive summary recent advances achieved regarding descriptors that aims recycling C/H/N‐containing chemicals offered. review initiated providing necessity development efficient then physics behind center introduced. Then progress relating to guidance reviewed. Following that, an extended discussion experimental or theoretical characterization beyond it provided. Finally, perspectives challenges area are

Language: Английский

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Comprehensive Understandings into Complete Reconstruction of Precatalysts: Synthesis, Applications, and Characterizations

Advanced Materials, Journal Year: 2021, Volume and Issue: 33(32)

Published: May 29, 2021

Reconstruction induced by external environment (such as applied voltage bias and test electrolytes) changes catalyst component catalytic behaviors. Investigations of complete reconstruction in energy conversion recently receive intensive attention, which promote the targeted design top-performance materials with maximum utilization good stability. However, advantages reconstruction, its strategies, extensive applications have not achieved profound understandings summaries it deserves. Here, this review systematically summarizes several important advances for first time, includes 1) fundamental characteristics completely reconstructed catalysts, their principles, 2) types reconstruction-involved precatalysts oxygen evolution reaction catalysis wide pH solution, origins limited degree well strategies/principles toward 3) novel material synthesis other electrocatalysis fields, 4) advanced situ/operando or multiangle/level characterization techniques to capture dynamic processes real contributors. Finally, existing major challenges unexplored/unsolved issues on studying chemistry are summarized, an outlook further development is briefly proposed. This will arouse attention diverse fields.

Language: Английский

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Nanostructured metal phosphides: from controllable synthesis to sustainable catalysis

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(13), P. 7539 - 7586

Published: Jan. 1, 2021

Metal phosphides (MPs) with unique and desirable physicochemical properties provide promising potential in implementable sustainable catalytic fields including electrocatalysis, photocatalysis, mild thermocatalysis, interdisciplinary hybrid systems.

Language: Английский

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Phosphorized CoNi₂S₄ Yolk‐Shell Spheres for Highly Efficient Hydrogen Production via Water and Urea Electrolysis

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(42), P. 22885 - 22891

Published: Aug. 5, 2021

Abstract Exploring earth‐abundant electrocatalysts with excellent activity, robust stability, and multiple functions is crucial for electrolytic hydrogen generation. Porous phosphorized CoNi 2 S 4 yolk‐shell spheres (P‐CoNi YSSs) were rationally designed synthesized by a combined hydrothermal sulfidation gas‐phase phosphorization strategy. Benefiting from the strengthened Ni 3+ /Ni 2+ couple, enhanced electronic conductivity, hollow structure, P‐CoNi YSSs exhibit activity durability towards hydrogen/oxygen evolution urea oxidation reactions in alkaline solution, affording low potentials of −0.135 V, 1.512 1.306 V (versus reversible electrode) at 10 mA cm −2 , respectively. Remarkably, when used as anode cathode simultaneously, catalyst merely requires cell voltage 1.544 water splitting 1.402 electrolysis to attain 100 h, outperforming most reported nickel‐based sulfides even noble‐metal‐based electrocatalysts. This work promotes application electrochemical production provides feasible approach urea‐rich wastewater treatment.

Language: Английский

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Halogen‐Doped Carbon Dots on Amorphous Cobalt Phosphide as Robust Electrocatalysts for Overall Water Splitting

Advanced Energy Materials, Journal Year: 2022, Volume and Issue: 12(14)

Published: Jan. 24, 2022

Abstract Designing a stable and efficient dual‐functional catalyst for the hydrogen evolution oxygen reactions (HER/OER) is of great significance to development production by water splitting. This work reports on novel halogen (X = F, Cl, Br)‐doped carbon dots modifying amorphous cobalt phosphide (X‐CDs/CoP), which can be tuned choice X‐CDs have urchin, Pinus bungeana , Albizia julibrissin type structures. The different characteristics various led formation mechanisms final As bifunctional catalyst, urchin‐shaped F‐CDs/CoP crystals achieve superior electrocatalytic performance, exhibiting excellent HER/OER activity sustained stability in an alkaline solution. For overall splitting, they provide current density 10 mA cm −2 require low cell voltage 1.48 V 1 M KOH. In addition, catalytic performance shows negligible degradation after 100 h, thus demonstrating long‐term cycling stability. Density functional theory calculations show that improved catalysts due coupling interface between CoP F‐CDs, optimizes hydrogen/oxygen adsorption energy accelerates splitting kinetics. provides guidance rational design transition metal electrocatalysts with outstanding performance.

Language: Английский

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Rapid complete reconfiguration induced actual active species for industrial hydrogen evolution reaction

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

Published: Oct. 2, 2022

Rational regulation of electrochemical reconfiguration and exploration activity origin are important foundations for realizing the optimization electrocatalyst activity, but rather challenging. Herein, we potentially develop a rapid complete strategy heterostructures CoC2O4 coated by MXene nanosheets (CoC2O4@MXene) during hydrogen evolution reaction (HER) process. The self-assembled CoC2O4@MXene nanotubular structure has high electronic accessibility abundant electrolyte diffusion channels, which favor reconfiguration. Such creates new actual catalytic active species Co(OH)2 transformed from CoC2O4, is coupled with to facilitate charge transfer decrease free energy Volmer step toward fast HER kinetics. reconfigured components require low overpotentials 28 216 mV at 10 1000 mA cm-2 in alkaline conditions decent stability natural seawater. This work gives insights understanding formation opens up way high-performance electrocatalysts.

Language: Английский

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Exclusive Strain Effect Boosts Overall Water Splitting in PdCu/Ir Core/Shell Nanocrystals

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(15), P. 8243 - 8250

Published: Jan. 15, 2021

Abstract Core/shell nanocatalysts are a class of promising materials, which achieve the enhanced catalytic activities through synergy between ligand effect and strain effect. However, it has been challenging to disentangle contributions from two effects, hinders rational design superior core/shell nanocatalysts. Herein, we report precise synthesis PdCu/Ir nanocrystals, can significantly boost oxygen evolution reaction (OER) via exclusive The heteroepitaxial coating four Ir atomic layers onto PdCu nanoparticle gives relatively thick shell eliminating effect, but creates compressive ca. 3.60%. strained catalysts deliver low OER overpotential high mass activity. Density functional theory (DFT) calculations reveal that in downshifts d‐band center weakens binding intermediates, causing also boosts hydrogen (HER) activity nanocrystals be served as excellent for both anode cathode overall water‐splitting electrocatalysis.

Language: Английский

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Identification of the Origin for Reconstructed Active Sites on Oxyhydroxide for Oxygen Evolution Reaction

Advanced Materials, Journal Year: 2022, Volume and Issue: 35(6)

Published: Nov. 21, 2022

The regulation of atomic and electronic structures active sites plays an important role in the rational design oxygen evolution reaction (OER) catalysts toward electrocatalytic hydrogen generation. However, precise identification for surface reconstruction behavior during OER remains elusive water-alkali electrolysis. Herein, irreversible accompanied by copper dynamic cobalt iron layered double hydroxide (CoFe LDH) precatalyst to form CoFeCuOOH species with high-valent Co is reported, identifying origin reconstructed through operando UV-Visible (UV-vis), situ Raman, X-ray absorption fine-structure (XAFS) spectroscopies. Density functional theory analysis rationalizes this typical structure causing transfer intramolecular electrons ligand holes, promoting sites. Specifically, unambiguous explored 18 O isotope-labeling differential electrochemical mass spectrometry (DEMS) supported theoretical calculation, confirming mechanism switch oxygen-vacancy-site (OVSM) pathway on lattice oxygen. This work enables elucidate vital active-site generation representative contribution OVSM efficient performance.

Language: Английский

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Enhancing Polysulfide Confinement and Electrochemical Kinetics by Amorphous Cobalt Phosphide for Highly Efficient Lithium–Sulfur Batteries

ACS Nano, Journal Year: 2020, Volume and Issue: 15(1), P. 739 - 750

Published: Dec. 28, 2020

The application of lithium–sulfur (Li–S) batteries is severely hampered by the shuttle effect and sluggish redox kinetics. Herein, amorphous cobalt phosphide grown on a reduced graphene oxide-multiwalled carbon nanotube (rGO-CNT-CoP(A)) designed as sulfur host to conquer above bottlenecks. differences between (CoP) crystalline CoP surface adsorption well conversion lithium polysulfides (LiPSs) are investigated systematical experiments density-functional theory (DFT) calculations. Specifically, not only strengthens chemical LiPSs but also greatly accelerates liquid-phase conversions nucleation growth Li2S. DFT calculation reveals that possesses higher binding energies lower diffusion energy barriers for LiPSs. In addition, features gap increased electronic concentrations adsorbed near Fermi level. These characteristics contribute enhanced chemisorption ability accelerated Simultaneously, prepared S/rGO-CNT-CoP(A) electrode delivers an impressive initial capacity 872 mAh g–1 at 2 C 617 can be obtained after 200 cycles, exhibiting excellent cycling stability. Especially, it achieves outstanding electrochemical performance even under high loading (5.3 mg cm–2) lean electrolyte (E/S = 7 μLE mg–1S) conditions. This work exploits potential materials contributes development highly efficient Li–S batteries.

Language: Английский

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Engineering Lattice Oxygen Activation of Iridium Clusters Stabilized on Amorphous Bimetal Borides Array for Oxygen Evolution Reaction

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(52), P. 27126 - 27134

Published: Oct. 9, 2021

Developing robust oxygen evolution reaction (OER) catalysts requires significant advances in material design and in-depth understanding for water electrolysis. Herein, we report iridium clusters stabilized surface reconstructed oxyhydroxides on amorphous metal borides array, achieving an ultralow overpotential of 178 mV at 10 mA cm-2 OER alkaline medium. The coupling induced the formation high valence cobalt species Ir-O-Co bridge between atomic scale, engineering lattice activation non-concerted proton-electron transfer to trigger multiple active sites intrinsic pH-dependent activity. oxidation mechanism (LOM) was confirmed by situ 18 O isotope labeling mass spectrometry chemical recognition negative peroxo-like species. Theoretical simulations reveal that performance this catalyst is intrinsically dominated LOM pathway, facilitating kinetics. This work not only paves avenue rational electrocatalysts, but also serves fundamental insights into participation promising application.

Language: Английский

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