Microenvironment Engineering of Single/Dual‐Atom Catalysts for Electrocatalytic Application

Advanced Materials, Год журнала: 2023, Номер 35(31)

Опубликована: Фев. 23, 2023

Single/dual-metal atoms supported on carbon matrix can be modulated by coordination structure and neighboring active sites. Precisely designing the geometric electronic uncovering structure-property relationships of single/dual-metal confront with grand challenges. Herein, this review summarizes latest progress in microenvironment engineering single/dual-atom sites via a comprehensive comparison single-atom catalyst (SACs) dual-atom catalysts (DACs) term design principles, modulation strategy, theoretical understanding structure-performance correlations. Subsequently, recent advances several typical electrocatalysis process are discussed to get general reaction mechanisms finely-tuned SACs DACs. Finally, full-scaled summaries challenges prospects given for This will provide new inspiration development atomically dispersed electrocatalytic application.

Язык: Английский

---

Construction of Co₄ Atomic Clusters to Enable Fe−N₄ Motifs with Highly Active and Durable Oxygen Reduction Performance

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(30)

Опубликована: Май 24, 2023

Abstract Fe−N−C catalysts with single‐atom Fe−N 4 configurations are highly needed owing to the high activity for oxygen reduction reaction (ORR). However, limited intrinsic and dissatisfactory durability have significantly restrained practical application of proton‐exchange membrane fuel cells (PEMFCs). Here, we demonstrate that constructing adjacent metal atomic clusters (ACs) is effective in boosting ORR performance stability catalysts. The integration uniform Co ACs on N‐doped carbon substrate (Co @/Fe 1 @NC) realized through a “pre‐constrained” strategy using molecular Fe(acac) 3 implanted precursors. as‐developed @NC catalyst exhibits excellent half‐wave potential ( E 1/2 ) 0.835 V vs. RHE acidic media peak power density 840 mW cm −2 H 2 −O cell test. First‐principles calculations further clarify catalytic mechanism identified modified ACs. This work provides viable precisely establishing atomically dispersed polymetallic centers efficient energy‐related catalysis.

Язык: Английский

---

Neodymium‐Evoked Valence Electronic Modulation to Balance Reversible Oxygen Electrocatalysis

Advanced Energy Materials, Год журнала: 2022, Номер 13(2)

Опубликована: Ноя. 23, 2022

Abstract Suffering from the competition adsorption between oxygen reduction reaction (ORR) and evolution (OER), development of high‐efficiency electrocatalysts with bifunctional properties still remains a challenge. Herein, novel effective neodymium‐evoked valence electronic perturbation strategy to improve balance reversible electrocatalysis metallic cobalt sites is proposed. To heighten coupling Nd Co, metal‐organic‐framework‐induced method chosen prepare target catalyst atomic Nd‐doped Co on an N‐doped carbon substrate. The as‐prepared presents excellent electrocatalytic low overpotential 288 mV at 10 mA cm −2 for OER high half‐wave potential 0.85 V ORR. robust stabilities both ORR are also proven. electrochemical in situ Raman spectra confirm surface dynamic change transformation intermediates by noting formation Co–OOH. Theoretical calculations verify that balanced owing strong 3d‐Nd 4f orbital effect below Fermi level. Moreover, practicability further demonstrated solid‐state rechargeable Zn‐Air batteries, which exhibit large power density long cycling life.

Язык: Английский

---

Heteroatom‐Driven Coordination Fields Altering Single Cerium Atom Sites for Efficient Oxygen Reduction Reaction

Advanced Materials, Год журнала: 2023, Номер 35(28)

Опубликована: Апрель 4, 2023

For current single-atom catalysts (SACs), modulating the coordination environments of rare-earth (RE) single atoms with complex electronic orbital and flexible chemical states is still limited. Herein, cerium (Ce) SAs supported on a P, S, N co-doped hollow carbon substrate (Ce SAs/PSNC) for oxygen reduction reaction (ORR) are reported. The as-prepared Ce SAs/PSNC possesses half-wave potential 0.90 V, turnover frequency value 52.2 s

Язык: Английский

---

Reconstruction of Highly Dense Cu−N₄Active Sites in Electrocatalytic Oxygen Reduction Characterized by Operando Synchrotron Radiation

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(40)

Опубликована: Авг. 22, 2022

The emerging star of single atomic site (SAS) catalyst has been regarded as the most promising Pt-substituted electrocatalyst for oxygen reduction reaction (ORR) in anion-exchange membrane fuel cells (AEMFCs). However, metal loading SAS directly affects whole device performance. Herein, we report a dual nitrogen source coordinated strategy to realize high dense Cu-N4 with 5.61 wt% supported on 3D N-doped carbon nanotubes/graphene structure wherein simultaneously performs superior ORR activity and stability alkaline media. When applied H2 /O2 AEMFC, it could reach an open-circuit voltage 0.90 V peak power density 324 mW cm-2 . Operando synchrotron radiation analyses identify reconstruction from initial /Cu-nanoclusters (NC) subsequent Cu-N3 /Cu-NC under working conditions, which gradually regulate d-band center central balance Gibbs free energy *OOH *O intermediates, benefiting activity.

Язык: Английский

---

Tailoring Oxygen Reduction Reaction Kinetics of Fe−N−C Catalyst via Spin Manipulation for Efficient Zinc–Air Batteries

Advanced Materials, Год журнала: 2024, Номер 36(25)

Опубликована: Апрель 9, 2024

The interaction between oxygen species and metal sites of various orbitals exhibits intimate correlation with the reduction reaction (ORR) kinetics. Herein, a new approach for boosting inherent ORR activity atomically dispersed Fe-N-C matrix is represented by implanting Fe atomic clusters nearby. as-prepared catalyst delivers excellent half-wave potentials 0.78 0.90 V in acidic alkaline solutions, respectively. decent can also be validated from high-performance rechargeable Zn-air battery. experiments density functional theory calculations reveal that electron spin-state monodispersed active transferred low spin (LS, t

Язык: Английский

---

N,O symmetric double coordination of an unsaturated Fe single-atom confined within a graphene framework for extraordinarily boosting oxygen reduction in Zn–air batteries

Energy & Environmental Science, Год журнала: 2023, Номер 16(6), С. 2629 - 2636

Опубликована: Янв. 1, 2023

A novel N,O symmetric double-coordinated configuration of unsaturated Fe single atoms confirmed within a graphene framework (Fe–N,O/G) is demonstrated experimentally and theoretically for highly active durable ORR catalyst in Zn-air batteries.

Язык: Английский

---

Bifunctional Single Atom Catalysts for Rechargeable Zinc–Air Batteries: From Dynamic Mechanism to Rational Design

Advanced Materials, Год журнала: 2023, Номер 35(35)

Опубликована: Июнь 7, 2023

Ever-growing demands for rechargeable zinc-air batteries (ZABs) call efficient bifunctional electrocatalysts. Among various electrocatalysts, single atom catalysts (SACs) have received increasing attention due to the merits of high utilization, structural tunability, and remarkable activity. Rational design SACs relies heavily on an in-depth understanding reaction mechanisms, especially dynamic evolution under electrochemical conditions. This requires a systematic study in mechanisms replace current trial error modes. Herein, fundamental oxygen reduction is first presented combining situ and/or operando characterizations theoretical calculations. By highlighting structure-performance relationships, rational regulation strategies are particularly proposed facilitate SACs. Furthermore, future perspectives challenges discussed. review provides thorough SACs, which expected pave avenue exploring optimum effective ZABs.

Язык: Английский

---

Altering the spin state of Fe-N-C through ligand field modulation of single-atom sites boosts the oxygen reduction reaction

Nano Energy, Год журнала: 2022, Номер 105, С. 108020 - 108020

Опубликована: Ноя. 21, 2022

Язык: Английский

---

Developing a class of dual atom materials for multifunctional catalytic reactions

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Ноя. 8, 2023

Dual atom catalysts, bridging single and metal/alloy nanoparticle offer more opportunities to enhance the kinetics multifunctional performance of oxygen reduction/evolution hydrogen evolution reactions. However, rational design efficient dual catalysts remains a blind area is challenging. In this study, we achieved controllable regulation from Co nanoparticles CoN4 atoms Co2N5 using an atomization sintering strategy via N-stripping thermal-migrating process. More importantly, could be extended fabrication 22 distinct catalysts. particular, with tailored spin states achieve ideally balanced adsorption/desorption intermediates, thus realizing superior activity. addition, it endows Zn-air batteries long-term stability for 800 h, allows water splitting continuously operate 1000 can enable solar-powered systems uninterrupted large-scale production throughout day night. This universal scalable provides controlled in energy conversion technologies.

Язык: Английский

---