Bimetallic Sites for Catalysis: From Binuclear Metal Sites to Bimetallic Nanoclusters and Nanoparticles

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(8), P. 4855 - 4933

Published: March 27, 2023

Heterogeneous bimetallic catalysts have broad applications in industrial processes, but achieving a fundamental understanding on the nature of active sites at atomic and molecular level is very challenging due to structural complexity catalysts. Comparing features catalytic performances different entities will favor formation unified structure-reactivity relationships heterogeneous thereby facilitate upgrading current In this review, we discuss geometric electronic structures three representative types (bimetallic binuclear sites, nanoclusters, nanoparticles) then summarize synthesis methodologies characterization techniques for entities, with emphasis recent progress made past decade. The supported nanoparticles series important reactions are discussed. Finally, future research directions catalysis based and, more generally, prospective developments both practical applications.

Language: Английский

---

Hydroxyl-Bonded Ru on Metallic TiN Surface Catalyzing CO₂ Reduction with H₂O by Infrared Light

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(50), P. 27415 - 27423

Published: Dec. 11, 2023

Synchronized conversion of CO2 and H2O into hydrocarbons oxygen via infrared-ignited photocatalysis remains a challenge. Herein, the hydroxyl-coordinated single-site Ru is anchored precisely on metallic TiN surface by NaBH4/NaOH reforming method to construct an infrared-responsive HO-Ru/TiN photocatalyst. Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (ac-HAADF-STEM) X-ray absorption spectroscopy (XAS) confirm atomic distribution species. XAS density functional theory (DFT) calculations unveil formation HO-RuN5-Ti Lewis pair sites, which achieves efficient polarization/activation dual coordination with C O atoms HO-Ru/TiN. Also, implanting species powerfully boosts separation transfer photoinduced charges. Under infrared irradiation, catalyst shows superior CO2-to-CO transformation activity coupled oxidation release O2, reduction rate can further be promoted about 3-fold under simulated sunlight. With key reaction intermediates determined in situ diffuse reflectance Fourier transform (DRIFTS) predicted DFT simulations, possible photoredox mechanism system proposed.

Language: Английский

---

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

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(31)

Published: Feb. 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.

Language: Английский

---

Interfacial Chemical Bond and Oxygen Vacancy‐Enhanced In₂O₃/CdSe‐DETA S‐scheme Heterojunction for Photocatalytic CO₂ Conversion

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 33(23)

Published: March 2, 2023

Abstract The S‐scheme heterojunctions have great potential for photocatalytic carbon dioxide reduction due to their unique carrier migration pathways, superior separation efficiencies, and high redox capacities. However, the precise process of oriented powerful electron transport remains a challenge. Herein, an InOCd bond‐modulated heterojunction In 2 O 3 /CdSe‐DETA is synthesized by simple microwave‐assisted hydrothermal method accelerated photogenerated transfer. Meanwhile, oxygen vacancies (Vo) capture effect. Consequently, thanks synergistic effect this In‐Vo‐In‐O‐Cd structural units at interface, electrons are extracted rapidly transferred surface‐active sites, which improves electronic coupling CO . This finding precisely adjusts transfer pathway shortens distance. chemical bond established in heterostructure with (Vo‐In ) provides new insights into reduction.

Language: Английский

---

Geometric and Electronic Engineering of Atomically Dispersed Copper‐Cobalt Diatomic Sites for Synergistic Promotion of Bifunctional Oxygen Electrocatalysis in Zinc–Air Batteries

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(25)

Published: April 11, 2023

The development of rechargeable zinc-air batteries is heavily dependent on bifunctional oxygen electrocatalysts to offer exceptional reduction/evolution reaction (ORR/OER) activities. However, the design such with high activity and durability challenging. Herein, a strategy proposed create an electrocatalyst comprised copper-cobalt diatomic sites highly porous nitrogen-doped carbon matrix (Cu-Co/NC) abundantly accessible metal optimal geometric electronic structures. Experimental findings theoretical calculations demonstrate that synergistic effect Cu-Co dual-metal metal-N4 coordination induce asymmetric charge distributions moderate adsorption/desorption behavior intermediates. This exhibits extraordinary electrocatalytic activities in alkaline media, half-wave potential 0.92 V for ORR low overpotential 335 mV at 10 mA cm-2 OER. In addition, it demonstrates acidic (0.85 V) neutral (0.74 media. When applied battery, achieves operational performance outstanding (510 h), ranking as one most efficient reported date. work importance engineering isolated boosting electrochemical energy devices.

Language: Английский

---

Review of Carbon Support Coordination Environments for Single Metal Atom Electrocatalysts (SACS)

Advanced Materials, Journal Year: 2023, Volume and Issue: 36(1)

Published: April 20, 2023

This topical review focuses on the distinct role of carbon support coordination environment single-atom catalysts (SACs) for electrocatalysis. The article begins with an overview atomic configurations in SACs, including a discussion advanced characterization techniques and simulation used understanding active sites. A summary key electrocatalysis applications is then provided. These processes are oxygen reduction reaction (ORR), evolution (OER), hydrogen (HER), nitrogen (NRR), dioxide (CO

Language: Английский

---

In Situ Synthesis of Chemically Bonded 2D/2D Covalent Organic Frameworks/O‐Vacancy WO₃ Z‐Scheme Heterostructure for Photocatalytic Overall Water Splitting

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(33)

Published: June 15, 2023

Abstract Covalent organic frameworks (COFs) have shown great promise for photocatalytic hydrogen evolution via water splitting. However, the four‐electron oxidation of remains elusive toward oxygen evolution. Enabling this pathway is critical to improve yield and maximize atom utilization efficiency. A Z‐scheme heterojunction proposed overcoming fundamental issues in COF‐based overall splitting (OWS), such as inefficient light absorption, charge recombination, poor ability. It that construction a novel 2D/2D through situ growth COFs on O‐vacancy WO 3 nanosheets (Ov‐WO ) WOC chemical bond can remarkably promote OWS. Benefiting from synergistic effect between enhanced built‐in electric field by interfacial bond, strong ability Ov‐WO 3, ultrathin structure TSCOF, both separation efficiency photogenerated electron–hole pairs be significantly enhanced. An impressive half‐rection rate 593 mmol h −1 g 146 (hydrogen) 68 (oxygen) µmol are achieved COF‐WO (TSCOFW) composite. This with two‐step excitation precisely cascaded charge‐transfer makes it responsible efficient solar‐driven OWS without sacrificial agent.

Language: Английский

---

Advances in heterogeneous single-cluster catalysis

Nature Reviews Chemistry, Journal Year: 2023, Volume and Issue: 7(11), P. 754 - 767

Published: Oct. 9, 2023

Language: Английский

---

Isolated Electron Trap‐Induced Charge Accumulation for Efficient Photocatalytic Hydrogen Production

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(25)

Published: April 20, 2023

The solar-driven evolution of hydrogen from water using particulate photocatalysts is considered one the most economical and promising protocols for achieving a stable supply renewable energy. However, efficiency photocatalytic splitting far satisfactory due to sluggish electron-hole pair separation kinetics. Herein, isolated Mo atoms in high oxidation state have been incorporated into lattice Cd0.5 Zn0.5 S (CZS@Mo) nanorods, which exhibit rate 11.32 mmol g-1 h-1 (226.4 μmol ; catalyst dosage 20 mg). Experimental theoretical simulation results imply that highly oxidized species lead mobile-charge imbalances CZS induce directional photogenerated electrons transfer, resulting effectively inhibited recombination greatly enhanced efficiency.

Language: Английский

---

Highly Selective Ethylene Production from Solar-Driven CO₂ Reduction on the Bi₂S₃@In₂S₃ Catalyst with In–S_V–Bi Active Sites

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(4), P. 2302 - 2312

Published: Jan. 30, 2023

Photothermal catalysis that utilizes solar energy to not only generate charge carriers but also supply heat input represents a potentially sustainable strategy for the efficient conversion of CO2 valuable chemicals. It is highly desirable develop photothermal catalysts with broadband light absorption across whole spectrum, conversion, and appropriate active sites. In this work, Bi2S3@In2S3 heterostructure catalyst fabricated via one-step solvothermal synthesis, where Bi2S3 serves as material synchronously affords photoexcited carriers. Experimental results indicate photoinduced trigger H2O-assisted reduction elevated temperature kinetically accelerates reaction. Furthermore, tightly bonded heterointerfaces provide unique In–SV–Bi centers consisting adjacent Bi atoms coupled sulfur vacancies, which reduces barriers activation C–C coupling, facilitating generation dimerization CO intermediates selective C2H4 production. The integration sites effect into induces high rate 11.81 μmol gcat–1 h–1 near 90% selectivity under simulated sunlight without extra input. catalytic mechanism expounded by in situ characterizations theoretical calculations. This work would some enlightening guidance construct direct transformation multicarbon (C2+) products energy.

Language: Английский

---