The concept of active site in heterogeneous catalysis

Nature Reviews Chemistry, Journal Year: 2022, Volume and Issue: 6(2), P. 89 - 111

Published: Jan. 6, 2022

Language: Английский

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The Critical Impacts of Ligands on Heterogeneous Nanocatalysis: A Review

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(10), P. 6020 - 6058

Published: May 4, 2021

Ligand utilization is a necessary and powerful technique for the colloidal synthesis of nanoparticles (NPs) with controllable sizes regulated morphologies. For catalysis applications, it commonly believed that surface ligands on metal NPs block active catalytic sites reduce activity. Nevertheless, since 2010, an increasing number research groups have demonstrated unexpected benefits improve activity and/or selectivity. These can be ascribed to construction inorganic–organic interface, through which series factors, such as steric, electronic, solubility effects, utilized produce favorable changes interfacial environment. Considering tremendous developments in this emerging field, compile comprehensive systematic overview recent advances. In Review, we summarize critical impacts heterogeneous nanocatalysis. First, introduce vital roles colloid syntheses shapes. Second, detrimental effects nanocatalysis are described basis traditional views. Third, strategies ligand removal reviewed compared. Fourth, has been conducted past decade, three main beneficial (steric, solubility) classified discussed. each effect, possible corresponding mechanism presented, typical examples provided. Recent advances regarding density functional theory (DFT) calculations regulation coverage dedicated explaining ligand-promotion searching optimal nanocatalysts. Fifth, stabilities cutting-edge ligand-capped nanocatalysts before after reactions Finally, highlight remaining challenges propose future perspectives. Although much progress achieved, activities multifaceted still debatable. We hope Review will deepen readers' understanding actual catalysis.

Language: Английский

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Chemically Modified Gold/Silver Superatoms as Artificial Elements at Nanoscale: Design Principles and Synthesis Challenges

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(4), P. 1683 - 1698

Published: Jan. 22, 2021

Pure and doped gold/silver clusters protected by monolayers of organic ligands have attracted much interest as novel functional materials owing to their nonbulk-like, size-specific properties. They can be viewed chemically modified superatoms because stabilities properties are governed the electron shell configurations Au/Ag cores. Chemically unique from conventional atoms in that they additional control parameters such surface modification, compositions, atomic packing, size, although both them follow similar Aufbau principles. Atomically precise synthesis structure determination X-ray crystallography deepened our understanding correlation between structures fundamental superatoms. However, remaining challenges for exploration using artificial elements at nanoscale include (1) establishment guiding principles electronic (2) development efficient, targeted according rational design guidelines functionalities. To address first task, we herein propose rationalize empirical icosahedral Au13/Ag13 with closed configuration platforms. The second task is addressed proposing functionalities hydride-mediated transformation processes synthesis. These efforts will lead construction a new periodic table open up world quasi-molecules made We hope this Perspective contribute creation paradigm based on superatoms, which parallels matured molecular science.

Language: Английский

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Theoretical Advances in Understanding and Designing the Active Sites for Hydrogen Evolution Reaction

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(14), P. 8404 - 8433

Published: June 30, 2022

As a fundamental step of water splitting and stepping stone toward exploring other multielectron transfer processes, the electrocatalytic hydrogen evolution reaction (HER) is an ideal model for both understanding electrocatalyst design. Here, we review fundamentals recent developments theoretical insights into HER, covering mechanistic aspects, key activity descriptors, local environment considerations, advances beyond computational electrode. Although it experimentally challenging to explore active sites mechanisms in process, show great potential identifying mechanisms. In this Review, especially focus depth on revealing designing HER. Major challenges ahead will also be discussed at end Review.

Language: Английский

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Gold nanoclusters for theranostic applications

Coordination Chemistry Reviews, Journal Year: 2020, Volume and Issue: 431, P. 213689 - 213689

Published: Dec. 5, 2020

Language: Английский

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Controlled growth of a high selectivity interface for seawater electrolysis

Proceedings of the National Academy of Sciences, Journal Year: 2022, Volume and Issue: 119(36)

Published: Aug. 29, 2022

Overall seawater electrolysis is an important direction for the development of hydrogen energy conversion. The key issues include how to achieve high selectivity, activity, and stability in reactions. In this report, heterostructures graphdiyne-RhOx-graphdiyne (GDY/RhOx/GDY) were constructed by situ-controlled growth GDY on RhOx nanocrystals. A double layer interface sp-hybridized carbon-oxide-Rhodium (sp-C∼O-Rh) was formed system. microstructures at are composed active sites sp-C∼O-Rh. obvious electron-withdrawing surface enhances catalytic activity with orders magnitude, while outer metal oxides guarantees stability. electron-donating withdrawing sp-C∼O-Rh structures enhance achieving high-performance overall very small cell voltages 1.42 1.52 V large current densities 10 500 mA cm-2 room temperatures ambient pressures, respectively. compositional structural superiority GDY-derived sp-C-metal-oxide center offers great opportunities engineer tunable redox properties performance beyond. This a typical successful example rational design systems.

Language: Английский

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Strategic Modulation of Target-Specific Isolated Fe,Co Single-Atom Active Sites for Oxygen Electrocatalysis Impacting High Power Zn–Air Battery

ACS Nano, Journal Year: 2022, Volume and Issue: 16(5), P. 7890 - 7903

Published: April 18, 2022

An effective modulation of the active sites in a bifunctional electrocatalyst is essentially desired, and it challenge to outperform state-of-the-art catalysts toward oxygen electrocatalysis. Herein, we report development having target-specific Fe-N4/C Co-N4/C isolated sites, exhibiting symbiotic effect on overall electrocatalysis performances. The dualism N-dopants binary metals lower d-band centers both Fe Co Fe,Co,N-C catalyst, improving overpotential electrocatalytic processes (ΔEORR-OER = 0.74 ± 0.02 V vs RHE). Finally, showed high areal power density 198.4 mW cm-2 158 respective liquid solid-state Zn-air batteries (ZABs), demonstrating suitable candidature material as air cathode ZABs.

Language: Английский

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Surface and Interface Coordination Chemistry Learned from Model Heterogeneous Metal Nanocatalysts: From Atomically Dispersed Catalysts to Atomically Precise Clusters

Chemical Reviews, Journal Year: 2022, Volume and Issue: 123(9), P. 5948 - 6002

Published: Dec. 27, 2022

The surface and interface coordination structures of heterogeneous metal catalysts are crucial to their catalytic performance. However, the complicated make it challenging identify molecular-level structure active sites thus precisely control To address this challenge, atomically dispersed (ADMCs) ligand-protected precise clusters (APMCs) have been emerging as two important classes model in recent years, helping build bridge between homogeneous catalysis. This review illustrates how chemistry these types determines performance from multiple dimensions. section ADMCs starts with local at metal–support interface, then focuses on effects coordinating atoms, including basicity hardness/softness. Studies also summarized discuss cooperativity achieved by dual remote effects. In APMCs, roles ligands supports determining activity, selectivity, stability APMCs illustrated. Finally, some personal perspectives further development for presented.

Language: Английский

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Layered Double Hydroxide-Derived Nanomaterials for Efficient Electrocatalytic Water Splitting: Recent Progress and Future Perspective

ACS Energy Letters, Journal Year: 2022, Volume and Issue: 7(10), P. 3311 - 3328

Published: Sept. 8, 2022

Layered double hydroxides (LDHs) have attracted intense interest in recent research and hold promise a vast range of applications. Because the layered structure diverse compositions, transition-metal-based LDHs are projected to function as active electrocatalysts for oxygen evolution reaction (OER) hydrogen (HER). Delamination LDH hexagonal platelet crystals nanometer level leads enhanced activity. However, several limitations, including collapse poor conductivity LDHs, impede their application electrochemical catalysis. Consequently, LDH-derived nanomaterials being employed high-performance overall water splitting. In this Review, we highlight progress development materials, bimetal oxides hydroxides, bimetallic nitrides/phosphides, sulfides/selenides, MOFs, remarkable Focus is placed on methodologies catalytic efficiency splitting, key problems, future perspectives.

Language: Английский

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Generation and identification of 1O2 in catalysts/peroxymonosulfate systems for water purification

Water Research, Journal Year: 2023, Volume and Issue: 245, P. 120614 - 120614

Published: Sept. 11, 2023

Language: Английский

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