Identification of the Active Species in Bimetallic Cluster Catalyzed Hydrogenation DOI
Shang‐Fu Yuan, Zong‐Jie Guan, Quan‐Ming Wang

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(25), P. 11405 - 11412

Published: June 14, 2022

Identification of the authentic active species cluster catalysis is rather challenging, and direct structural evidence quite valuable difficult to obtain. Two "isostructural" clusters, Ag25Cu4Cl6(dppb)6(PhC≡C)12(SO3CF3)3 (1) Ag25Cu4Cl6H8(dppb)6(PhC≡C)12(SO3CF3)3 (2H) (dppb 1,4-bis(diphenylphosphine)butane), have been successfully isolated structurally characterized. Both these clusters a centered icosahedron Ag13 core with same peripheral composition structure. The only difference that 2H has eight hydrides but 1 none, is, kernels are Ag135+ Ag13H85+ in 2H, respectively. catalytic reduction 4-nitrophenol (4-NP) 4-aminophenol (4-AP) as model reaction assessed two clusters. Cluster very 100% yield within 2 h, whereas shows low conversion (∼8%) under conditions. Interestingly, high activity was observed when converted oxidation H2O2 unprecedented transformation reduced nanocluster an Ag(I)Cu(I) bimetallic compound provides excellent platform determine real terms metal catalysis. present work presents clear performance nanoclusters can be modulated by properly regulating state their constituted atoms.

Language: Английский

Electrocatalytic reduction of nitrate – a step towards a sustainable nitrogen cycle DOI
Hui Xu, Yuanyuan Ma, Jun Chen

et al.

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(7), P. 2710 - 2758

Published: Jan. 1, 2022

This review provides an overview of electrocatalytic reduction nitrate, including the reaction mechanisms, reactor design principles, product detection methods, and performance evaluation which can provide a sustainable nitrogen cycle.

Language: Английский

Citations

656
Bimetallic Sites for Catalysis: From Binuclear Metal Sites to Bimetallic Nanoclusters and Nanoparticles DOI Creative Commons
Lichen Liu, Avelino Corma

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

Citations

294
Engineering luminescent metal nanoclusters for sensing applications DOI

Shuyu Qian,

Ziping Wang,

Zhongxiang Zuo

et al.

Coordination Chemistry Reviews, Journal Year: 2021, Volume and Issue: 451, P. 214268 - 214268

Published: Oct. 21, 2021

Language: Английский

Citations

139
Surface-Clean Au25 Nanoclusters in Modulated Microenvironment Enabled by Metal–Organic Frameworks for Enhanced Catalysis DOI
He Wang, Xiyuan Liu, Weijie Yang

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(48), P. 22008 - 22017

Published: Nov. 21, 2022

Metal nanoclusters (NCs) with atomically precise structures have sparked interest in catalysis. Unfortunately, their high aggregation tendency and the spatial resistance of surface ligands pose significant challenges. Herein, Au25 NCs are encapsulated into isoreticular metal-organic frameworks (MOFs), namely UiO-66-X (X = H, NH2, OH, NO2), followed by removal on NCs. The resulting surface-clean NCs, protected MOF confinement, exhibit much superior activity stability respect to pristine oxidative esterification furfural. Remarkably, experimental theoretical results jointly demonstrate that diverse functional groups modulate electronic state, giving rise discriminated substrate adsorption energy Au25@UiO-66-X. As a result, electron density suitable ability dominate trend: Au25@UiO-66-NH2 > Au25@UiO-66-OH Au25@UiO-66 Au25@UiO-66-NO2. This work develops new strategy for stabilization metal pore wall-engineered MOFs enhanced

Language: Английский

Citations

120
Supercrystal engineering of atomically precise gold nanoparticles promoted by surface dynamics DOI
Qiaofeng Yao, Lingmei Liu,

Sami Malola

et al.

Nature Chemistry, Journal Year: 2022, Volume and Issue: 15(2), P. 230 - 239

Published: Nov. 10, 2022

Language: Английский

Citations

110
Creation of High‐Performance Heterogeneous Photocatalysts by Controlling Ligand Desorption and Particle Size of Gold Nanocluster DOI
Tokuhisa Kawawaki, Yuki Kataoka,

Momoko Hirata

et al.

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(39), P. 21340 - 21350

Published: May 26, 2021

Recently, the creation of new heterogeneous catalysts using unique electronic/geometric structures small metal nanoclusters (NCs) has received considerable attention. However, to achieve this, it is extremely important establish methods remove ligands from ligand-protected NCs while preventing aggregation NCs. In this study, ligand-desorption process during calcination was followed for metal-oxide-supported 2-phenylethanethiolate-protected gold (Au) 25-atom five experimental techniques. The results clearly demonstrate that consists ligand dissociation on surface NCs, adsorption generated compounds support and desorption support, temperatures at which these processes occurred were elucidated. Based obtained knowledge, we established a method form metal-oxide layer Au their aggregation, thereby succeeding in creating water-splitting photocatalyst with high activity stability.

Language: Английский

Citations

109
Suppression of kernel vibrations by layer-by-layer ligand engineering boosts photoluminescence efficiency of gold nanoclusters DOI Creative Commons
Yuan Zhong, Jiangwei Zhang, Tingting Li

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Feb. 7, 2023

The restriction of structural vibration has assumed great importance in attaining bright emission luminescent metal nanoclusters (NCs), where tremendous efforts are devoted to manipulating the surface landscape yet remain challenges for modulation kernel. Here, we report efficient suppression kernel achieving enhancement intensity, by rigidifying NCs and propagating as-developed strains into core. Specifically, a layer-by-layer triple-ligands engineering is deployed allow solution-phase Au with strong core-dictated fluorescence, up high absolute quantum yields 90.3 ± 3.5%. as-rigidified imposed synergistic supramolecular interactions greatly influences low-frequency acoustic kernel, resulting subtle change frequency but reduction amplitude oscillation. This scenario therewith impedes non-radiative relaxation electron dynamics, rendering emission. presented study exemplifies linkage between chemistry core-state NCs, proposes strategy brighter emitting regulating their interior core-involved motion.

Language: Английский

Citations

99
Doping‐Mediated Energy‐Level Engineering of M@Au12 Superatoms (M=Pd, Pt, Rh, Ir) for Efficient Photoluminescence and Photocatalysis DOI
Haru Hirai, Shinjiro Takano, Takuya Nakashima

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(36)

Published: May 24, 2022

We synthesized a series of MAu12 (dppe)5 Cl2 (MAu12 ; M=Au, Pd, Pt, Rh, or Ir; dppe=1,2-bis(diphenylphosphino)ethane), which have icosahedral M@Au12 superatomic cores, and systematically investigated their electronic structures, photoluminescence (PL) photocatalytic properties. The energy gap between the highest occupied molecular orbital (HOMO) lowest unoccupied (LUMO) was expanded when doping an M element positioned at lower left periodic table. PL quantum yield enhanced with increase in HOMO-LUMO reached 0.46-0.67 for (M=Pt, Ir) under deaerated conditions. bright PLs from were assigned to phosphorescence based on quenching by O2 . acted as more efficient stable photocatalyst than Au13 intramolecular [2+2] cycloaddition bisenone via oxidative cycle. This study provides rational guides designing photoluminescent gold superatoms heterometal elements.

Language: Английский

Citations

91
N-Heterocyclic Carbene-Stabilized Gold Nanoclusters with Organometallic Motifs for Promoting Catalysis DOI
Hui Shen, Qingyuan Wu,

Sami Malola

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(24), P. 10844 - 10853

Published: June 7, 2022

The complexity of heterogeneous metal catalysts makes it challenging to gain insights into their catalytic mechanisms. Thus, there exists a huge gap between catalysis and organometallic catalysis. With the success in preparation highly robust atomically precise nanocluster (i.e., [Au16(NHC-1)5(PA)3Br2]3+ [Au17(NHC-1)4(PA)4Br4]+, where NHC-1 is bidentate NHC ligand, PA phenylacetylide) with surface motifs anchored on metallic core, we demonstrate this work how core works synergistically enhance More importantly, discovery allows development stable recyclable achieve efficient hydroamination alkynes an extremely low catalyst dosage (0.002 mol %), helping bridge homogeneous modification nanocatalysts provides new design principle enhanced

Language: Английский

Citations

87
Ultrasmall Coinage Metal Nanoclusters as Promising Theranostic Probes for Biomedical Applications DOI
Yang Ge, Ziping Wang, Fanglin Du

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(22), P. 11879 - 11898

Published: May 18, 2023

Ultrasmall coinage metal nanoclusters (NCs, <3 nm) have emerged as a novel class of theranostic probes due to their atomically precise size and engineered physicochemical properties. The rapid advances in the design applications NC-based are made possible by atomic-level engineering NCs. This Perspective article examines (i) how functions NCs for applications, (ii) probe is designed its properties affect performance, (iii) used diagnose treat various diseases. We first summarize tailored terms biocompatibility tumor targeting. focus our discussion on bioimaging-directed disease diagnosis, photoinduced therapy, nanomedicine, drug delivery, optical urinalysis. Lastly, an outlook challenges opportunities future development provided.

Language: Английский

Citations

86