Toward Active-Site Tailoring in Heterogeneous Catalysis by Atomically Precise Metal Nanoclusters with Crystallographic Structures

Chemical Reviews, Journal Year: 2020, Volume and Issue: 121(2), P. 567 - 648

Published: Sept. 17, 2020

Heterogeneous catalysis involves solid-state catalysts, among which metal nanoparticles occupy an important position. Unfortunately, no two from conventional synthesis are the same at atomic level, though such regular can be highly uniform nanometer level (e.g., size distribution ∼5%). In long pursuit of well-defined nanocatalysts, a recent success is atomically precise nanoclusters protected by ligands in range tens to hundreds atoms (equivalently 1–3 nm core diameter). More importantly, have been crystallographically characterized, just like protein structures enzyme catalysis. Such merge features homogeneous catalysts ligand-protected centers) and enzymes protein-encapsulated clusters few bridged ligands). The with their total available constitute new class model hold great promise fundamental research, including dependent activity, control catalytic selectivity structure surface ligands, structure–property relationships atomic-level, insights into molecular activation mechanisms, identification active sites on nanocatalysts. This Review summarizes progress utilization for These nanocluster-based enabled heterogeneous research single-atom single-electron levels. Future efforts expected achieve more exciting understanding tailoring design high activity under mild conditions.

Language: Английский

---

Cucurbiturils‐Mediated Noble Metal Nanoparticles for Applications in Sensing, SERS, Theranostics, and Catalysis

Advanced Functional Materials, Journal Year: 2020, Volume and Issue: 31(1)

Published: Sept. 28, 2020

Abstract Noble metal nanoparticles (NMNPs), which spring up like mushrooms, are gaining momentum owing to their unique physicochemical characteristics. Cucurbiturils, a class of synthetic macrocycles with intriguing and peculiar host–guest properties, have stimulated tremendous research interest in recent years. The marriage NMNPs cucurbiturils is expected integrate enhance the excellent characteristics both components, e.g., precisely controlled particle size, stability, assembly, surface functionality, biocompatibility, tunable optical high catalytic activities. This review systematically outlines progress on fabricating strategies important applications cucurbiturils‐mediated sensing, surface‐enhanced Raman scattering, theranostics, catalysis. A brief outlook future development also presented.

Language: Английский

---

N-heterocyclic carbene coordinated metal nanoparticles and nanoclusters

Coordination Chemistry Reviews, Journal Year: 2022, Volume and Issue: 458, P. 214425 - 214425

Published: Feb. 3, 2022

Language: Английский

---

Platonic and Archimedean solids in discrete metal-containing clusters

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 52(1), P. 383 - 444

Published: Dec. 19, 2022

This review presents the symmetrical beauty of metal cluster structures from perspective Platonic and Archimedean solids, further provides some insights into design synthesis unknown clusters.

Language: Английский

---

Site-specific substitution in atomically precise carboranethiol-protected nanoclusters and concomitant changes in electronic properties

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Jan. 30, 2025

We report the synthesis of [Ag17(o1-CBT)12]3- abbreviated as Ag17, a stable 8e⁻ anionic cluster with unique Ag@Ag12@Ag4 core-shell structure, where o1-CBT is ortho-carborane-1-thiol. By substituting Ag atoms Au and/or Cu at specific sites we created isostructural clusters [AuAg16(o1-CBT)12]3- (AuAg16), [Ag13Cu4(o1-CBT)12]3- (Ag13Cu4) and [AuAg12Cu4(o1-CBT)12]3- (AuAg12Cu4). These substitutions make systematic modulation their structural electronic properties. show that preferentially occupies core, while localizes in tetrahedral shell, influencing stability diversity clusters. The band gap expands systematically (2.09 eV for Ag17 to 2.28 AuAg12Cu4), altering optical absorption emission. Ultrafast measurements reveal longer excited-state lifetimes Cu-containing clusters, highlighting effect heteroatom incorporation. results demonstrate tunable platform designing nanoclusters tailored properties, implications optoelectronics catalysis. Tuning structure composition atomically precise metal leads property changes which, however, are still poorly understood. Here, authors synthesize precisely substituted analogues study luminescence

Language: Английский

---

Recent progress in functional atom-precise coinage metal clusters protected by alkynyl ligands

Coordination Chemistry Reviews, Journal Year: 2021, Volume and Issue: 453, P. 214315 - 214315

Published: Nov. 24, 2021

Language: Английский

---

Metal–Organic Frameworks-Mediated Assembly of Gold Nanoclusters for Sensing Applications

Journal of Analysis and Testing, Journal Year: 2022, Volume and Issue: 6(2), P. 163 - 177

Published: May 7, 2022

Language: Английский

---

Light-Activated Intercluster Conversion of an Atomically Precise Silver Nanocluster

ACS Nano, Journal Year: 2021, Volume and Issue: 15(10), P. 15781 - 15793

Published: Oct. 4, 2021

Noble metal nanoclusters protected with carboranes, a 12-vertex, nearly icosahedral boron-carbon framework system, have received immense attention due to their different physicochemical properties. We synthesized ortho-carborane-1,2-dithiol (CBDT) and triphenylphosphine (TPP) coprotected [Ag42(CBDT)15(TPP)4]2- (shortly Ag42) using ligand-exchange induced structural transformation reaction starting from [Ag18H16(TPP)10]2+ Ag18). The formation of Ag42 was confirmed UV-vis absorption spectroscopy, mass spectrometry, transmission electron microscopy, X-ray photoelectron infrared multinuclear magnetic resonance spectroscopy. Multiple optical features, which exhibit characteristic patterns, its molecular nature. is the highest nuclearity silver nanocluster carboranes reported so far. Although these clusters are thermally stable up 200 °C in solid state, light-irradiation solutions dichloromethane results conversion [Ag14(CBDT)6(TPP)6] Ag14). Single crystal diffraction Ag14 exhibits Ag8-Ag6 core-shell structure this nanocluster. Other spectroscopic microscopic studies also confirm Ag14. Time-dependent spectrometry revealed that light-activated intercluster went through two sets intermediate clusters. first set intermediates, [Ag37(CBDT)12(TPP)4]3- [Ag35(CBDT)8(TPP)4]2- were formed after 8 h light irradiation, second comprised [Ag30(CBDT)8(TPP)4]2-, [Ag26(CBDT)11(TPP)4]2-, [Ag26(CBDT)7(TPP)7]2- 16 irradiation. After 24 h, complete. Density functional theory calculations reveal kernel-centered excited state orbitals responsible for transformation. Interestingly, showed near-infrared emission at 980 nm (1.26 eV) lifetime >1.5 μs, indicating phosphorescence, while shows red luminescence 626 (1.98 550 ps, fluorescence. Femtosecond nanosecond transient transitions between electronic energy levels associated carrier dynamics. Formation states shown be core

Language: Английский

---

Copper‐Sulfur‐Nitrogen Cluster Providing a Local Proton for Efficient Carbon Dioxide Photoreduction

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(48)

Published: Oct. 6, 2023

Atomically precise Cu clusters are highly desirable as catalysts for CO2 reduction reaction (CO2 RR), and they provide an appropriate model platform elaborating their structure-activity relationship. However, efficient overall photocatalytic RR with H2 O using assembled Cu-cluster aggregates single component photocatalyst has not been reported. Herein, we report a stable crystalline Cu-S-N cluster local protonated N-H groups (denoted Cu6 -NH). The catalyst exhibits suitable redox potentials, high structural stability, active catalytic species, narrow band gap, which account its outstanding performance under visible light, ≈100 % selectivity CO evolution. Remarkably, systematic isostructural control experiments, in situ infrared spectroscopy, density functional theory calculations revealed that the pyrimidine N atoms -NH act proton relay station, providing during RR. This efficiently lowers energy barrier formation of *COOH intermediate, is rate-limiting step, enhancing performance. work lays foundation development atomically metal-cluster-based photocatalysts.

Language: Английский

---

Facile Construction of New Hybrid Conjugation via Boron Cage Extension

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(6), P. 3577 - 3587

Published: Feb. 6, 2023

Aromatic polycyclic systems have been extensively utilized as structural subunits for the preparation of various functional molecules. Currently, aromatics-based are predominantly generated from extension two-dimensional (2D) aromatic rings. In contrast, compounds based on three-dimensional (3D) aromatics such boron clusters less studied. Here, we report three types cluster-cored tricyclic molecular systems, which constructed a 2D ring, 3D nido-carborane, and an alkyne. These new can be facilely accessed by Pd-catalyzed B-H activation subsequent cascade heteroannulation carborane pyridine with alkyne in isolated yield up to 85% under mild conditions without any additives. Computational results indicate that newly ring fusion carborane, pyridyl is non-aromatic. However, not only leads 1H chemical shift considerably downfield shifted owing strong diatropic current embedded but also devotes new/improved physicochemical properties including increased thermal stability, emergence absorption band, largely red-shifted emission band enhanced efficiency. Besides, number bright, color-tunable solid emitters spanning over all visible light obtained absolute luminescence efficiency 61%, contrast aggregation-caused quenching of, e.g., Rhodamine B containing 2D-aromatics-fused structure. This work demonstrates hybrid conjugated might promising scaffolds construction

Language: Английский

---