Regioselective hydrogenation of alkenes over atomically dispersed Pd sites on NHC-stabilized bimetallic nanoclusters

Shen, Hsin‐Hui; Qu, Wu; Hazer, Maryam Sabooni Asre; Tang, Xiongkai; Han, Ying‐Zi; Qin, Ruixuan; Ma, Chuxin; Malola, Sami; Teo, Boon K.; Häkkinen, Hannu

doi:10.1016/j.chempr.2022.04.017

Cited by 39 publications

(43 citation statements)

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“…Surface ligands can not only maintain the structural integrity of cluster-based catalysts, but also modulate the coordination environment of active sites. In this context, surface additives often create delicate sites for the activation of reactants and control reaction pathways, just as an enzyme does, thereby beneficial for selective catalysis. , One recent example refers to the regioselective hydrogenation of alkenes by NHC-stabilized bimetallic nanoclusters of PdAu 9 (NHC Bn ) 7 X 2 (NHC Bn is dibenzylbenzimidazolin-2-ylidene, X is Br or Cl) . In the cluster, the atomically dispersed Pd site was located onto an Au 9 ring stabilized by NHC and halide ligands (Figure a).…”

Section: Atomically Precise Metal Clusters As Model Catalystsmentioning

confidence: 99%

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

et al. 2022

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

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Section: Atomically Precise Metal Clusters As Model Catalystsmentioning

confidence: 99%

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

et al. 2022

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“…Such a structure allows the catalyst to distinguish different alkenes in catalytic hydrogenation, due to the inherent steric effect of the NHC ligands, leading to a high selectivity in the regioselective hydrogenation of dienes such as linalool. [41] Moreover, this mass-diffusion barrier may affect the local concentration of the reactants on the surface of noble metal catalysts. Toma et al reported quaternary ammonium additive for electrocatalytic CO 2 reduction on Ag surfaces that changes the Faradaic efficiency for CO from 25 % on Ag foil to 97 % and reduces the current density of the hydrogen evolution reaction by a factor of 440 (Figure 10 b 1 , b 2 ).…”

Section: Ligand-assisted Local Environment Construction On Noble Meta...mentioning

confidence: 99%

“…reported a catalyst containing atomically dispersed Pd sites on N ‐heterocyclic carbene (NHC)‐stabilized Au nanoclusters. Such a structure allows the catalyst to distinguish different alkenes in catalytic hydrogenation, due to the inherent steric effect of the NHC ligands, leading to a high selectivity in the regioselective hydrogenation of dienes such as linalool [41] . Moreover, this mass‐diffusion barrier may affect the local concentration of the reactants on the surface of noble metal catalysts.…”

Section: The Roles Of the Ligand In Surface‐engineering Of Noble Meta...mentioning

confidence: 99%

“…which may impose a significant influence on the selectivity of the catalysts in a series of electrochemical reactions. [40][41][42][43][44][45][46] To date, the effects of the ligand on the shape control of noble metal nanocrystals have been well summarized in previous review papers. [21,22] Herein, we make a summary of recent findings of the effects of the ligand on the controlled synthesis and surface-engineering of noble metal nanocrystals, including the results from many groups in this field and those from our group.…”

Section: Introductionmentioning

confidence: 99%

“…Second, there is usually an electron transfer between the ligand and the nanocrystal surface, which may substantially change the interaction between the reactants and the noble metal nanocrystals, leading to distinctive electrocatalytic properties [37–39] . Third, the ligand may help construct unique local environments on the surface of noble metal nanocrystals, which may impose a significant influence on the selectivity of the catalysts in a series of electrochemical reactions [40–46] …”

Section: Introductionmentioning

confidence: 99%

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Effects of Ligands on Synthesis and Surface‐Engineering of Noble Metal Nanocrystals for Electrocatalysis

Liu

Gao

2022

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Noble metal nanocrystals are a family of important catalysts for a broad range of processes (especially electrocatalytic ones), which are usually obtained as a hybrid each containing a metallic core and a ligand shell. It is well recognized that the ligand plays a critical role in regulating the crystal growth into different shapes and maintaining the colloidal stability of the nanocrystals. Recently, more effects of the ligand were revealed in controlling both the synthesis and the surface property of noble metal nanocrystals, which could be maneuvered to achieve distinctive catalytic properties. In this review, we present a summary of the roles of the ligand based on typical results from the literature. The review begins with a discussion on the roles of the ligand in the controlled synthesis of noble metal nanocrystals, including the shape control, the reduction potential control for suppressing self-nucleation and galvanic replacement reaction, and the electroless plating effect for noble metal/non-noble metal co-reduction. The following section includes a discussion of the effects of the ligand on the surface property of noble metal nanocrystals, including the ensemble size engineering, the ligand-metal electron transfer, and the local microenvironment construction, toward designable electrocatalytic properties. At the end, we provide our perspectives on the future research of ligand engineering as an advanced technique for tailoring electrocatalytic properties of noble metal nanocrystals.

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Atomically precise Cu₃₂ nanoclusters with selenide doping: Synthesis, bonding, and catalysis

Huo,

Ren,

Wang

et al. 2024

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Copper nanoclusters with stable compositions and precise structures have long been sought after, as they possess properties that are absent in gold and silver counterparts. However, the creation of copper nanoclusters with novel compositions, structures, and functionalities remains largely unexplored in the literature. In this study, we demonstrate that selenide doping is an effective method for fabricating stable copper nanostructures through controlled synthesis and structure determination of a copper–selenide nanocluster. The nanocluster of [Cu32Se7(BnSe)18(PPh3)6]+ (denoted as Cu32Se7, Bn is benzyl) has been prepared by reducing copper salts in the presence of organic diselenides. The atomic structure of the Cu32Se7 cluster, accurately determined through single‐crystal X‐ray diffraction, reveals a core–shell arrangement of Cu20Se7@Cu12(BnSe)18(PPh3)6, where Se2− anions are well dispersed in the Cu20 framework. Notably, this cluster represents a rare example of copper–selenide semiconductor nanoclusters. Experimental and theoretical analysis shows strong interactions between Se ligands and metal atoms, resulting in high stability of the Cu32Se7 cluster. Furthermore, the cluster exhibits excellent catalytic performance in the hydroboration reaction of alkynes, producing a range of vinylboron compounds with adjustable structures and functions. Importantly, the cluster undergoes no structural or nuclearity changes during the reaction, as confirmed by extended X‐ray absorption fine structure and X‐ray photoelectron spectroscopy studies. This study not only presents a molecular cluster model highlighting the effectiveness of selenide dopants in fabricating new copper nanostructures but also paves the way for utilizing stable copper nanoclusters in diverse and exciting areas beyond catalysis.

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Regioselective hydrogenation of alkenes over atomically dispersed Pd sites on NHC-stabilized bimetallic nanoclusters

Cited by 39 publications

References 54 publications

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

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

Effects of Ligands on Synthesis and Surface‐Engineering of Noble Metal Nanocrystals for Electrocatalysis

Atomically precise Cu₃₂ nanoclusters with selenide doping: Synthesis, bonding, and catalysis

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Regioselective hydrogenation of alkenes over atomically dispersed Pd sites on NHC-stabilized bimetallic nanoclusters

Cited by 39 publications

References 54 publications

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

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

Effects of Ligands on Synthesis and Surface‐Engineering of Noble Metal Nanocrystals for Electrocatalysis

Atomically precise Cu32 nanoclusters with selenide doping: Synthesis, bonding, and catalysis

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Atomically precise Cu₃₂ nanoclusters with selenide doping: Synthesis, bonding, and catalysis