Trace thioether inserted polyamine patches on a support mediate uniform gold nanoclusters as ultrahigh active catalysts

Li, Chenhui; Xu, Siyuan; Jin, Ming; Wan, Decheng

doi:10.1039/d1ta03220h

Cited by 11 publications

(30 citation statements)

References 55 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The ratio of surface areas ( S 1 and S 2 ) of samples 1 and 2 is S 1 / S 2 = π D 1 2 / π D 2 2 Combination of eqs – leads to TOF 2 / TOF 1 = italickD 2 / D 1 Thus, the linear relationship in Figure implies that dppb, as a stronger ligand than amine, hardly suppresses the catalytic activity of AuNCs, at least for the substrate of 4-NP. This is very different from the coligand of thioether, which actually suppresses the catalytic activity …”

Section: Resultsmentioning

confidence: 87%

“…This is very different from the coligand of thioether, which actually suppresses the catalytic activity. 44 Recycling 8 times leads to no appreciable degeneration of the catalytic performance (Figure 9), and the stability should be attributed to several factors. One is that in a reductive environment, Au exclusively exists as Au(0), and solubility of Au(0) in water is limited (around 1 ppb, as detected with ICP-OES).…”

Section: Catalytic Performance Of Au-s-pei-dppbmentioning

confidence: 97%

“…The synthesis is based on a literature procedure. 44 Typically, a solution of PEI (dehydrated, 1.77 g, 40.7 mmol NH) in ethanol (30 mL) is mixed with the polymer beads (15 g, ∼72 mmol benzyl chloride) and heated at 80 °C for 6 h under stirring and under a N 2 atmosphere. The beads were separated by filtration, fully washed in sequence with aqueous NaOH (5 wt %), deionized water, and absolute ethanol, and dried in vacuum to yield beads (15.30 g, 91%).…”

Section: Functionalization Of the Support With Pei (S-pei)mentioning

confidence: 99%

“…For example, the presence of trace thioethers could suppress the catalytic activity. 44 The reduction of 4-NP is employed to evaluate whether phosphine ligands suppress the catalytic performance of Au-s-PEI-dppb.…”

Section: Catalytic Performance Of Au-s-pei-dppbmentioning

confidence: 99%

“…Very recently, we highlighted the role of a molecular patch on in situ supporting uniform AuNCs. 44 Unlike the unstable and uneven patches prepared through self-assembly of amphiphilic polymers, a molecular patch is featured with good stability, uniformity, and a nanoscale size. PEI belongs to a family of globular macromolecules with a series of sizes available and is onestep available and bears dense active amino groups.…”

Section: Introductionmentioning

confidence: 99%

See 4 more Smart Citations

Uniform Gold Nanoclusters Supported on Mesoporous Polymer Beads Decorated with Polyaminophosphine Patches for the Catalytic Reduction of 4-Nitrophenol

Yao

Jin

et al. 2023

ACS Appl. Nano Mater.

Self Cite

View full text Add to dashboard Cite

In the jigsaw puzzle of quality gold nanoclusters (AuNCs), those protected by weak ligands or coligands are still rarely available. Here, we provide an example in the case of supported AuNCs. Branched polyethylenimine (PEI, diameter of 1.86 nm) is introduced as discrete molecular patches onto the support of mesoporous polymer beads. Each patch is derived into polyaminophosphine with 2-(diphenylphosphino) benzaldehyde (dppb). The molecular patch is of nanoscale and uniform size. The polymer beads after PEI loading bear unimodal pores (3.9 nm), and the specific surface area is of 390 m 2 g −1 . AuNCs are obtained by mildly heating the mixture of the functionalized beads and aqueous chloroauric acids. Uniform AuNCs with a diameter of 1.2 ± 0.2 nm (∼53 Au atoms) are obtained when each PEI patch bears 17 dppb ligands, smaller than that of 3.5 nm in the absence of any dppb, suggesting that dppb enhances the nucleation of AuNCs. The heteroleptic AuNCs show ultrahigh catalytic performance (TOF = 391 h −1 ) for the reduction of 4-nitrophenol, where the dppb ligands hardly suppress the catalytic activity. The catalyst is well recoverable and durable for the reduction of 4-nitrophenol.

show abstract

Section: Resultsmentioning

confidence: 87%

Section: Catalytic Performance Of Au-s-pei-dppbmentioning

confidence: 97%

Section: Functionalization Of the Support With Pei (S-pei)mentioning

confidence: 99%

Section: Catalytic Performance Of Au-s-pei-dppbmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Uniform Gold Nanoclusters Supported on Mesoporous Polymer Beads Decorated with Polyaminophosphine Patches for the Catalytic Reduction of 4-Nitrophenol

Yao

Jin

et al. 2023

ACS Appl. Nano Mater.

Self Cite

View full text Add to dashboard Cite

show abstract

Highly Efficient and Robust Platinum Nanocluster Catalyst Mediated by Polyamine Amidine‐Decorated Mesoporous Polymer Beads

Li,

Jin

et al. 2024

ChemNanoMat

View full text Add to dashboard Cite

Platinum nanoclusters (PtNCs) are promising in catalysis due to their large specific surface area and unique physicochemical properties. Here, ultrasmall and uniform PtNCs are facilely synthesized with the mediation of amidine‐functionalized polyamines patched on mesoporous poly(divinylbenzene‐4‐vinylbenzyl chloride) beads. When each ligand patch has 14 amidines, ultrafine PtNCs (with the size as low as 1.1 ± 0.1 nm) are formed as a result of several factors: deprotonated amidines (carbenes) strongly passivate on Pt atoms, amidines act as co‐stabilizers along with weak polyamine ligands, and PtNCs are confined to discrete ligand patches. When one ligand patch contains 9.3 amidines, the resulting PtNCs (1.7 ± 0.3 nm) reach the highest turnover frequency of 536 h‐1 for the catalytic reduction of 4‐nitrophenol in a batch reaction. This catalyst remains rather stable in a continuous flow test as a 4‐nitrophenol conversion of over 95% is still achieved after running consecutively for 10 h.

show abstract

Polystyrene Microspheres Decorated with Au₄Cu₅ Nanoclusters and their Application in Catalytic Reduction of 4‐Nitrophenol

et al. 2021

View full text Add to dashboard Cite

Ultrasmall nanoclusters are emerging nanocatalysts due to their distinct physico-chemical properties. However, the instability and agglomeration of these nanoclusters restrict their practical application. Herein, we designed a negatively charged crosslinked polystyrene (PS) microsphere as support and decorated it with positively charged ultrasmall [Au 4 Cu 5 (Dppm) 2 (C 6 H 11 S) 6 ] + [BPh 4 ] À (Au 4 Cu 5 , in which Dppm stands for bis-(diphenylphos-phino)methane) nanoclusters through strong electrostatic adsorption, as evidenced by X-ray photoelectron spectroscopy. The PS@Au 4 Cu 5 nanocomposites were well-dispersed in water, exhibiting enhanced catalytic activity for the reduction reaction of 4-nitrophenol to produce 4-aminophenol. These findings open promising opportunities for supported nanocluster catalysis. Results and DiscussionThe characterization of Au 4 Cu 5 and PS microspheres Scheme 1 illustrates the synthetic method employed to produce the PS@Au 4 Cu 5 nanocomposites. Firstly, the Au 4 Cu 5

show abstract

Trace thioether inserted polyamine patches on a support mediate uniform gold nanoclusters as ultrahigh active catalysts

Abstract: Ultrasmall and uniform gold nanoclusters (AuNCs), either freestanding or supported, are usually indirectly available unless mediated with abundant strong ligands, but strong ligands usually suppress the catalytic activity towards certain...

Cited by 11 publications

References 55 publications

Uniform Gold Nanoclusters Supported on Mesoporous Polymer Beads Decorated with Polyaminophosphine Patches for the Catalytic Reduction of 4-Nitrophenol

Uniform Gold Nanoclusters Supported on Mesoporous Polymer Beads Decorated with Polyaminophosphine Patches for the Catalytic Reduction of 4-Nitrophenol

Highly Efficient and Robust Platinum Nanocluster Catalyst Mediated by Polyamine Amidine‐Decorated Mesoporous Polymer Beads

Polystyrene Microspheres Decorated with Au₄Cu₅ Nanoclusters and their Application in Catalytic Reduction of 4‐Nitrophenol

Contact Info

Product

Resources

About

Trace thioether inserted polyamine patches on a support mediate uniform gold nanoclusters as ultrahigh active catalysts

Abstract: Ultrasmall and uniform gold nanoclusters (AuNCs), either freestanding or supported, are usually indirectly available unless mediated with abundant strong ligands, but strong ligands usually suppress the catalytic activity towards certain...

Cited by 11 publications

References 55 publications

Uniform Gold Nanoclusters Supported on Mesoporous Polymer Beads Decorated with Polyaminophosphine Patches for the Catalytic Reduction of 4-Nitrophenol

Uniform Gold Nanoclusters Supported on Mesoporous Polymer Beads Decorated with Polyaminophosphine Patches for the Catalytic Reduction of 4-Nitrophenol

Highly Efficient and Robust Platinum Nanocluster Catalyst Mediated by Polyamine Amidine‐Decorated Mesoporous Polymer Beads

Polystyrene Microspheres Decorated with Au4Cu5 Nanoclusters and their Application in Catalytic Reduction of 4‐Nitrophenol

Contact Info

Product

Resources

About

Polystyrene Microspheres Decorated with Au₄Cu₅ Nanoclusters and their Application in Catalytic Reduction of 4‐Nitrophenol