Unveiling the Formation Mechanism for Binary Semiconductor Nanoclusters: a Two-Step Pathway to a Double-Shell Structured Copper Sulfide Nanocluster
0
Citation
68
Reference
10
Related Paper
Abstract:
This work represents an important step in the quest to unveil the formation mechanism of atomically precise binary semiconductor nanoclusters. In this study, we develop an acid-assisted C–S bond cleavage approach, wherein the C–S bonds in the metal thiolate precursor can be readily cleaved to release S2– with the assistance of a suitable acid in the presence of Cu2O as the catalyst. This process spontaneously fosters the formation of a [−Cu–S–Cu−] framework and promotes the structural growth into a high nuclearity assembly. Specifically, by employing Cu(I) tert-butyl thiolate ([CuStBu]∞) and carboxylate acid CH2═CHCOOH as the copper/sulfur precursor and C–S bond "scissor", a high-nuclearity nanocluster [S–Cu56] (Cu56S12(OOCCH═CH2)12(SC(CH3)3)20) featuring a double-shell configuration has been effectively prepared in high yield. Importantly, the [CuStBu]∞ precursor and the intermediate [S–Cu14] (Cu14(StBu)8(OOCCH═CH2)6) cluster have also been successfully isolated and structurally characterized, which ultimately enables the establishment of a two-step formation pathway for the [S–Cu56] nanocluster. Furthermore, in contrast to conventional reduction synthetic routes for metal nanoclusters containing Cu(0) or Cu(I), the acid-assisted C–S bond cleavage approach represents an oxidation process with respect to the constituent metals, yielding highly charged Cu(II) cations in the copper sulfide nanocluster.Keywords:
Nanoclusters
Bond cleavage
Cleavage (geology)
Copper sulfide
Copper sulfide
Cite
Citations (37)
Nanoclusters
Noble metal
Cite
Citations (1)
To know the anodic reaction mechnism of cuprous sulfide in sulfuric acid solution, the following experiments were made; the measurements of the electrode potentials, anodic polarization behaviours and galvanostatic polarization behaviours of the Cu2S-CuS sulfide system, and observations of the copper concentration by X-ray microanalyser (XMA) and crystal structure by X-ray reflection of the sulfide electrode surface.(1) The electrode potentials of the Cu2S-CuS sulfide system show three characteristic values for Cu2S, Cu1.8S and CuS sulfide, respectively.(2) Cuprous sulfide was dissolved anodically in sulfuric acid solution through the following two processes; \phantom(1) i(i) Cu2S→CuS+Cu2++2e \phantom(1) (ii) CuS→Cu2++S+2e. (3) The apparent activation energy for the diffusion of copper atom in cuprous sulfide was about 3.4 kcal/mol.
Copper sulfide
Sulfide Minerals
Lead sulfide
Cite
Citations (2)
Nanoclusters
Cite
Citations (2)
Cleavage (geology)
Cyanogen bromide
Bond cleavage
Peptide bond
Cite
Citations (320)
Copper sulfide
Zinc sulfide
Cobalt sulfide
Cadmium sulfide
Selected area diffraction
Lead sulfide
Sodium sulfide
Cite
Citations (49)
Silver sulfide
Copper sulfide
Silver bromide
Silver iodide
Lead sulfide
Silver nanoparticle
Cite
Citations (0)
Data on the structures and properties of nanoclusters and nanocluster systems are analysed. A classification of nanoclusters and nanosystems based on the method of their preparation is proposed. Methods for assembling nanoclusters to give nanostructures, the main principles of assembling and the types of nanosystems are described. The appearance of new properties upon combination of nanoclusters into a nanosystem is noted. The bibliography includes 274 references.
Nanoclusters
Cite
Citations (115)
Nanoclusters
Cite
Citations (0)
In this chapter, strategies for lignin linkages cleavage beginning with C α O–H/ArO–H or C α –OH bonds heterolysis are summarized, primarily focusing on lignin alkaline hydrolysis, acidolysis, and their corresponding tandem processes. Chapter 8.1 focuses on the base-catalyzed cleavage of the C β –OAr bond beginning with C α O–H or ArO–H heterolysis to oxygen anion, which further induces the cleavage of the lignin C β –OAr bond. Chapter 8.2 summarizes the various acid-catalyzed methods for the C β –OAr bond cleavage beginning with C α –OH heterolysis, which further induce the C β –OAr bond cleavage via a C α =C β –OAr intermediate.
Heterolysis
Cleavage (geology)
Bond cleavage
Cite
Citations (0)