Effect of Different Heteroatoms Anchoring a Cu Single-Atom Catalyst on Acetylene Hydrochlorination

Abstract

A Cu-based catalyst has the advantages of low price and high reserves as well as catalytic activity in acetylene hydrochlorination. In order to better design and prepare efficient Cu single-atom catalysts (SACs) for acetylene hydrochlorination, a single Cu atom anchored by different heteroatoms was investigated by constructing the CuX4 (X = B, C, N, O, P) structure using the spin-polarized density functional theory (DFT). According to the results, the N-doped substrate significantly increased the charge of the Cu atom, and B- and P-doped substrates provided multiple active sites, while the O-doped substrate could not stably anchor the single Cu atom. In general, different catalysts had different dominant mechanisms, and it was found that the charge transfer between single metal atoms and substrates could be used as a descriptor of the catalytic performance. This work reveals the effect mechanisms of the local coordination environment for Cu SACs catalyzing acetylene hydrochlorination, as well as provides theoretical insights for the rational design of efficient Cu-based catalysts.

Excess Copper Chloride Induces Active Sites over Cu-Ligand Catalysts for Acetylene Hydrochlorination

“…The second shell site with more positive charge exhibits generally higher activities than the first one (Table S6). Similar activity–charge correlation results were also reported by research on Cu single-atom catalysts for acetylene hydrochlorination . The inspection of CuCl x -( i Pr 2 PCl) y catalysts validates the universality of the conclusions.…”

“…Similar activity−charge correlation results were also reported by research on Cu single-atom catalysts for acetylene hydrochlorination. 53 The inspection of CuCl x -( i Pr 2 PCl) y catalysts validates the universality of the conclusions. So far, the experimental and theoretical results are able to rationalize the fact that copper chloride is generally excess in ligand-modified Cu-based catalysts (Figure 4e).…”

“…The chain electron transfer mechanism results in a gradient distribution of Cu atomic charge (also see Figure S22). Given that atomic charge was regarded as one of the descriptors for the activity of catalysts in acetylene hydrochlorination, , there is a crucial issue raised, namely, whether the catalytic activities of diverse Cu sites is correspondingly different?…”

Electrocatalysts for value-added electrolysis coupled with hydrogen evolution

“…For example, the N-doped substrates significantly increase the charge of the metal atoms (single/dual atoms), and B- and P-doped substrates provide multiple active sites on the exposed surface. 135 Lu et al reported an ultrafast method for successfully engineering the surface of Ni foam into a hydrophilic S-doped Ni/Fe (oxy)hydroxide layer with multiple levels of porosity and with a large surface area and numerous active sites. In terms of site-selectivity governed by the S-doped NiFe-LDH/NF, it could be regulated by the local charge distribution of the Ni atoms, leading to the formation of Ni 2+ sites with excellent activity and thus favoring the interfacial catalytic reaction.…”

Hydrochlorination of acetylene catalyzed by mesoporous carbon with hierarchical assembly of polyimide nanosheets

“…In the past few decades, gold-based catalysts have been some of the most promising catalysts among the many transition metal catalysts, such as Au-based, [7][8][9][10][11][12] Pd-based, [13][14][15] Ru-based, [16][17][18][19][20] Bi-based 21 and Cu-based [22][23][24][25][26] catalysts, owing to their excellent catalytic activity and stability, but the high cost and low reserve prohibit the large-scale utilization of Au-based catalysts for acetylene hydrochlorination. Recently, carbonaceous materials have generally been employed in various reactions, such as the CO 2 reduction reaction, 27 the oxygen reduction reaction, 28 cellulose hydrolysis, 29 hydrazine oxidation, 30 and so on.…”