Spontaneous dispersion of metallic nickel centers in inert metal substrate for the selective hydrogenation of carbon-carbon triple bonds

doi:10.1016/S1872-2067(24)60048-3

Abstract

Abstract:

Single-site metal catalysts with maximal utilization of active centers and desired target product selectivity represent a hot research topic within the realms of both academic and industry. However, the synthetic strategy is generally complicated and requires the precise control of interplay between metal centers and supporting materials. Herein, a simple spontaneous dispersion and universal strategy are developed to construct all-metal catalyst systems containing isolated metallic centers utilizing the spontaneous dispersion behaviors of transition metal centers Ni in inert substrate (Al, Mg and Ti). Ni/Al and Ni/Mg show remarkable performances in the model reaction of acetylene semi-hydrogenation with state-of-the-art site-specific activity, high ethylene selectivity and good stability. Especially, Ni/Al is reported for the first time to be an eligible low-cost catalyst for the selective hydrogenation of carbon-carbon triple bonds, surpassing the benchmark Lindlar catalyst. The reaction mechanism of acetylene semi-hydrogenation over Ni/Al catalyst is well clarified via the combination of kinetic analyses, spectroscopy investigation and theoretical calculations. The innovative approach developed herein not only expands the synthetic strategies toward single-site metal catalysts but also holds promise for practical applications in diverse chemical transformations due to the intrinsic advantages of all-metal systems.

Key words: Isolated metallic site, All-metal catalyst, Selective hydrogenation, Ni-based catalyst, Spontaneous dispersion

Xin Deng, Caiyan Zheng, Weijie Li, Jiamin Wang, Di Yang, Zhenpeng Hu, Landong Li. Spontaneous dispersion of metallic nickel centers in inert metal substrate for the selective hydrogenation of carbon-carbon triple bonds[J]. Chinese Journal of Catalysis, 2024, 61: 259-268.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60048-3

https://www.cjcatal.com/EN/Y2024/V61/I6/259

Figures/Tables 6

Scheme 1. Structure model of Ni species supported on metal oxide (a) and metal substrate (b). Single-site metallic catalyst system employed in this study highlighted by red dot line.

Fig. 1. Characterization of Ni/Al system. (a) Ni 2p XPS of Ni/Al samples. (b) HS-LEIS spectra of Ni/Al sample at different etching depths with 4 He+. (c) AC-STEM images of Ni/Al sample. Scale bar = 1 nm.

Fig. 2. Catalytic performance of acetylene hydrogenation over Ni/Al catalysts. (a) Temperature-dependent behavior of Ni/Al catalysts in acetylene hydrogenation. (b) Arrhenius plot for acetylene hydrogenation over Ni/Al catalyst; Reaction conditions: 0.1 g catalyst, 1% C2H2, 20% H2, balanced with He, GHSV = 24000 mL g-1 h-1. (c) Stability test of Ni/Al catalyst at 420 K. Reaction condition: 0.1 g catalyst, 1% C2H2, 20% H2, balanced with He, GHSV = 24000 mL g-1 h-1. (d) Comparison of the acetylene semi-hydrogenation performance between Ni/Al catalyst and representative non-noble metal catalysts in the literature [14?-16,34???????-42].

Fig. 3. Reaction process of acetylene semi-hydrogenation over Ni/Al catalyst. (a) Temperature-programmed desorption profiles of H2, C2H2 and C2H4 over Ni/Al sample. (b) Primary isotope effect observed in acetylene semi-hydrogenation over Ni/Al catalyst. (c) Reaction orders of H2 and C2H2 in acetylene semi-hydrogenation over Ni/Al catalyst at 373, 393 and 413 K, respectively. (d) Pulse-response experiments of C2H2 feeding to Ni/Al catalyst in H2-D2 stream at 410 K. Reaction condition: 0.2 g catalyst, 10 mL min-1 H2, 10 mL min-1 D2, 50 mL min-1 N2, with two C2H2 pulse introduced intermittently.

Fig. 4. Calculated reaction pathways and energy profiles of acetylene hydrogenation over Ni/Al catalyst with the optimized structures shown inset. (a) Reaction between adsorbed hydrogen and adsorbed acetylene, (b) reaction between adsorbed hydrogen and gas-phase acetylene. Al, Ni, C and H atoms are shown in blue, crimson, grey and white, respectively. Energy barrier in the unit of eV shown in square brackets.

Table 1 Liquid-phase semi-hydrogenation of alkynes/alkynols over Ni/Al catalyst a.

Entry	Conversion (%)	Selectivity (%)
1	100	96
2	100	91
3	100	89
4	100	82
5	100	83
6	100	85
7	100	90
8	100	93
9	100	81
10	100	92
11	100	97
12	100	95

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