Molecular adaptability and reactivity in Ni6(SR)12-catalyzed adipic acid synthesis

doi:10.1016/S1872-2067(26)65020-6

Abstract

Abstract:

Constructing the active sites of a heterogeneous catalyst, controlling the accessibility of molecules to active sites and ultimately tailoring its catalytic property are of utmost significance yet highly challenging. Herein, we report two systems of atomically precise cluster catalysts for the cyclohexanone electrooxidation reaction, which correspond to 2-phenylethanethiol-protected Ni₆(SC₂H₄Ph)₁₂ and 1-dodecanethiol-protected Ni₆(SC₁₂H₂₅)₁₂. The two clusters are identified to have similar metal active cores while their distinct surrounding environments access to the metal cores are capable of discriminating between water and cyclohexanone, exhibiting substantially influences on their activity and selectivity. Our studies reveal that water molecules are preferably adsorbed onto the surface of the Ni₆(SC₁₂H₂₅)₁₂, thereby pushing the cyclohexanone molecule away from the metal core, which favors the oxygen evolution reaction on the Ni₆(SC₁₂H₂₅)₁₂ catalyst. In contrast, the cyclohexanone is adaptively pulled toward the Ni core by the 2-phenylethanethiol ligands of Ni₆(SC₂H₄Ph)₁₂, in which the C=O group of the cyclohexanone can approach, adsorb and convert over the Ni sites and 2-phenylethanethiol ligands have stronger electron interactions with Ni core facilitating the cyclohexanone oxidation reaction on the Ni₆(SC₂H₄Ph)₁₂ catalyst and hence achieving high faradaic efficiency and high yield for adipic acid. This study challenges the conventional heterogeneous catalysts without atomic-precision structure and instead couples the complementary roles of the inner and outer environments of the cluster catalysts to tailor their catalytic properties.

Key words: Electrooxidation, Cyclohexanone, Adipic acid, Molecular adaptability, Clusters

Qingxi Zhai, Yiqi Tian, Hao Wang, Shisi Tang, Qiang Yuan, Xu Liu, Weiping Ding, Fan Tian, Yan Zhu. Molecular adaptability and reactivity in Ni₆(SR)₁₂-catalyzed adipic acid synthesis[J]. Chinese Journal of Catalysis, 2026, 86: 225-235.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65020-6

https://www.cjcatal.com/EN/Y2026/V86/I7/225

Figures/Tables 6

Fig. 1. (a) Typical catalytic process of cyclohexanone electrooxidation to adipic acid accompanied with the competitive pathway of OER. (b) Representative strategies for the cyclohexanone oxidation to adipic acid over the Ni-based heterogeneous catalysts. (c) Cluster catalysis of two Ni6(SR)12 systems for cyclohexanone electrooxidation to adipic acid.

Fig. 2. (a) Crystal structures of Ni6(SC2H4Ph)12 (left) and Ni6(SC12H25)12 (right). (b) Atomic-packing patterns of Ni6(SC2H4Ph)12 (left) and Ni6(SC12H25)12 (right) in their single crystals along z axis. (c) Excitation analysis cooperating with their partial density of states and theoretical UV-vis absorption spectra of Ni6(SC2H4Ph)12 (left) and Ni6(SC12H25)12 (right) derived from DFT and TDDFPT calculations. α, β and γ respectively denote the characteristic absorption bands presented in the UV-vis spectra of the two clusters.

Fig. 3. (a) LSV curves of the Ni6(SC2H4Ph)12 and Ni6(SC12H25)12 catalysts in 1.0 mol L-1 KOH with and without 0.1 mol L-1 cyclohexanone. (b) Corresponding current densities at 1.6 V vs. RHE from the LSV curves in 1.0 mol L-1 KOH with and without 0.1 mol L-1 cyclohexanone. (c) Differences in current densities were plotted against scan rates to calculate the electrochemical double-layer capacitance (Cdl) in 1.0 mol L-1 KOH with 0.1 mol L-1 cyclohexanone. (d) Adipic acid productivity over the two catalysts at different potentials in 1.0 mol L-1 KOH with 0.1 mol L-1 cyclohexanone. (e) FEs of adipic acid over the two catalysts at different potentials in 1.0 mol L-1 KOH with 0.1 mol L-1 cyclohexanone. (f) Comparison of catalytic performances for COR over the two clusters with other Ni-based catalysts reported (details shown in Tables S3 and S4).

Fig. 4. (a) The OCP of the Ni6(SC12H25)12 and Ni6(SC2H4Ph)12 catalysts in 1 mol L-1 KOH solution before and after 0.1 mol L-1 CHN was injected. (b-e) The Bode plots of the Ni6(SC12H25)12 and Ni6(SC2H4Ph)12 catalysts in KOH with CHN and without CHN. (f) I-t curves of Ni6(SC12H25)12 and Ni6(SC2H4Ph)12 at different potentials (V vs. RHE) in normal pulse voltammetry. The NPV measurements were conducted in 1 mol L-1 KOH with 0.1 mol L-1 cyclohexanone and the current density was recorded at 300-s interval after each potential pulse was increased in potential amplitude from 0.9 to 1.7 V vs. RHE.

Fig. 5. The snapshots of molecular diffusion dynamics from 150 H2O and 5 CHN onto Ni6(SC2H4Ph)12 (a) and Ni6(SC6H13)12 (b) models, respectively. Atom notations: Ni, green; S, yellow; C, gray; H, white; O, red. (c) The pair distribution function (g(r)) curves for the interatomic distance between Ni atoms of the clusters and O atoms from H2O or CHN molecules. The dotted curves corresponded to the integrals from g(r). (d) The pair distribution function (g(r)) curves for the interatomic distance between Ni atoms of the clusters and O atoms of CHN molecules. (e) The distances from the geometric center of the Ni-S cores to the O atoms of CHN with the reaction time.

Fig. 6. Time-resolved in situ FTIR spectra of CHN molecule adsorbed onto different samples: (a) no catalyst; (b) Ni6(SC2H4Ph)12 cluster; (c) Ni6(SC12H25)12 cluster. (d) The simulated infrared spectra of pure CHN molecule, CHN molecule absorbed onto Ni6(SC2H4Ph)12 cluster and CHN molecule absorbed onto Ni6(SC12H25)12 cluster. (e) The simulated absorption mode of CHN molecule on Ni6(SC2H4Ph)12 cluster. (f) The simulated absorption mode of CHN molecule on Ni6(SC12H25)12 cluster. The arrows showed the vibration directions of species. (g) Free energy diagrams for the cyclohexanone electrooxidation to adipic acid on Ni sites of Ni6(SC2H4Ph)12 and Ni6(SC12H25)12. The molecular structures of the adsorbed species were shown in Fig. S17. Atom notations: Ni, green; S, yellow; C, gray; H, white; O, red.

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Molecular adaptability and reactivity in Ni₆(SR)₁₂-catalyzed adipic acid synthesis

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