Metal-Organic Framework-Derived Ni-S/C Catalysts for Selective Alkyne Hydrogenation

Ning Li; Shaoxia Weng; Alan J McCue; Yuanfei Song; Yufei He; Yanan Liu; Junting Feng; Dianqing Li

doi:10.1021/acsami.3c09531

Metal-Organic Framework-Derived Ni-S/C Catalysts for Selective Alkyne Hydrogenation

Ning Li, Shaoxia Weng, Alan J McCue, Yuanfei Song, Yufei He, Yanan Liu^* (Corresponding Author), Junting Feng, Dianqing Li^* (Corresponding Author)

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

Abstract

A carbon matrix-supported Ni catalyst with surface/subsurface S species is prepared using a sacrificial metal-organic framework synthesis strategy. The resulting highly dispersed Ni-S/C catalyst contains surface discontinuous and electron-deficient Ni δ+ sites modified by p-block S elements. This catalyst proved to be extremely active and selective for alkyne hydrogenation. Specifically, high intrinsic activity (TOF = 0.0351 s -1) and superior selectivity (>90%) at complete conversion were achieved, whereas an analogous S-free sample prepared by the same synthetic route performed poorly. That is, the incorporation of S in Ni particles and the carbon matrix exerts a remarkable positive effect on catalytic behavior for alkyne hydrogenation, breaking the activity-selectivity trade-off. Through comprehensive experimental studies, enhanced performance of Ni-S/C was ascribed to the presence of discontinuous Ni ensembles, which promote desorption of weakly π-bonded ethylene and an optimized electronic structure modified via obvious p-d orbital hybridization.

Original language	English
Pages (from-to)	48135–48146
Number of pages	12
Journal	ACS Applied Materials & Interfaces
Volume	15
Issue number	41
Early online date	4 Oct 2023
DOIs	https://doi.org/10.1021/acsami.3c09531
Publication status	Published - 18 Oct 2023

Bibliographical note

Acknowledgements
This work was financially supported by the National Natural Science Foundation of China (22278017), the Fundamental Research Funds for the Central Universities (buctrc202303, JD2325), and the Young Elite Scientists Sponsorship Program by BAST (No. BYESS2023087).

Data Availability Statement

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsami.3c09531

Keywords

MOF-derivedmetal catalysts
S-modified Ni particles
S-doped carbon matrix
isolated Niδ+-S sites
selective acetylene hydrogenation

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title = "Metal-Organic Framework-Derived Ni-S/C Catalysts for Selective Alkyne Hydrogenation",

abstract = "A carbon matrix-supported Ni catalyst with surface/subsurface S species is prepared using a sacrificial metal-organic framework synthesis strategy. The resulting highly dispersed Ni-S/C catalyst contains surface discontinuous and electron-deficient Ni δ+ sites modified by p-block S elements. This catalyst proved to be extremely active and selective for alkyne hydrogenation. Specifically, high intrinsic activity (TOF = 0.0351 s -1) and superior selectivity (>90%) at complete conversion were achieved, whereas an analogous S-free sample prepared by the same synthetic route performed poorly. That is, the incorporation of S in Ni particles and the carbon matrix exerts a remarkable positive effect on catalytic behavior for alkyne hydrogenation, breaking the activity-selectivity trade-off. Through comprehensive experimental studies, enhanced performance of Ni-S/C was ascribed to the presence of discontinuous Ni ensembles, which promote desorption of weakly π-bonded ethylene and an optimized electronic structure modified via obvious p-d orbital hybridization. ",

keywords = "MOF-derivedmetal catalysts, S-modified Ni particles, S-doped carbon matrix, isolated Niδ+-S sites, selective acetylene hydrogenation",

author = "Ning Li and Shaoxia Weng and McCue, {Alan J} and Yuanfei Song and Yufei He and Yanan Liu and Junting Feng and Dianqing Li",

note = "Acknowledgements This work was financially supported by the National Natural Science Foundation of China (22278017), the Fundamental Research Funds for the Central Universities (buctrc202303, JD2325), and the Young Elite Scientists Sponsorship Program by BAST (No. BYESS2023087).",

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AU - Li, Ning

AU - Weng, Shaoxia

AU - McCue, Alan J

AU - Song, Yuanfei

AU - He, Yufei

AU - Liu, Yanan

AU - Feng, Junting

AU - Li, Dianqing

N1 - Acknowledgements This work was financially supported by the National Natural Science Foundation of China (22278017), the Fundamental Research Funds for the Central Universities (buctrc202303, JD2325), and the Young Elite Scientists Sponsorship Program by BAST (No. BYESS2023087).

PY - 2023/10/18

Y1 - 2023/10/18

N2 - A carbon matrix-supported Ni catalyst with surface/subsurface S species is prepared using a sacrificial metal-organic framework synthesis strategy. The resulting highly dispersed Ni-S/C catalyst contains surface discontinuous and electron-deficient Ni δ+ sites modified by p-block S elements. This catalyst proved to be extremely active and selective for alkyne hydrogenation. Specifically, high intrinsic activity (TOF = 0.0351 s -1) and superior selectivity (>90%) at complete conversion were achieved, whereas an analogous S-free sample prepared by the same synthetic route performed poorly. That is, the incorporation of S in Ni particles and the carbon matrix exerts a remarkable positive effect on catalytic behavior for alkyne hydrogenation, breaking the activity-selectivity trade-off. Through comprehensive experimental studies, enhanced performance of Ni-S/C was ascribed to the presence of discontinuous Ni ensembles, which promote desorption of weakly π-bonded ethylene and an optimized electronic structure modified via obvious p-d orbital hybridization.

AB - A carbon matrix-supported Ni catalyst with surface/subsurface S species is prepared using a sacrificial metal-organic framework synthesis strategy. The resulting highly dispersed Ni-S/C catalyst contains surface discontinuous and electron-deficient Ni δ+ sites modified by p-block S elements. This catalyst proved to be extremely active and selective for alkyne hydrogenation. Specifically, high intrinsic activity (TOF = 0.0351 s -1) and superior selectivity (>90%) at complete conversion were achieved, whereas an analogous S-free sample prepared by the same synthetic route performed poorly. That is, the incorporation of S in Ni particles and the carbon matrix exerts a remarkable positive effect on catalytic behavior for alkyne hydrogenation, breaking the activity-selectivity trade-off. Through comprehensive experimental studies, enhanced performance of Ni-S/C was ascribed to the presence of discontinuous Ni ensembles, which promote desorption of weakly π-bonded ethylene and an optimized electronic structure modified via obvious p-d orbital hybridization.

KW - MOF-derivedmetal catalysts

KW - S-modified Ni particles

KW - S-doped carbon matrix

KW - isolated Niδ+-S sites

KW - selective acetylene hydrogenation

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DO - 10.1021/acsami.3c09531

M3 - Article

C2 - 37792067

SN - 1944-8244

VL - 15

SP - 48135

EP - 48146

JO - ACS Applied Materials & Interfaces

JF - ACS Applied Materials & Interfaces

IS - 41

ER -

Metal-Organic Framework-Derived Ni-S/C Catalysts for Selective Alkyne Hydrogenation

Abstract

Bibliographical note

Data Availability Statement

Keywords

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