Bridging and terminal hydroxyl groups of Zr(OH)<sub>4</sub> as active sites for the ultraselective transformation of biomass-based alcohols

Tang, Xiaoqi; Wang, Ganping; Qin, Jiaheng; Song, Jie; Tan, Jiajun; Dong, Linkun; Mao, Weiwen; Li, Tong; Fang, Jian; Long, Yu

doi:10.1039/d3cy01477k

Catal. Sci. Technol.

2024

DOI: 10.1039/d3cy01477k

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Bridging and terminal hydroxyl groups of Zr(OH)₄ as active sites for the ultraselective transformation of biomass-based alcohols

Xiaoqi Tang,

Ganping Wang,

Jiaheng Qin

et al.

Abstract: Developing a cost-effective and multi-functional heterogenous catalyst for various biomass transformation is important in both academic and industrial communities. Dehydration and oxidative dehydrogenation of biomass-based alcohols are important and fundamental...

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2024

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Cited by 4 publications

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Physically hybrid Zr(OH)₄ + CuO catalyzed selective aniline oxidation: A new Ph‐N˙OH mediated mechanism

Qin,

Liu,

Zhao

et al. 2024

AIChE Journal

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Developing the sustainable and cost‐effective heterogeneous catalytic system for controlling chemoselectivity holds substantial importance in fine organic chemicals. Herein we construct a unique Zr(OH)4 + CuO physically hybrid system for selective oxidation of anilines. Zr(OH)4 alone leads to azoxybenzene formation, and Zr(OH)4 + CuO shifts the reaction favorably toward nitrosobenzene. The proximity study indicates Zr(OH)4 + CuO outperforms its counterparts synthesized through methods like ball‐milling, loading, and coprecipitation, because the closer proximity exhibits stronger chemical interaction, restricting the activity of Zr‐OH hydroxyl sites. Through mechanistic experiments, in situ DRIFT‐IR and DFT calculations, a new Ph‐OH intermediate mechanism is firstly proposed. Two Ph‐OH self‐condensate to form azoxybenzene for only Zr(OH)4, whereas Zr(OH)4 + CuO could promote rapid transformation of Ph‐OH to nitrosobenzene on CuO through a hydrogen transfer process. Moreover, Zr(OH)4 + CuO displays good recyclability and robust scalability. This is the first report demonstrating the utilization of a physically hybrid catalyst to adjust the selectivity of the aniline oxidation reaction.

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Physically hybrid Zr(OH)₄ + CuO catalyzed selective aniline oxidation: A new Ph‐N˙OH mediated mechanism

Qin,

Liu,

Zhao

et al. 2024

AIChE Journal

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Zr(OH)₄‐Catalyzed Semi‐Hydrogenation of Phenylacetylene with Terminal Zr−O−H as Active Site: Inactive for Free Styrene

Wu,

Li,

Che

et al. 2024

Angewandte Chemie

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In the field of industrial semi‐hydrogenation of trace alkynes amidst alkene feedstocks, the pivotal challenge lies in circumventing the hydrogenation of alkenes. Herein, we present Zr(OH)4 as an innovative catalyst for the semi‐hydrogenation of phenylacetylene, demonstrating remarkable selectivity towards styrene (>96%), while exhibiting inactivity towards free styrene. Notably, Zr(OH)4 achieves a 95% conversion of quasi‐industry 1 mol% phenylacetylene within styrene, with a mere 0.44% styrene loss. Experimental and theoretical results confirm both terminal Zr‐O‐H and bridge Zr‐O‐H can dissociate H2, while the terminal Zr‐O‐H plays a crucial role on activating phenylacetylene through the sequential hydrogenation process of C6H5C≡CH→C6H5C=CH2→C6H5CH=CH2. The high rate of phenylacetylene removal is attributed to its strong adsorption capacity, while Zr(OH)4 has a significantly weaker adsorption capacity for styrene.

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Zr(OH)₄‐Catalyzed Semi‐Hydrogenation of Phenylacetylene with Terminal Zr−O−H as Active Site: Inactive for Free Styrene

Wu,

Li,

Che

et al. 2024

Angew Chem Int Ed

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Bridging and terminal hydroxyl groups of Zr(OH)₄ as active sites for the ultraselective transformation of biomass-based alcohols

Abstract: Developing a cost-effective and multi-functional heterogenous catalyst for various biomass transformation is important in both academic and industrial communities. Dehydration and oxidative dehydrogenation of biomass-based alcohols are important and fundamental...

Cited by 4 publications

References 61 publications

Physically hybrid Zr(OH)₄ + CuO catalyzed selective aniline oxidation: A new Ph‐N˙OH mediated mechanism

Physically hybrid Zr(OH)₄ + CuO catalyzed selective aniline oxidation: A new Ph‐N˙OH mediated mechanism

Zr(OH)₄‐Catalyzed Semi‐Hydrogenation of Phenylacetylene with Terminal Zr−O−H as Active Site: Inactive for Free Styrene

Zr(OH)₄‐Catalyzed Semi‐Hydrogenation of Phenylacetylene with Terminal Zr−O−H as Active Site: Inactive for Free Styrene

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Bridging and terminal hydroxyl groups of Zr(OH)4 as active sites for the ultraselective transformation of biomass-based alcohols

Abstract: Developing a cost-effective and multi-functional heterogenous catalyst for various biomass transformation is important in both academic and industrial communities. Dehydration and oxidative dehydrogenation of biomass-based alcohols are important and fundamental...

Cited by 4 publications

References 61 publications

Physically hybrid Zr(OH)4 + CuO catalyzed selective aniline oxidation: A new Ph‐N˙OH mediated mechanism

Physically hybrid Zr(OH)4 + CuO catalyzed selective aniline oxidation: A new Ph‐N˙OH mediated mechanism

Zr(OH)4‐Catalyzed Semi‐Hydrogenation of Phenylacetylene with Terminal Zr−O−H as Active Site: Inactive for Free Styrene

Zr(OH)4‐Catalyzed Semi‐Hydrogenation of Phenylacetylene with Terminal Zr−O−H as Active Site: Inactive for Free Styrene

Contact Info

Product

Resources

About

Bridging and terminal hydroxyl groups of Zr(OH)₄ as active sites for the ultraselective transformation of biomass-based alcohols

Physically hybrid Zr(OH)₄ + CuO catalyzed selective aniline oxidation: A new Ph‐N˙OH mediated mechanism

Physically hybrid Zr(OH)₄ + CuO catalyzed selective aniline oxidation: A new Ph‐N˙OH mediated mechanism

Zr(OH)₄‐Catalyzed Semi‐Hydrogenation of Phenylacetylene with Terminal Zr−O−H as Active Site: Inactive for Free Styrene

Zr(OH)₄‐Catalyzed Semi‐Hydrogenation of Phenylacetylene with Terminal Zr−O−H as Active Site: Inactive for Free Styrene