A Magnetically Separable Pd Single‐Atom Catalyst for Efficient Selective Hydrogenation of Phenylacetylene

Zhao, Linmin; Qin, Xuetao; Zhang, Xirui; Cai, Xiangbin; Huang, Fei; Jia, Zhimin; Diao, Jiangyong; Xiao, Dequan; Jiang, Zheng; Lu, Ruifeng; Wang, Ning; Li, Hongyang; Ma, Ding

doi:10.1002/adma.202110455

Cited by 73 publications

(42 citation statements)

References 50 publications

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“…Reaction rates at different temperatures were measured and the activation energies (E a ) of Pd/Nb 2 C were fitted to be 39.5 kJ/mol (Fig. 5c ), suggesting the superiority of Pd/Nb 2 C among Pd-based catalyst reported previously under similar reaction conditions 56 , 57 . To shed light on the original of excellent catalytic performance of Pd/Nb 2 C, the experiments of kinetic isotope effect (KIE) were accomplished using D 2 as feed gas in phenylacetylene hydrogenation 58 , 59 .…”

Section: Resultssupporting

confidence: 63%

Tripodal Pd metallenes mediated by Nb2C MXenes for boosting alkynes semihydrogenation

et al. 2023

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Abstract2D metallene nanomaterials have spurred considerable attention in heterogeneous catalysis by virtue of sufficient unsaturated metal atoms, high specific surface area and surface strain. Nevertheless, the strong metallic bonding in nanoparticles aggravates the difficulty in the controllable regulation of the geometry of metallenes. Here we propose an efficient galvanic replacement strategy to construct Pd metallenes loaded on Nb2C MXenes at room temperature, which is triggered by strong metal-support interaction based on MD simulations. The Pd metallenes feature a chair structure of six-membered ring with the coordination number of Pd as low as 3. Coverage-dependent kinetic analysis based on first-principles calculations reveals that the tripodal Pd metallenes promote the diffusion of alkene and inhibit its overhydrogenation. As a consequence, Pd/Nb2C delivers an outstanding turnover frequency of 10372 h−1 and a high selectivity of 96% at 25 oC in the semihydrogenation of alkynes without compromising the stability. This strategy is general and scalable considering the plentiful members of the MXene family, which can set a foundation for the design of novel supported-metallene catalysts for demanding transformations.

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Section: Resultssupporting

confidence: 63%

Tripodal Pd metallenes mediated by Nb2C MXenes for boosting alkynes semihydrogenation

et al. 2023

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“…Reaction rates at different temperatures were measured and the activation energies (E a ) of Pd/Nb 2 C were tted to be 39.5 kJ/mol (Fig. 5c), suggesting the superiority of Pd/Nb 2 C among Pd-based catalyst reported previously under similar reaction conditions 50,51 . To shed light on the original of excellent catalytic performance of Pd/Nb 2 C, the experiments of kinetic isotope effect (KIE) were accomplished using D 2 as feed gas in phenylacetylene hydrogenation 52,53 .…”

Section: Resultssupporting

confidence: 60%

Tripodal Pd metallenes mediated by Nb2C MXenes for boosting alkynes semihydrogenation

Zhao

Qiu

Huang

et al. 2022

Preprint

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2D metallene nanomaterials have spurred considerable attention in heterogeneous catalysis by virtue of sufficient unsaturated metal atoms, high specific surface area and surface strain. Nevertheless, the strong metallic bonding in nanoparticles aggravates the difficulty in the controllable regulation of the geometry of metallenes. Here we propose an efficient galvanic replacement strategy to construct Pd metallenes loaded on Nb2C MXenes at room temperature, which is triggered by ultra-strong metal-support interaction based on MD simulation. A combination of electron microscopy, synchrotron X-ray absorption spectroscopy characterizations and theoretical calculations confirm that the Pd metallenes feature a chair structure of six-membered ring with the coordination number of Pd as low as 3. The tripodal Pd metallenes promote the diffusion of alkenes as the effective Pd atoms directly bonded with alkenes decreased compared with traditional Pd (111). As a consequence, the Pd/Nb2C delivers an outstanding turnover frequency of 10372 h− 1 and a high selectivity of 96% at 25 oC in the semihydrogenation of alkynes without compromising the stability. This strategy is general and scalable considering the plentiful members of the MXene family, which can set a foundation for the design of novel supported-metallene catalysts for demanding transformations.

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“…Impressively, the TOF value increases after the CpCo- fragments bonding on Pt/SiO 2 and further increases with the CpCo- coverage. The highest TOF on 200CpCo-Pt/SiO 2 (17 964.0 h –1 ) is also higher than most reported Pt and Pd-based catalysts. − In addition, the reusability of 200CpCo-Pt/SiO 2 was tested. It is found that the selectivity and conversion are nearly similar after the consecutive recycling runs (Figure S14c).…”

Section: Resultsmentioning

confidence: 92%

Direct Bonding of CpCo- Fragments on Pt Nanoparticles and their Electronic Effect for Alkyne Semihydrogenation

et al. 2022

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Additives are commonly used to improve the catalytic performance of supported metal nanoparticles. However, depositing additives with a clear structure, location, and composition remains challenging. Herein, we report the bonding of cobaltocene fragments (CpCo-) on Pt nanoparticles via a self-limiting way like atomic layer deposition. The electron density of Pt increases after the formation of the stable CpCo-Pt bond and is quantitatively controlled by the CpCo-coverage. The higher Pt electron density originates from the d orbital of Co and π-orbital of Cp. As a result of the electronic effect of the CpCo-, the adsorption of olefins on the Pt surface is weakened and activation energy for C�C bond hydrogenation increases, resulting in high selectivity in alkyne semihydrogenation. Our method can be further utilized to precisely tailor the electronic structure of active species for enhanced catalytic performance by sample changing the type of the fragments.

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A Magnetically Separable Pd Single‐Atom Catalyst for Efficient Selective Hydrogenation of Phenylacetylene

Abstract: an external magnetic field since it contains magnetic Ni particles. Thus, the combination of atomically dispersed metallic atoms and magnetic Ni@G support can pave the way to design more promising catalysts for selective hydrogenation reactions in industrial applications.

Cited by 73 publications

References 50 publications

Tripodal Pd metallenes mediated by Nb2C MXenes for boosting alkynes semihydrogenation

Tripodal Pd metallenes mediated by Nb2C MXenes for boosting alkynes semihydrogenation

Tripodal Pd metallenes mediated by Nb2C MXenes for boosting alkynes semihydrogenation

Direct Bonding of CpCo- Fragments on Pt Nanoparticles and their Electronic Effect for Alkyne Semihydrogenation

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