Electronic Modulation of Pd-Based Bimetallic Catalysts with Sulfur-Doped Carbon Support for Phenylacetylene Semihydrogenation

Wang, Zheng-Shu; Yang, Chenglong; Xu, Shilong; Nan, Hang; Shen, Shan‐Cheng; Liang, Hai‐Wei

doi:10.1021/acs.inorgchem.0c00458

Cited by 24 publications

(25 citation statements)

References 45 publications

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“…Different from the conventional perception that sulfur was poisonous to noble metal, recent studies indicated that S-doped carbon may be a promising support for noble-metal catalysts. − Chen et al investigated the ORR performance and durability of S-doped graphene-supported Pt nanoparticles . The negative shift of S 2p binding energy strongly manifested the electrons transferred from Pt nanoparticles to the S-doped graphene support.…”

Section: The Influence Of Carbon Properties On Emsimentioning

confidence: 99%

Engineering the Electronic Interaction between Metals and Carbon Supports for Oxygen/Hydrogen Electrocatalysis

Yan

Peng

Liang

2021

ACS Materials Lett.

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Carbon materials-supported metal catalysts are of great significance to the renewable energy conversion. More than a support to immobilize metal nanoparticles and improve atomic usage, the carbon materials can also impact the catalysis performance in a way of engineering the electronic structure of active metal components. The modulation of such an electronic metal−support interaction (EMSI) for designing efficient catalysts has been a hotspot in recent years. Benefiting from the development of advanced characterization techniques and theoretical simulations, one can shed light on the key points regarding EMSI and construct the relationship between EMSI and catalysis performance. In this Review, we summarize the recent work concerning the electronic interaction between carbon supports and metals, and discuss the underlying factors, including the nature of metal, metal morphology, metal particle size, carbon structure, heteroatom doping, carbon coating, and interfacial binding. The relationship between EMSI and the catalytic performance, by taking hydrogen/oxygen electrocatalysis for examples, is highlighted. These summaries would deepen the understanding of EMSI and favor the progress of carbon-supported metal catalysts.

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Section: The Influence Of Carbon Properties On Emsimentioning

confidence: 99%

Engineering the Electronic Interaction between Metals and Carbon Supports for Oxygen/Hydrogen Electrocatalysis

Yan

Peng

Liang

2021

ACS Materials Lett.

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“…Selective catalytic hydrogenation among various catalytic processes is a kind of important reaction, as it produces high-value chemicals through the control of the hydrogenation degree of a low-value reactant. − The process of phenylacetylene semihydrogenation is of great significance because phenylacetylene is considered to be a harmful feedstock for polystyrene industrial production in the polymerization process of styrene. − Therefore, it is desired to achieve a high selectivity of styrene while keeping a high conversion of phenylacetylene during the reaction process. It is generally accepted that palladium catalysts are mostly used to achieve a high catalytic performance for this reaction.…”

Section: Introductionmentioning

confidence: 99%

Promotion Effect of the X-Zeolite Host on Encapsulated Platinum Clusters for Selective Hydrogenation of Phenylacetylene to Styrene

et al. 2021

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The microenvironment surrounding the metal clusters on a carrier produces a tremendous influence on its catalytic performance. In this work, the promotion effect of the zeolitic inner host on catalytic performance of encapsulated platinum nanoclusters is reported. In the reaction of phenylacetylene semihydrogenation to styrene, Pt@X-zeolite, where platinum nanoclusters are encapsulated into the inner microporosity of the X-zeolite, exhibits an ∼3.37 times increased turnover frequency and a much better selectivity of 87.6% in comparison to the referenced Pt/Xzeolite of 79.3% selectivity to styrene at the same reaction conditions, in which the platinum nanoclusters are located at the exterior of the zeolite. Meanwhile, the Pt@X-zeolite displays a higher stability after 10 cycles of the reaction. Through the detailed characteristics, the excellent performance of Pt@X-zeolite is mainly due to the promotion of the zeolitic framework on the encapsulated Pt clusters, resulting in "electron-deficient" Pt clusters, leading to a stronger interaction with the π* molecular orbitals of phenylacetylene and thus enhancing the activation and conversion of phenylacetylene. The zeolite cavity wrapped with encapsulated Pt clusters regulates the adsorption trend of phenylacetylene through the acetylene group on it, promotes the desorption of styrene, and strengthens its selectivity. Meanwhile, Pt@X-zeolite has an excellent stability through the zeolite framework, which protects the Pt species from being lost. This investigation reveals the importance of the zeolitic microenvironment on the catalytic performance of encapsulated metal species and deepens the cognition for this type of catalyst.

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“…In addition, the excellent atomic dispersion of as‐prepared Pd 1 /BP SACs (0.3 wt%, 0.6 wt%, 1.5 wt%) results in a reasonably high turnover frequency (TOF) of 0.3 s −1 in the semi‐hydrogenations of 3‐butynylbenzene (Table S2, Supporting Information). [ 43–50 ] It is worth mentioning that little aggregated Pd atoms in Pd 1 /BP after the hydrogenation reactions suggest atomic dispersion of single metal atoms on BP can be maintained (Figure S30, Supporting Information).…”

Section: Resultsmentioning

confidence: 99%

Zero‐Valent Palladium Single‐Atoms Catalysts Confined in Black Phosphorus for Efficient Semi‐Hydrogenation

Chen

Yam

et al. 2021

Advanced Materials

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Single‐atom catalysts (SACs) represent a new frontier in heterogeneous catalysis due to their remarkable catalytic properties and maximized atomic utilization. However, single atoms often bond to the support with polarized electron density and thus exhibit a high valence state, limiting their catalytic scopes in many chemical transformations. Here, it is demonstrated that 2D black phosphorus (BP) acts as giant phosphorus (P) ligand to confine a high density of single atoms (e.g., Pd1, Pt1) via atomic layer deposition. Unlike other 2D materials, BP with relatively low electronegativity and buckled structure favors the strong confinement of robust zero‐valent palladium SACs in the vacancy site. Metallic Pd1/BP SAC shows a highly selective semi‐hydrogenation of phenylacetylene toward styrene, distinct from metallic Pd nanoparticles that facilitate the formation of fully hydrogenated products. Density functional theory calculations reveal that Pd atom forms covalent‐like bonding with adjacent P atoms, wherein H atoms tend to adsorb, aiding the dissociative adsorption of H2. Zero‐valent Pd in the confined space favors a larger energy gain for the synthesis of partially hydrogenated product over the fully hydrogenated one. This work provides a new route toward the synthesis of zero‐valent SACs on BP for organic transformations.

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Electronic Modulation of Pd-Based Bimetallic Catalysts with Sulfur-Doped Carbon Support for Phenylacetylene Semihydrogenation

Cited by 24 publications

References 45 publications

Engineering the Electronic Interaction between Metals and Carbon Supports for Oxygen/Hydrogen Electrocatalysis

Engineering the Electronic Interaction between Metals and Carbon Supports for Oxygen/Hydrogen Electrocatalysis

Promotion Effect of the X-Zeolite Host on Encapsulated Platinum Clusters for Selective Hydrogenation of Phenylacetylene to Styrene

Zero‐Valent Palladium Single‐Atoms Catalysts Confined in Black Phosphorus for Efficient Semi‐Hydrogenation

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