Highly Selective Semihydrogenation via a Wettability-Regulated Mass Transfer Process

Zhang, Minghui; Duan, Xiaozheng; Zhu, Yunbo; Yan, Yaming; Zhao, Tianyi; Liu, Mingjie; Jiang, Lei

doi:10.1021/acscatal.2c01325

Cited by 7 publications

(7 citation statements)

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“…[34][35][36][37][38][39][40][41] Moreover, by adjusting the wettability of catalysts, the reaction pathway and selectivity can be altered. [42][43][44][45] Therefore, surface wettability design and modulation have become an important strategy for developing highly active heterogeneous catalysts and catalytic systems. [46][47][48][49][50][51][52][53] In this study, via surface wettability and reaction interfacial microenvironment modulation, we report an efficient SMPD system for • OH generation as illustrated in Figure 1a.…”

Section: Introductionmentioning

confidence: 99%

Hydrophobicity Promoted Efficient Hydroxyl Radical Generation in Visible‐Light‐Driven Photocatalytic Oxidation

Chen,

Sheng,

Zhou

et al. 2024

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Hydroxyl radical (•OH) with strong oxidation capability is one of the most important reactive oxygen species. The generation of •OH from superoxide radicals (•O2−) is an important process in visible‐light‐driven photocatalysis, but the conversion generally suffers from slow reaction kinetics. Here, a hydrophobicity promoted efficient •OH generation in a visible‐light‐driven semiconductor‐mediated photodegradation reaction is reported. Hydrophobic TiO2 that is synthesized by modifying the TiO2 surface with a thin polydimethylsiloxane (PDMS) layer and rhodamine B (RhB) are used as model semiconductors and dye molecules, respectively. The surface hydrophobicity resulted in the formation of a solid–liquid–air triphase interface microenvironment, which increased the local concentration of O2. In the meanwhile, the saturated adsorption quantity of RhB on hydrophobic TiO2 is improved by five‐fold than that on untreated TiO2. These advantages increased the density of the conduction band photoelectrons and •O2− generation, and stimulated the conversion of •O2− to •OH. This consequently not only increased the kinetics of the photocatalytic reaction by an order of magnitude, but also altered the oxidation route from conventional decolorization to mineralization. This study highlights the importance of surface wettability modulation in boosting •OH generation in visible‐light‐driven photocatalysis.

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Section: Introductionmentioning

confidence: 99%

Hydrophobicity Promoted Efficient Hydroxyl Radical Generation in Visible‐Light‐Driven Photocatalytic Oxidation

Chen,

Sheng,

Zhou

et al. 2024

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“…To address above issues, one of the effective ways is to encapsulate metal NPs by porous supports, in which metal NPs could not only be prevented from aggregation by the protection of supports but also generate the unique and intriguing catalytic properties. Unfortunately, the encapsulation generally results in a decrease in catalytic activity, and the obtained turnover frequency (TOF) values are quite low because of partial blockage of the transfer and diffusion of substrates and products (8)(9)(10)(11)(12). Beyond conventional porous supports (8,13,14), metal-organic frameworks (MOFs) have been recognized as the most appropriate candidate to mimic enzymes for cascade catalysis (15,16) because their ordered arrangement of metal nodes and organic ligands and tunable geometry of cavities or channels provide the confined environment akin to enzymes (17).…”

Section: Introductionmentioning

confidence: 99%

Nanocavity in hollow sandwiched catalysts as substrate regulator for boosting hydrodeoxygenation of biomass-derived carbonyl compounds

Zheng,

Cao,

Lin

et al. 2024

Sci. Adv.

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Hydrodeoxygenation of oxygen-rich molecules toward hydrocarbons is attractive yet challenging in the sustainable biomass upgrading. The typical supported metal catalysts often display unstable catalytic performances owing to the migration and aggregation of metal nanoparticles (NPs) into large sizes under harsh conditions. Here, we develop a crystal growth and post-synthetic etching method to construct hollow chromium terephthalate MIL-101 (named as HoMIL-101) with one layer of sandwiched Ru NPs as robust catalysts. Impressively, HoMIL-101@Ru@MIL-101 exhibits the excellent activity and stability for hydrodeoxygenation of biomass-derived levulinic acid to gamma-valerolactone under 50°C and 1-megapascal H 2 , and its activity is about six times of solid sandwich counterparts, outperforming the state-of-the-art heterogeneous catalysts. Control experiments and theoretical simulation clearly indicate that the enrichment of levulinic acid and H 2 by nanocavity as substrate regulator enables self-regulating the backwash of both substrates toward Ru NPs sandwiched in MIL-101 shells for promoting reaction with respect to solid counterparts, thus leading to the substantially enhanced performance.

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“…[14] Recently, Zhao, Liu and co-authors reported that a surface hydrophilic gel support increases the selectivity of styrene in Pd catalyzed semi-selective hydrogenation of phenylacetylene into styrene owing to the quick desorption of styrene from hydrophilic catalyst surface. [15] Generally, the porous silicas, polymer gels and supported ionic liquid phases (SILPs) with different surface wettability are used to support metal NPs. [16][17][18] In most cases, the alkyl group with different carbon chain length/substituents was used to modulate the surface wettability of silicas.…”

Section: Introductionmentioning

confidence: 99%

“…Jiang and co‐workers reported the grafting of perfluoroalkyl groups onto MOF to regulate the hydrophobic environment around Pd NPs and it was found that both catalytic activity and stability of supported Pd were promoted in the dehydrogenative coupling of organosilanes, attributed to the enrichment of hydrophobic reactants around active sites [14] . Recently, Zhao, Liu and co‐authors reported that a surface hydrophilic gel support increases the selectivity of styrene in Pd catalyzed semi‐selective hydrogenation of phenylacetylene into styrene owing to the quick desorption of styrene from hydrophilic catalyst surface [15] …”

Section: Introductionmentioning

confidence: 99%

Tuning the Surface Wettability of Pd/COFs for Selective Hydrogenation

et al. 2023

ChemCatChem

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Covalent organic frameworks (COFs) with imine linkage are promising solid supports to disperse ultra-fine metal nanoparticles (NPs), but the modulation of their surface wettability, an important parameter affecting the catalytic performance of metal NPs, is still very challenging. Here, we report the preparation of two imine-linked COFs with moderate and strong surface hydrophobicity by changing the carbon chain length of side oxyalkyl groups. Ultra-small Pd NPs with an average size of ~2.0 nm was successfully loaded on the two COFs, attributed to the strong interactions of Pd NPs and imine linkage as evidenced by the electron donating from imine linkage to Pd NPs by XPS characterizations. The TOF of Pd/COF is much higher than commercial Pd/C (714 h À 1 vs 489 h À 1 ) in the hydrogenation of nitrobenzene, which is attributed to the electron rich Pd, the hydrophobic surface and crystalline structure of COFs. Pd NPs on COFs with strong hydrophobicity are more active than those on COFs with moderate hydrophilicity in the hydrogenation of moderate lipophilic nitro compounds such as nitrobenzene, methyl nitrobenzene and nitronaphthalene. Reversed tendency was observed for the hydrogenation of moderate hydrophilic p-amino-nitrobenzene. The modulation of the surface wettability of COFs provides an efficient strategy to improve the catalytic performance of supported metal NPs.

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Highly Selective Semihydrogenation via a Wettability-Regulated Mass Transfer Process

Cited by 7 publications

References 50 publications

Hydrophobicity Promoted Efficient Hydroxyl Radical Generation in Visible‐Light‐Driven Photocatalytic Oxidation

Hydrophobicity Promoted Efficient Hydroxyl Radical Generation in Visible‐Light‐Driven Photocatalytic Oxidation

Nanocavity in hollow sandwiched catalysts as substrate regulator for boosting hydrodeoxygenation of biomass-derived carbonyl compounds

Tuning the Surface Wettability of Pd/COFs for Selective Hydrogenation

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