Phosphorus coordinated Rh single-atom sites on nanodiamond as highly regioselective catalyst for hydroformylation of olefins

Gao, Peng; Liang, Guanfeng; Ru, Tong; Liu, Xiao Yan; Qi, Haifeng; Wang, Aiqin; Chen, Fen‐Er

doi:10.21203/rs.3.rs-242712/v1

Cited by 4 publications

(4 citation statements)

References 46 publications

(52 reference statements)

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“…Last two decades has witnessed the great efforts made in heterogenizing the homogeneous rhodium-based catalysts. Generally, singly dispersed Rh atoms can be supported on porous organic polymers [135][136][137][138] and inorganic solids 128,[139][140][141][142][143] . However, the heterogeneous catalysts have relatively lower activity comparing with homogeneous catalysts and the catalytic mechanism of the former is not clear yet.…”

Section: Hydroformylationmentioning

confidence: 99%

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Enhancing Heterogeneous Catalysis by Electronic Property Regulation of Single Atom Catalysts

Luo¹,

Wang²

2023

Acta Physico Chimica Sinica

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Past decades have witnessed the flourish of single atom catalysts (SACs) owing to their high atom-utilization efficiency and completely exposed active sites, which endows SACs with remarkably enhanced catalytic activities for various reactions. In the early development stage of SACs, researchers focus on the improvement of the catalytic performance of the catalysts, whereas the intrinsic catalytic reaction mechanism and the relationship between the electronic states of the metal sites and catalytic performance are usually ignored. Moreover, some sophisticated and complex structures, such as dualatom SACs, heteroatomic doped SACs, SACs with precise second coordination shell, and other synergetic catalysts containing SACs, were fabricated recently. The insight into electronic metal-support interaction (EMSI) aids the understanding of the catalytic mechanism and thus serves as a guide for the fabrication of heterogeneous catalysts. Notably, the uniform active sites and characteristic local coordination configuration of SACs provide excellent platforms to study EMSI and bridge the gap between homogeneous and heterogeneous catalysts, which will contribute to the understanding of structure-performance relationships and enhance the development of SACs and rational design of heterogeneous catalysts. EMSI is especially important in heterogeneous catalysis. Through the rational design of the local coordination environment of SACs, the electronic structure of active sites can be accurately regulated, which will shift their d-band centers. This significantly alters the adsorption capability of intermediates and influences the final catalytic performance of the catalysts. With the development of advanced operando characterization techniques, the evolution of configuration, electronic properties, and local coordination environment could be revealed, thus providing researchers with a clear picture of the intrinsic mechanism of the catalytic system. In addition, with the aid of theoretical calculations, catalyst screening will be considerably more convenient, which will significantly reduce the number of aimless trials. After the optimal structure is determined, researchers should devise precise fabrication methods to realize the configuration. Herein, we initially introduce the basic principles and effects of EMSI. The stabilization, electronic property regulation, and electron transfer tunneling effects of EMSI are the foundation of SACs synthesis and catalytic mechanism elucidation, of which the former requires strong coordination stabilization energies while the latter focuses on the electronic state evolution of the active sites. Subsequently, EMSI applications in several important heterogeneous catalysis processes, such as selective hydrogenation, alcohol oxidation, water-gas shift reaction, and hydroformylation, are reviewed. Finally, the review discusses the challenges and future prospects for the future development of EMSI on SACs.

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Section: Hydroformylationmentioning

confidence: 99%

“…Meanwhile, Chen and co-workers reported nanodiamondsupported phosphorus coordinated Rh1 catalyst, Rh1/PNP-ND 140 . The EMSI between Rh single atoms and phosphorus in PNP ligands resulted in relatively high electron density of Rh atoms, together with large angle in gem-dicarbonyl Rh(CO)2 on Rh1/PNP-ND, contributed to the high b/l ratio.…”

Section: Hydroformylationmentioning

confidence: 99%

Enhancing Heterogeneous Catalysis by Electronic Property Regulation of Single Atom Catalysts

Luo¹,

Wang²

2023

Acta Physico Chimica Sinica

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“…1,2 Among them, atomically dispersed metal catalysts exhibit good catalytic activity and chemical selectivity due to their uniform geometric and electronic structures, 3 which greatly promote the development of synthetic chemistry and heterogeneous catalysis. 4 Possessing the properties of unsaturated coordination active sites and easy recycling, 5 atomically dispersed metal catalysts have drawn extensive attention in various reactions, such as dehydrogenation of alkanes, 6 hydroformylation of olefins, 7 and hydrogenation of alkynes 8,9 or nitro groups. 10 Amine is an indispensable organic intermediate in synthetic chemistry 11 and is widely employed in agriculture and medicine.…”

Section: ■ Introductionmentioning

confidence: 99%

Atomic-Dispersed Rh Enables Efficient Catalytic Nitrile Hydrogenation: Size Effect and Metal-Dependent Effect

et al. 2023

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The hydrogenation of nitriles to amines, as an atom-economical synthetic route, has attracted wide attention in industrial production. Despite that some catalysts for nitrile hydrogenation have been investigated in recent years, achieving high activity and selectivity in this process remains a major challenge. Here, we fabricated an atomically dispersed Rh catalyst anchored on defect-rich nanodiamond-graphene (ND@G) via a deposition–precipitation strategy (Rh1/ND@G), which showed the highest activity (TOF = 2592 h–1) in the hydrogenation of benzonitrile reaction among all the known catalysts under mild reaction conditions (333 K, 0.6 MPa H2), and delivered high selectivity (>99%) toward secondary amines. Significantly, we prepared the Rh-cluster catalyst (Rh n /ND@G) and a series of atomically dispersed M1 catalysts (M = Rh, Ru, Pd, Ir, and Pt) to understand the size effect and metal-dependent effect in the hydrogenation of benzonitrile. Experimental and theoretical investigations revealed that the Rh1/ND@G catalyst has higher selectivity toward dibenzylamine than Rh n /ND@G, as it is less likely to form benzylamine on the Rh1 active sites. Meanwhile, the difference of adsorption energies (as a catalyst descriptor) between benzylideneimine and benzonitrile was used to understand the activity of benzonitrile hydrogenation influenced by the metal-dependent effect of M1 catalysts. Modulating the size and metal-dependent effects could lead to high catalytic performance, paving the way to design efficient nitrile hydrogenation catalysts.

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“…Hydroformylation reactions produce aldehydes from syngas and olefins, whose global capacity is more than 10 million tons per year. − Although the currently used Rh-based homogeneous catalysts are highly active and selective, , the separation process is challenging and the intrinsic disadvantages of noble metal leaching and phosphine-containing wastes are difficult to overcome. − Therefore, many heterogeneous catalysts have been developed to increase the recyclability. The methods of heterogenizing include immobilization of Rh-phosphine catalysts, − doping of additives to inorganic Rh catalysts, − and using supported Rh single atom catalysts. − However, the synthesis of these catalysts is relatively complex and the space–time yield is lower than those of the homogeneous counterparts.…”

Section: Introductionmentioning

confidence: 99%

Insights into the Activity Screening and Hydroformylation Kinetics of Rh-Based Bimetallic Phosphides

et al. 2021

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Heterogeneous hydroformylation is of great industrial and economic interest. Here, we proposed a screening strategy to search highly active Rh-based bimetallic phosphide catalysts and successfully predicted Rh 7 Pd 1 P 4 as a new active site, which was more active than other phosphide catalysts. Experimental verifications confirmed the synthesis of bimetallic phosphides and the activity enhancement for styrene hydroformylation. The kinetics of styrene hydroformylation was studied based on the ratedetermining step (RDS) achieved from density functional theory (DFT) calculations. The proposed two-parameter kinetics was more consistent with the experimental data than previously used first-order or zero-order models. By changing the reaction pressure, the RDS could be identified by experiments with the help of the kinetic model. The RDS identified from the experiments and the kinetic model agreed well with the DFT calculations, which further proved the accuracy of the kinetic model.

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Phosphorus coordinated Rh single-atom sites on nanodiamond as highly regioselective catalyst for hydroformylation of olefins

Cited by 4 publications

References 46 publications

Enhancing Heterogeneous Catalysis by Electronic Property Regulation of Single Atom Catalysts

Enhancing Heterogeneous Catalysis by Electronic Property Regulation of Single Atom Catalysts

Atomic-Dispersed Rh Enables Efficient Catalytic Nitrile Hydrogenation: Size Effect and Metal-Dependent Effect

Insights into the Activity Screening and Hydroformylation Kinetics of Rh-Based Bimetallic Phosphides

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