Direct conversion of methane to oxygenates on porous organic polymers supported Rh mononuclear complex catalyst under mild conditions

Li, Bin; Song, Xinshan; Feng, Siquan; Qiao, Yuan; Jiang, Miao; Li, Yan; Ding, Yunjie

doi:10.1016/j.apcatb.2021.120208

Cited by 18 publications

(10 citation statements)

References 52 publications

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“…[123] This work provides a promising way to use highly efficient non-noble metal AFCs for methane conversions under mild conditions, which has triggered a new wave of research on lowtemperature conversion of methane catalyzed by SACs (e.g., Cu 1 / ZSM-5, Cr 1 /TiO 2 , Au 1 /WO 3 , Rh 1 -Cu/POPs, and so on). [126][127][128][129] 4.1.3. Crosscoupling Reactions Among various strategies to synthesize complex COSs for pharmaceuticals and fine chemicals, the construction of carbon─ carbon bond through metal-catalyzed crosscoupling reactions (including C-C or C-N coupling) is one of the most efficient and widely used pathways in both laboratory and industry.…”

Section: Catalytic Oxidation Reactionsmentioning

confidence: 99%

“…[ 123 ] This work provides a promising way to use highly efficient non‐noble metal AFCs for methane conversions under mild conditions, which has triggered a new wave of research on low‐temperature conversion of methane catalyzed by SACs (e.g., Cu 1 /ZSM‐5, Cr 1 /TiO 2 , Au 1 /WO 3 , Rh 1 –Cu/POPs, and so on). [ 126–129 ]…”

Section: Heterogeneous Catalysis Applications Of Afcsmentioning

confidence: 99%

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Emerging Ultrahigh‐Density Single‐Atom Catalysts for Versatile Heterogeneous Catalysis Applications: Redefinition, Recent Progress, and Challenges

Liao

et al. 2022

Small Structures

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In recent years, single‐atom catalysts (SACs) with high metal loading have emerged in different heterogeneous catalysis fields and shown extraordinary catalytic properties. When there are enough coordination atoms (or functional groups) on the supports, it is possible to achieve a limit monolayer atom loading on the surface of supports with ultrahigh atom density (5–15 atoms nm−2) and extremely close site distance (0.2–0.5 nm), by using appropriate synthesis methods and procedures. These high‐density metal atoms usually have no or less metal bonds, which are mostly isolated by support atoms to form 3D foam‐like atomic constructions. Herein, a new notion of metal atomic foam catalysts (AFCs) is propsed to redefine these ultrahigh‐density SACs accommodated by specific supports. This new paradigm of 3D atomic construction for SACs has potential significance for both theoretical research and industrial applications. The latest major advancements in the controllable synthesis of AFCs on various supports (e.g., polymer, carbon, and metallic compound) via different methods (bottom‐up or top‐down approaches) are summarized. The latent catalytic principles and typical application cases of AFCs are emphasized in a wide range of heterogeneous catalysis fields (e.g., thermocatalysis, photocatalysis, electrocatalysis, etc.). The challenges and prospects of this newly 3D ultrahigh‐density AFCs materials in practical industrial application are pointed out as well.

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Section: Catalytic Oxidation Reactionsmentioning

confidence: 99%

Section: Heterogeneous Catalysis Applications Of Afcsmentioning

confidence: 99%

Emerging Ultrahigh‐Density Single‐Atom Catalysts for Versatile Heterogeneous Catalysis Applications: Redefinition, Recent Progress, and Challenges

Liao

et al. 2022

Small Structures

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“…Among them, 2173 and 2117 cm –1 peaks were gas-phase CO, which disappeared after Ar purging. The remained 2058 and 1982 cm –1 peaks were associated with the symmetric and asymmetric stretching vibration of the gem-dicarbonyl species Rh(CO) 2 . , In contrast, a new peak at 2004 cm –1 emerged along with the weakening of 2058 and 1973 cm –1 two peaks when the CO containing 1000 ppm H 2 S passed through the Rh 1 /PIPs catalyst, illustrating that part of carbonyl adsorption types on single Rh sites transformed from the dicarbonyl CO to the monocarbonyl one (Figure b). , In Figure c, there were no obvious peaks in the fingerprint region using CO. While several peaks at 417–422 cm –1 appeared in Figure d using CO containing 1000 ppm H 2 S as a probe molecule, which was probably attributed to the Rh–S bond .…”

Section: Resultsmentioning

confidence: 93%

“…The remained 2058 and 1982 cm −1 peaks were associated with the symmetric and asymmetric stretching vibration of the gem-dicarbonyl species Rh(CO) 2 . 26,50 In contrast, a new peak at 2004 cm −1 emerged along with the weakening of 2058 and 1973 cm −1 two peaks when the CO containing 1000 ppm H 2 S passed through the Rh 1 /PIPs catalyst, illustrating that part of carbonyl adsorption types on single Rh sites transformed from the dicarbonyl CO to the monocarbonyl one (Figure 2b). 51,52 In Figure 2c, there were no obvious peaks in the fingerprint region using CO.…”

Section: Methodsmentioning

confidence: 98%

“…Research on the influence of sulfur on the activity and selectivity of catalysis mainly focuses on several certain reactions, such as hydrogenation, dehydrogenation, steam reforming, oxidation, and so forth. − Furthermore, sulfur poisoning has always been studied in homogeneous catalysis and heterogeneous nanocatalysis or alloy catalysis, ,, while it is very rarely reported in heterogeneous single-metal-site catalysis. Heterogeneous single-metal-site catalysts (HSMSCs) possess the highest atom utilization and remarkable activity similar to or beyond that of homogeneous catalysis as well as the merit of easy separation and high stability in heterogeneous catalysis. , As a bridge between homogeneous and heterogeneous catalysis, HSMSCs have received a lot of research attention and have been successfully applied in various kinds of reactions, such as the olefin hydrocarboxylation reaction, which is a simple and promising way to directly produce organic carboxylic acids. − As important bulk chemicals, carboxylic acids are widely applied in pharmaceuticals, cosmetics, plastics, polymers, and other manufacturing fields. , Simultaneously, carboxylic acids are versatile intermediates for the preparation of a vast array of derivatives, such as esters, ketones, amides, and alcohols. − Therefore, research on the influence of sulfur species on HSMSCs in hydrocarboxylation not only diversifies its theory but also possesses significance in industrial applications.…”

Section: Introductionmentioning

confidence: 99%

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Sulfur-Promoted Hydrocarboxylation of Olefins on Heterogeneous Single-Rh-Site Catalysts

Qiao

Feng

et al. 2022

ACS Catal.

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Sulfur poisoning is a severe problem in industrial applications, attracting broad interest in fundamental research studies. Although a number of studies about sulfur resistance have been implemented in many reactions on nanoparticle catalysts, few investigations focus on carbonylation reactions using heterogeneous single-metal-site catalysts (HSMSCs). Herein, we present an unanticipated sulfur-promoted performance in olefin hydrocarboxylation reactions on a single-Rh-site catalyst supported on porous ionic polymers (Rh1/PIPs) with 1000 ppm H2S in CO feed. Ex situ EXAFS and in situ DRIFTS revealed a ternary cycle mechanism of olefin hydrocarboxylation reactions with Rh–H complexes as predominant active species in both pure and H2S-containing feedstock. Moreover, the transformation of the Rh mononuclear complex with the addition of H2S was also demonstrated. Density functional theory studies were performed to verify the feasibility of the proposed pathway and confirm that the energy barriers of transition states with the sulfur ligand were much lower than those in normal feed, for example, a decline of 3.4 kcal/mol for the rate-determining step of migration and insertion of CO. This work provides a distinctive example for the insight of sulfur effect on carbonylation, which could be potentially beneficial for further applications of HSMSCs.

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Carbonylation Reactions Using Single‐Atom Catalysts

Jurado,

Posada‐Pérez,

Axet

2024

ChemCatChem

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The development of highly efficient and selective catalysts for carbonylation reactions represents a significant challenge in catalysis. Single‐atom catalysts (SACs) have postulated as promising candidates able to combine the strengths of both homogeneous and heterogeneous catalysts. In this paper, we review recent advances in tailoring solid supports for SACs to enhance their catalytic performance in carbonylation reactions. We first discuss the effect of supports on the hydroformylation reaction catalysed by SACs, followed by recent advances for methanol, ethanol, and dimethyl ether carbonylation reactions, focusing on the design of halide‐free catalysts with improved activity and stability. Overall, this review highlights the importance of tailoring solid supports for SACs to achieve highly active and selective catalysts in carbonylation reactions, paving the way for future developments in sustainable catalysis.

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Direct conversion of methane to oxygenates on porous organic polymers supported Rh mononuclear complex catalyst under mild conditions

Cited by 18 publications

References 52 publications

Emerging Ultrahigh‐Density Single‐Atom Catalysts for Versatile Heterogeneous Catalysis Applications: Redefinition, Recent Progress, and Challenges

Emerging Ultrahigh‐Density Single‐Atom Catalysts for Versatile Heterogeneous Catalysis Applications: Redefinition, Recent Progress, and Challenges

Sulfur-Promoted Hydrocarboxylation of Olefins on Heterogeneous Single-Rh-Site Catalysts

Carbonylation Reactions Using Single‐Atom Catalysts

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