Platinum supported on nanosilica and fibrous nanosilica for hydrogenation reactions

Xantini, Z.; Erasmus, Elizabeth

doi:10.1016/j.poly.2020.114769

Cited by 11 publications

(5 citation statements)

References 55 publications

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“…Moreover, the η4 adsorption mode significantly aids this reaction, leading to the production of a mixture of HCAL, COL, and HCOL from CAL hydrogenation. , Therefore, catalyst modification is crucial to enhance selective CO bond hydrogenation for achieving exclusive selectivity to specific target products. Although there are reports of selective hydrogenation of CAL to a particular product with a noble/non-noble metal catalyst, controlling reaction efficiency and selectivity to a particular hydrogenated product in the presence of monometallic catalysts is a challenging task. − Among few notable contributions in this regard the Yang and Liu group has made significant contributions to this field by developing a metal–organic framework (MOF) based monometallic catalyst (Co) as well as a bimetallic catalyst (Co–Mo, Co–W, and Co–Pt) and achieved high selectivity toward COL under optimal reaction conditions. , However, achieving maximum activity and selectivity with these non-noble metal-based catalysts still remains a challenge. Next, to assess the catalytic activity of the synthesized materials, we selected cinnamaldehyde (CAL) as a model substrate for hydrogenation.…”

Section: Resultsmentioning

confidence: 99%

Co–Ti Bimetallic Complex-Induced Phase Modulation of Co@Black TiO₂ for Catalytic Hydrogenation of Cinnamaldehyde

Mishra,

Mrugesh,

Subramanian

et al. 2024

Inorg. Chem.

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Transition-metal-doped black titania, primarily in the anatase phase, shows promise for redox reactions, water splitting, hydrogen generation, and organic pollutant removal, but exploring other titania phases for broader catalytic applications is underexplored. This study introduces a synthetic approach using a Co–Ti bimetallic complex bridged by a 1,10-phenanthroline-5,6-dione ligand as a precursor for the synthesis of cobalt-doped black titania [Co@L2N@b-TiO2]. The synthesis involves precise control of pyrolysis conditions, yielding a distinct structure dominated by the rutile phase over anatase, with active cobalt encapsulated within a nitrogen-doped graphitic layer, primarily as Co0 rather than CoII and CoIII. The synthesized material is employed for the selective hydrogenation of cinnamaldehyde (CAL) to cinnamyl alcohol (COL) under industrially viable conditions. The efficiency and selectivity of Co@L2N@b-TiO2 was compared with other catalysts, including cobalt-doped rutile TiO2 (Co@r-TiO2), anatase TiO2 (Co@a-TiO2), and black titania (Co@b-TiO2) as well as materials pyrolyzed under different atmospheres and temperatures, materials with phenanthroline ligands, and materials lacking any ligands. The superior performance of Co@L2N@b-TiO2 is attributed to its high surface area, stable Co0 within the nitrogen-doped graphitic layer, and composition of rutile and anatase phases of TiO2 and Ti2O3 (referred to as RAT), along with the synergistic interaction between RAT and Co0. These factors significantly influence the efficiency and selectivity of COL over hydrocinnamaldehyde (HCAL) and hydrocinnamyl alcohol (HCOL), indicating potential for broader applications beyond catalysis, particularly in designing of black titania-based materials.

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Section: Resultsmentioning

confidence: 99%

Co–Ti Bimetallic Complex-Induced Phase Modulation of Co@Black TiO₂ for Catalytic Hydrogenation of Cinnamaldehyde

Mishra,

Mrugesh,

Subramanian

et al. 2024

Inorg. Chem.

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“…The large surface area of the DFNS promotes more active sites for grafting functional groups with excellent chemical, mechanical, and thermal stability [30] . These features have made it an ideal candidate as a support material for many organic amine moieties, [31] organometallic complexes, [32] organic molecules, [33] metals, [34] metal oxides, [35] peptides, [36] polymers, [37] proteins, [38] enzymes, [39] etc. Therefore, DFNS ‐based materials have broad applications in drug delivery, gas capture, energy storage, biosensing, molecular probes, affinity ligands, and various adsorbents [36,40] .…”

Section: Introductionmentioning

confidence: 99%

Adenine‐Functionalized Dendritic Fibrous Nanosilica as Bifunctional Catalyst for CO₂ Fixation into Cyclic Carbonate

et al. 2023

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Cycloaddition of CO2 with epoxide to form cyclic carbonate is one of the most promising approaches to mitigate the rising level of CO2 in the atmosphere. Therefore, the design and synthesis of new materials which can efficiently catalyze such reactions has become an important research area. This article reports on the synthesis of a new material, adenine functionalized dendritic fibrous nanosilica (DAD), by functionalizing the surface of dendritic fibrous nanosilica (DFNS) with an N‐containing heterocyclic nucleobase adenine using a bifunctional isocyanate crosslinker ((EtO)3Si(CH2)3NCO). The surface amine functionalities enable DAD to show selective CO2 adsorption (0.44 mmol/g, at 1 bar CO2 pressure and 298 K temperature) due to acid‐base interaction between CO2 and amine groups. Moreover, DAD efficiently catalyzes the fixation of CO2 with a variety of epoxides into corresponding cyclic carbonates in the presence of TBAB (tetrabutylammonium bromide) co‐catalyst under solvent‐free conditions. The DFNS skeleton of DAD offers a high surface area for enhanced CO2 adsorption, while its organic surface groups, adenine and carbamide, boost the selectivity and activate the epoxide ring and CO2 for cycloaddition reaction. The strong covalent linkage of surface groups in DAD renders robust structural integrity, enabling the catalyst to be recycled multiple times with negligible reduction in its catalytic performance.

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“…4,5 Great efforts for this reaction have been devoted to designing metal-based selective catalysts, including employing bimetallic alloys, 6 metal−support interaction, 7−9 and steric hindrance. 10−13 In general, noble metals, including Pt, 11,14 Pd, 7,15 and Au, 16 can efficiently catalyze hydrogenation of CAL, but the poor reserves limit their wide applications.…”

Section: Introductionmentioning

confidence: 99%

“…In the past few decades, selective hydrogenation of cinnamaldehyde (CAL) to cinnamyl alcohol (COL), − a chemical widely used in fragrances and perfumes, has attracted much attention due to the intrinsic difficulty with thermodynamically easier hydrogenation of CC bonds. , Great efforts for this reaction have been devoted to designing metal-based selective catalysts, including employing bimetallic alloys, metal–support interaction, − and steric hindrance. − In general, noble metals, including Pt, , Pd, , and Au, can efficiently catalyze hydrogenation of CAL, but the poor reserves limit their wide applications.…”

Section: Introductionmentioning

confidence: 99%

Enhanced Selective Hydrogenation of Cinnamaldehyde to Cinnamyl Alcohol over Silica-Coated Pt–Co_xO_y Hybrid Nanoparticles

Wang,

Hu,

Wang

et al. 2023

ACS Appl. Mater. Interfaces

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Selective hydrogenation of cinnamaldehyde (CAL) to cinnamyl alcohol (COL) is difficult due to the intrinsic difficulty with thermodynamically easier hydrogenation of C�C bonds. In this work, Pt−Co x O y hybrid nanoparticles encapsulated in mesoporous silica nanospheres (Pt−Co x O y @mSiO 2 ) were synthesized by a sol−gel method, which showed greatly improved COL selectivity for hydrogenation of CAL. At 80 °C and 1.0 MPa of H 2 , Pt−Co x O y @mSiO 2 achieved a CAL conversion of 98.7% with a COL selectivity of 93.5%. In contrast, Pt@mSiO 2 yields 3phenylpropanol (HCOL) as the major product with HCOL selectivity of 67.2%, while PtCo@mSiO 2 yields 3-phenylpropionaldehyde with selectivity of 51.8% under the same conditions. The enhanced catalytic performance of Pt−Co x O y @mSiO 2 for hydrogenation of CAL to COL is ascribed to the Pt surface electron deficiency induced by metal−oxide interaction, and the protection of active NPs by silica shells results in good catalytic stability.

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Platinum supported on nanosilica and fibrous nanosilica for hydrogenation reactions

Cited by 11 publications

References 55 publications

Co–Ti Bimetallic Complex-Induced Phase Modulation of Co@Black TiO₂ for Catalytic Hydrogenation of Cinnamaldehyde

Co–Ti Bimetallic Complex-Induced Phase Modulation of Co@Black TiO₂ for Catalytic Hydrogenation of Cinnamaldehyde

Adenine‐Functionalized Dendritic Fibrous Nanosilica as Bifunctional Catalyst for CO₂ Fixation into Cyclic Carbonate

Enhanced Selective Hydrogenation of Cinnamaldehyde to Cinnamyl Alcohol over Silica-Coated Pt–Co_xO_y Hybrid Nanoparticles

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Platinum supported on nanosilica and fibrous nanosilica for hydrogenation reactions

Cited by 11 publications

References 55 publications

Co–Ti Bimetallic Complex-Induced Phase Modulation of Co@Black TiO2 for Catalytic Hydrogenation of Cinnamaldehyde

Co–Ti Bimetallic Complex-Induced Phase Modulation of Co@Black TiO2 for Catalytic Hydrogenation of Cinnamaldehyde

Adenine‐Functionalized Dendritic Fibrous Nanosilica as Bifunctional Catalyst for CO2 Fixation into Cyclic Carbonate

Enhanced Selective Hydrogenation of Cinnamaldehyde to Cinnamyl Alcohol over Silica-Coated Pt–CoxOy Hybrid Nanoparticles

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Co–Ti Bimetallic Complex-Induced Phase Modulation of Co@Black TiO₂ for Catalytic Hydrogenation of Cinnamaldehyde

Co–Ti Bimetallic Complex-Induced Phase Modulation of Co@Black TiO₂ for Catalytic Hydrogenation of Cinnamaldehyde

Adenine‐Functionalized Dendritic Fibrous Nanosilica as Bifunctional Catalyst for CO₂ Fixation into Cyclic Carbonate

Enhanced Selective Hydrogenation of Cinnamaldehyde to Cinnamyl Alcohol over Silica-Coated Pt–Co_xO_y Hybrid Nanoparticles