Heterogeneous Catalysis for Selective Hydrogenation

A special issue of Catalysts (ISSN 2073-4344). This special issue belongs to the section "Catalytic Materials".

Deadline for manuscript submissions: closed (15 May 2024) | Viewed by 11540

Special Issue Editors

Key Lab of Applied Chemistry of Zhejiang Province, Department of Chemistry, Zhejiang University, Hangzhou 310027, China
Interests: heterogeneous catalysis; methane activation; selective hydrogenation; ethylene production; nanomaterials

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Guest Editor
College of Materials & Environmental Engineering, Hangzhou Dianzi University, Hangzhou 310036, China
Interests: heterogeneous catalysis; nanomaterials; selective hydrogenation; selective oxidation; environmental catalysis

Special Issue Information

Dear Colleagues,

Hydrogenation is one of the most important reactions in the chemical industry. Approximately 25% of chemical transformations include at least one catalytic hydrogenation step. In hydrogenation transformations, selective hydrogenation is undoubtedly the most useful reaction as it provides an economic and sustainable route to creating pharmaceuticals, materials, and fundamental feedstock chemicals. This Special Issue aims to address the challenges and opportunities for selective hydrogenation reactions in heterogeneous catalysis. We will highlight and collect the latest progress in selective hydrogenation of alkynes, CO2, nitro arenes, unsaturated carbonyl compounds, and biomass derivatives, etc. We encourage submissions of original research, reviews, mini-reviews, and perspectives that address the experimental and theoretical aspects of heterogeneous catalysis for selective hydrogenation. Specific subjects include but are not limited to:

  • Development of highly active catalysts for selective hydrogenation
  • Theoretical calculations and microkinetic modeling to elucidate mechanisms of selective hydrogenation reactions
  • Advanced characterization techniques for studying selective hydrogenation reactions
  • Design and application of novel reactors for selective hydrogenation reactions

Dr. Shihui Zou
Dr. Juanjuan Liu
Guest Editors

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Keywords

  • heterogeneous catalysis
  • selective hydrogenation
  • nanomaterials
  • reduction
  • metal catalysts

Published Papers (9 papers)

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Research

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14 pages, 7516 KiB  
Article
Catalytic Hydrogenation of γ-Butyrolactone to Butanediol over a High-Performance Cu-SiO2 Catalyst
by Xiaoni Ren, Mo Zhou, Wenguang Yu, Mingyuan Zheng and Qingda An
Catalysts 2024, 14(5), 297; https://doi.org/10.3390/catal14050297 - 29 Apr 2024
Viewed by 805
Abstract
High-performance Cu catalysts were developed for the selective hydrogenation of γ-butyrolactone (GBL) to 1,4-butanediol (BDO). Among the various catalysts prepared by ammonia evaporation (AE) and impregnation (IM) methods with silica or MFI zeolite supports, the 5% Cu-SiO2-AE catalyst was the best [...] Read more.
High-performance Cu catalysts were developed for the selective hydrogenation of γ-butyrolactone (GBL) to 1,4-butanediol (BDO). Among the various catalysts prepared by ammonia evaporation (AE) and impregnation (IM) methods with silica or MFI zeolite supports, the 5% Cu-SiO2-AE catalyst was the best one. It exhibited 95% selectivity for BDO and 71% conversion of GBL after 2–8 h reaction at 200 °C and 4 MPa H2, with high stability in five-cycle runs. Comprehensive characterizations showed that the AE method favored generating nano Cu particles with an average size of 2.9 nm on the 5% Cu-SiO2-AE catalyst. The silica support derived from a sol demonstrated an advantage over the MFI zeolite in the preparation of a highly dispersed and stable Cu catalyst, in view of its anti-sintering and robust composition of Cu0, Cu+, and Cu2+ in the cycling operation. The reaction pathways for GBL to BDO over the Cu catalysts were found to commonly involve reversible reactions of hydrogenation and dehydrogenation, along with subsequent dehydration to form THF. The high performance of the Cu catalysts in the conversion of GBL to BDO was attributed to the high dispersion of Cu, the presence of stable active sites, and fewer strong acid sites in the catalyst. Full article
(This article belongs to the Special Issue Heterogeneous Catalysis for Selective Hydrogenation)
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11 pages, 436 KiB  
Article
Synthesis of Helional by Hydrodechlorination Reaction in the Presence of Mono- and Bimetallic Catalysts Supported on Alumina
by Oreste Piccolo, Iztok Arčon, Gangadhar Das, Giuliana Aquilanti, Andrea Prai, Stefano Paganelli, Manuela Facchin and Valentina Beghetto
Catalysts 2024, 14(4), 255; https://doi.org/10.3390/catal14040255 - 12 Apr 2024
Cited by 1 | Viewed by 791
Abstract
Hydrodechlorination reaction of 3-(benzo-1,3-dioxol-5-yl)-3-chloro-2-methylacrylaldehyde in the presence of different low metal content heterogeneous mono- or bimetallic catalysts was tested for the synthesis of the fragrance Helional® (3-[3,4-methylendioxyphenyl]-2-methyl-propionaldehyde). In particular, mono Pd/Al2O3, Rh/Al2O3 or bimetallic Pd-Cu/Al [...] Read more.
Hydrodechlorination reaction of 3-(benzo-1,3-dioxol-5-yl)-3-chloro-2-methylacrylaldehyde in the presence of different low metal content heterogeneous mono- or bimetallic catalysts was tested for the synthesis of the fragrance Helional® (3-[3,4-methylendioxyphenyl]-2-methyl-propionaldehyde). In particular, mono Pd/Al2O3, Rh/Al2O3 or bimetallic Pd-Cu/Al2O3, Rh-Cu/Al2O3 catalysts were tested in different reaction conditions from which it emerged that mono-Rh/Al2O3 was the best performing catalyst, allowing achievement of 100% substrate conversion and 99% selectivity towards Helional® in 24 h at 80 °C, p(H2) 1.0 MPa in the presence of a base. To establish correlations between atomic structure and catalytic activity, catalysts were characterized by Cu, Rh and Pd K-edge XANES, EXAFS analysis. These characterizations allowed verification that the formation of Pd-Cu alloys and the presence of Cu oxide/hydroxide species on the surface of the Al2O3 support are responsible for the very low catalytic efficiency of bimetallic species tested. Full article
(This article belongs to the Special Issue Heterogeneous Catalysis for Selective Hydrogenation)
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15 pages, 3391 KiB  
Article
Investigating the Impact of Na2WO4 Doping in La2O3-Catalyzed OCM Reaction: A Structure–Activity Study via In Situ XRD-MS
by Danyu Wang, Junyu Lang, Zhehao Qiu, Ningxujin Ding and Yong Yang
Catalysts 2024, 14(2), 150; https://doi.org/10.3390/catal14020150 - 18 Feb 2024
Viewed by 971
Abstract
The La2O3 catalyst exhibits good performance in OCM reactions for its promising C2 selectivity and yield. Previous studies have affirmed that the formation of carbonates in La2O3 impedes the catalyst’s activity as a result of poisoning [...] Read more.
The La2O3 catalyst exhibits good performance in OCM reactions for its promising C2 selectivity and yield. Previous studies have affirmed that the formation of carbonates in La2O3 impedes the catalyst’s activity as a result of poisoning from CO2 exposure. In this study, a series of Na2WO4-impregnated La2O3 catalysts were synthesized to investigate the poisoning-resistant effect. The bulk phase and kinetics of the catalysts were analyzed in reactors employed with in situ XRD-MS and online MS, focusing on the CO2 adsorption on La2O3 and the phase transition process to La2O2CO3 in temperature zone correlated to OCM light-off. In situ XRD analysis revealed that, with Na2WO4 doped, CO2 exposure at elevated temperatures formed La2O2CO3 in tetragonal crystal phases, exhibiting distinctive differences from the hexagonal phase carbonates in undoped commercial La2O3. The ability to develop tetragonal or monoclinic La2O2CO3 was suggested as a descriptor to assess the sensitivity of La2O3 catalysts to CO2 adsorption, a tunable characteristic found in this study through varying Na2WO4 doping levels. Coupled XRD-MS analysis of CO2 adsorption uptake and phase change further confirmed a positive dependence between the resistivity of La2O3 catalyst to CO2 adsorption and its low-temperature C2 selectivity. The results extended the previous CO2 poisoning effect from multiple perspectives, offering a novel modification approach for enhancing the low-temperature performance of La2O3 catalysts in OCM. Full article
(This article belongs to the Special Issue Heterogeneous Catalysis for Selective Hydrogenation)
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13 pages, 5736 KiB  
Article
Temperature-Dependent Hydrogenation, Hydrodeoxygenation, and Hydrogenolysis of Anisole on Nickel Catalysts
by Shuya Zhang, Xiaochen Liu, Yuanjie Xu and Yu Tang
Catalysts 2023, 13(11), 1418; https://doi.org/10.3390/catal13111418 - 6 Nov 2023
Viewed by 1271
Abstract
Hydrogenation stands out as one of the most promising techniques for converting biomass-derived molecules into valuable products. The expected products of upgrading biomass molecules include hydrocarbon, oxygenate, and methane. Ni-based catalysts have attracted considerable interest owing to their unique properties and relatively low [...] Read more.
Hydrogenation stands out as one of the most promising techniques for converting biomass-derived molecules into valuable products. The expected products of upgrading biomass molecules include hydrocarbon, oxygenate, and methane. Ni-based catalysts have attracted considerable interest owing to their unique properties and relatively low cost. In this work, NiO prepared by the calcination and urea precipitation methods, namely NiO–C and NiO–U, is investigated for the hydrogenation of anisole. It is found that reaction temperature exerts a significant influence on the hydrogenation pathways. At 150 °C, C–reduced NiO proves more inclined towards hydrogenation, while U–reduced NiO demonstrates a tendency for hydrodeoxygenation (HDO). Moreover, as the temperature rises, both nickel catalysts change the reaction route to hydrogenolysis and eventually only produce methane at 300 °C, whereas metallic Ni is formed as the catalytic active phase. In situ FTIR experiments suggest the hydrogenolysis pathway and the formation of methane. This work investigates a route to produce methane from biomass molecules. Full article
(This article belongs to the Special Issue Heterogeneous Catalysis for Selective Hydrogenation)
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18 pages, 4210 KiB  
Article
Palladium-Rhenium Catalysts for Selective Hydrogenation of Furfural: Influence of Catalyst Preparation on Structure and Performance
by Simon T. Thompson and H. Henry Lamb
Catalysts 2023, 13(9), 1239; https://doi.org/10.3390/catal13091239 - 25 Aug 2023
Viewed by 1196
Abstract
PdRe/Al2O3 catalysts are highly selective for hydrogenation of furfural to furfuryl alcohol (FAL). Moreover, the synergy between the metals can result in greater specific activity (higher turnover frequency, TOF) than exhibited by either metal alone. Bimetallic catalyst structure depends strongly [...] Read more.
PdRe/Al2O3 catalysts are highly selective for hydrogenation of furfural to furfuryl alcohol (FAL). Moreover, the synergy between the metals can result in greater specific activity (higher turnover frequency, TOF) than exhibited by either metal alone. Bimetallic catalyst structure depends strongly on the metal precursors employed and their addition sequence to the support. In this work, PdRe/Al2O3 catalysts were prepared by: (i) co-impregnation (CI) and sequential impregnation (SI) of γ-Al2O3 using HReO4 and Pd(NO3)2, (ii) SI using NH4ReO4 and [Pd(NH3)4(NO3)2], (iii) HReO4 addition to a reduced and passivated Pd/Al2O3 catalyst, and (iv) impregnation with the double complex salt (DCS), [Pd(NH3)4(ReO4)2]. Raman spectroscopy and temperature-programmed reduction (TPR) evidence larger supported PdO crystallites in catalysts prepared using Pd(NO3)2 than [Pd(NH3)4(NO3)2]. Surface [ReO4] species detected by Raman exhibit TPR peak temperatures from ranging 85 to 260 °C (versus 375 °C for Re/Al2O3). After H2 reduction at 400 °C, the catalysts were characterized by chemisorption, temperature-programmed hydride decomposition (TPHD), CO diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and scanning transmission electron microscopy (STEM) with energy-dispersive x-ray (EDX) spectroscopy. The CI catalyst containing supported Pd–Re alloy crystallites had a TOF similar to Pd/Al2O3 but higher (61%) FAL selectivity. In contrast, catalysts prepared by methods (ii–iv) containing supported Pd-Re nanoparticles exhibit higher TOFs and up to 78% FAL selectivity. Full article
(This article belongs to the Special Issue Heterogeneous Catalysis for Selective Hydrogenation)
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17 pages, 7087 KiB  
Article
The Effect of Polymer Matrix on the Catalytic Properties of Supported Palladium Catalysts in the Hydrogenation of Alkynols
by Eldar Talgatov, Assemgul Auyezkhanova, Alima Zharmagambetova, Lyazzat Tastanova, Farida Bukharbayeva, Aigul Jumekeyeva and Talgat Aubakirov
Catalysts 2023, 13(4), 741; https://doi.org/10.3390/catal13040741 - 13 Apr 2023
Cited by 2 | Viewed by 1164
Abstract
Palladium catalysts were obtained by the adsorption method involving the sequential deposition of polyvinylpyrrolidone (PVP) and then palladium ions on a modified zinc oxide surface without high-temperature calcination and reduction stages. The immobilized PVP-palladium catalysts were characterized by scanning electron microscopy (SEM), transmission [...] Read more.
Palladium catalysts were obtained by the adsorption method involving the sequential deposition of polyvinylpyrrolidone (PVP) and then palladium ions on a modified zinc oxide surface without high-temperature calcination and reduction stages. The immobilized PVP-palladium catalysts were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Brunauer–Emmett–Teller (BET), infrared spectroscopy (IRS), X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and elemental analysis methods. It was found that the introduction of polymer into the catalyst’s composition promotes the dispersion and uniform distribution of active phase nanoparticles (PdO, Pd0) on the surface of zinc oxide. The catalysts were tested in the hydrogenation of complex acetylene alcohol, 3,7,11-trimethyldodecyn-1-ol-3 (C15-yn) under mild conditions (0.1 MPa, 40 °C). For comparison, studies on stereoselective hydrogenation of the short-chain alcohol 2-hexynol-1 were performed. It was shown that modification of the catalyst with polymer improves its catalytic properties. High C15-alkenol selectivity (98%), activity (W = 70 × 10−6 mol/s), and stability (turnover number (TON) 62,000) were achieved on a Pd-PVP/ZnO catalyst. Varying the active phase made it possible to reduce the metal content without deteriorating the catalytic performance of the catalyst. Full article
(This article belongs to the Special Issue Heterogeneous Catalysis for Selective Hydrogenation)
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17 pages, 3549 KiB  
Article
Crystal-Plane-Dependent Guaiacol Hydrodeoxygenation Performance of Au on Anatase TiO2
by Bin Zhao, Xiaoqiang Zhang, Jingbo Mao, Yanli Wang, Guanghui Zhang, Zongchao Conrad Zhang and Xinwen Guo
Catalysts 2023, 13(4), 699; https://doi.org/10.3390/catal13040699 - 4 Apr 2023
Cited by 4 | Viewed by 1377
Abstract
TiO2-supported catalysts have been widely used for a range of both liquid-phase and gas-phase hydrogenation reactions. However, little is known about the effect of their different crystalline surfaces on their activity during the hydrodeoxygenation process. In this work, Au supported on [...] Read more.
TiO2-supported catalysts have been widely used for a range of both liquid-phase and gas-phase hydrogenation reactions. However, little is known about the effect of their different crystalline surfaces on their activity during the hydrodeoxygenation process. In this work, Au supported on anatase TiO2, mainly exposing 101 or 001 facets, was investigated for the hydrodeoxygenation (HDO) of guaiacol. At 300 °C, the strong interaction between the Au and TiO2-101 surface resulted in the facile reduction of the TiO2-101 surface with concomitant formation of oxygen vacancies, as shown by the H2-TPR and H2-TPD profiles. Meanwhile, the formation of Auδ−, as determined by CO-DRIFT spectra and in situ XPS, was found to promote the demethylation of guaiacol producing methane. However, this strong interaction was absent on the Au/TiO2-001 catalyst since TiO2-001 was relatively difficult to be reduced compared with TiO2-101. The Au on TiO2-001 just served as the active site for the dissociation of hydrogen without the formation of Auδ−. The hydrogen atoms spilled over to the surface of TiO2-001 to form a small amount of oxygen vacancies, which resulted in lower activity than that over Au/TiO2-101. The catalytic activity of the Au/TiO2 catalyst for hydrodeoxygenation will be controlled by tuning the crystal plane of the TiO2 support. Full article
(This article belongs to the Special Issue Heterogeneous Catalysis for Selective Hydrogenation)
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21 pages, 6817 KiB  
Article
Hydrogenation of Carbon Monoxide in the Liquid Phase: Influence of the Synthetic Methods on Characteristics and Activity of Hydrogenation Catalysts
by Kalim A. Sheikh, Ricki Drexler, Thomas A. Zevaco, Jörg Sauer and Michael Bender
Catalysts 2023, 13(3), 482; https://doi.org/10.3390/catal13030482 - 27 Feb 2023
Cited by 2 | Viewed by 1935
Abstract
Oxygenate fuels are a promising solution to urban air pollution, reducing soot emissions by big margins. Formaldehyde is a major building block for the synthesis of oxygen-rich fuels. Herein we report the synthesis, characterisation and testing of ruthenium on alumina catalysts for the [...] Read more.
Oxygenate fuels are a promising solution to urban air pollution, reducing soot emissions by big margins. Formaldehyde is a major building block for the synthesis of oxygen-rich fuels. Herein we report the synthesis, characterisation and testing of ruthenium on alumina catalysts for the methanol-mediated CO hydrogenation towards oxygenates with the formaldehyde oxidation state. We varied the synthesis parameters and could see interesting correlation between synthesis parameters, final metal loading, crystallite sizes and catalyst activity. The catalysts were tested in a high-pressure three-folded reactor plant in the CO hydrogenation in methanolic media. Interesting relationships between catalyst synthesis, structure and activity could be gained from these experiments. Full article
(This article belongs to the Special Issue Heterogeneous Catalysis for Selective Hydrogenation)
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Review

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18 pages, 4664 KiB  
Review
Application of Heterogeneous Catalysis in Formic Acid-Based Hydrogen Cycle System
by Zhenzhen Wang, Junfeng Qian, Zhonghua Sun, Zhihui Zhang, Mingyang He and Qun Chen
Catalysts 2023, 13(8), 1168; https://doi.org/10.3390/catal13081168 - 30 Jul 2023
Cited by 2 | Viewed by 1308
Abstract
H2 has aroused significant attention as an unpolluted and renewable energy carrier. However, the efficient storage and controllable release of H2 are urgent to be addressed. Through the hydrogenation of CO2 (bicarbonate) to produce formic acid (formate) and reverse dehydrogenation [...] Read more.
H2 has aroused significant attention as an unpolluted and renewable energy carrier. However, the efficient storage and controllable release of H2 are urgent to be addressed. Through the hydrogenation of CO2 (bicarbonate) to produce formic acid (formate) and reverse dehydrogenation reactions, a carbon-neutral formic acid-based hydrogen cycle system can be established. Given the excellent recyclability and facile separation of heterogeneous catalysis, the development of heterogeneous catalysts for these reversible interconversions is thoroughly summarized, with a special focus on the structure–activity relationship and the mechanistic insight. Finally, the challenges and opportunities surrounding the formic acid-based hydrogen cycle system are discussed. It is hoped that this review will provide guidance and an idea for the design and development of efficient heterogeneous catalysts for the carbon-neutral H2 storage and release system. Full article
(This article belongs to the Special Issue Heterogeneous Catalysis for Selective Hydrogenation)
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