Ni-Containing Catalysts

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

Deadline for manuscript submissions: closed (30 April 2019) | Viewed by 56275

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Institut d’Alembert, Sorbonne Université, CNRS UMR7190, 2 pl de la Gare de Ceinture, 78210 St Cyr L’Ecole, France
Interests: kinetics; catalysis; thermodynamics; fuels; catalytic process; catalytic pollution control processes; chemistry of combustion
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CNRS, Institut Jean Le Rond d’Alembert, Sorbonne Université, Paris, France
Interests: catalysis; chemical engineering; process intensification; thermochemistry
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Murray Raney used Nickel for the first time as a hydrogentation catalyst over one century ago. Since then, the field of Nickel catalysis has seen tremendous advances. During the 1970s, Nickel found extensive use as a catalyst not only for cross-coupling reactions of alkenes/alkynes, such as nucleophilic allylation, oligomerization, and cycloisomerization, etc., but also for C/H activation, oxidative cyclidation, and reduction reactions. More recently, it has been used in the formulation of catalysts assessing important environmental issues, such as CO2 chemical utilization, or as dopant of molybdenum, sulfide-containing catalysts for desulfuration processes. 

Several key properties of nickel such as its thermal stability and redox behavior mean Nickel-containing catalysts are still challenging for a very large range of innovative reaction developments and industrialization. 

The purpose of this Special Issue is to update the most recent advances concerning Nickel catalysts, supported or not, for innovative reaction development.

Prof. Patrick Da Costa
Dr. Maria Elena Galvez
Guest Editors

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Published Papers (13 papers)

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Editorial

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3 pages, 157 KiB  
Editorial
Ni-Containing Catalysts
by Patrick Da Costa
Catalysts 2021, 11(5), 645; https://doi.org/10.3390/catal11050645 - 19 May 2021
Cited by 1 | Viewed by 1745
Abstract
Murray Raney used Nickel for the first time as a hydrogenation catalyst over one century ago [...] Full article
(This article belongs to the Special Issue Ni-Containing Catalysts)

Research

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12 pages, 4242 KiB  
Article
Carbon Deposition Behavior of Ni Catalyst Prepared by Combustion Method in Slurry Methanation Reaction
by Keming Ji, Fanhui Meng, Jiayao Xun, Ping Liu, Kan Zhang, Zhong Li and Junhua Gao
Catalysts 2019, 9(7), 570; https://doi.org/10.3390/catal9070570 - 28 Jun 2019
Cited by 10 | Viewed by 2899
Abstract
Ni/Al2O3 catalyst prepared by combustion method was applied in a slurry methanation reaction to study the catalytic performance, especially the regeneration performance. The catalyst properties were characterized by (X-Ray diffraction) XRD, Inductively coupled plasma atomic emission spectrometer (ICP-AES), Nitrogen adsorption-desorption, [...] Read more.
Ni/Al2O3 catalyst prepared by combustion method was applied in a slurry methanation reaction to study the catalytic performance, especially the regeneration performance. The catalyst properties were characterized by (X-Ray diffraction) XRD, Inductively coupled plasma atomic emission spectrometer (ICP-AES), Nitrogen adsorption-desorption, Transmission electron microscopy (TEM), Thermogravimetric analysis (TG/DTG), Temperature programmed oxidation (TPO), and H2 chemisorption before and after reaction. The results show that the catalyst deactivation was mainly due to carbon deposition, which exhibited amorphous carbon films and formed by the disproportionation of CO. The carbon deposition was formed on the catalyst surface and existed as carbon films during the reaction, then it gradually separated from the catalyst surface, generated an overlapping multi-layer three-dimensional carbon structure, which covered the active site and blocked the pores. As a result, the metal surface area of catalyst decreases, as well as the activity. The carbon deposition could be removed by oxidative calcination without destroying the catalyst structure, the active sites could be re-exposed and the catalyst activity could be recovered. Full article
(This article belongs to the Special Issue Ni-Containing Catalysts)
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16 pages, 4859 KiB  
Article
Computational Investigation of Nickel-Mediated B–H Activation and Regioselective Cage B–C(sp2) Coupling of o-Carborane
by Wei-Hua Mu, Wen-Zhu Liu, Rui-Jiao Cheng, Li-Juan Dou, Pin Liu and Qiang Hao
Catalysts 2019, 9(6), 548; https://doi.org/10.3390/catal9060548 - 18 Jun 2019
Cited by 3 | Viewed by 3124
Abstract
Density functional theory (DFT) methods including LC-ωPBE, CAM-B3LYP, B3LYP, and B3LYP-D3, combined with double Zeta all-electron DZVP basis set, have been employed to conduct computational investigations on nickel-mediated reaction of o-carboranylzirconacycle, n-hexene, and 2-bromophenyltrimethylsilylacetylene in toluene solution. A multistep mechanism leading [...] Read more.
Density functional theory (DFT) methods including LC-ωPBE, CAM-B3LYP, B3LYP, and B3LYP-D3, combined with double Zeta all-electron DZVP basis set, have been employed to conduct computational investigations on nickel-mediated reaction of o-carboranylzirconacycle, n-hexene, and 2-bromophenyltrimethylsilylacetylene in toluene solution. A multistep mechanism leading to the C,C,B-substituted carborane-fused tricyclics, including (1) sequential insertion of alkene and alkyne into Ni–C bonds; (2) double 1,2-migration of the TMS group; (3) B–H activation assisted by Cs2CO3 additive; and (4) reduction cage B–C (sp2) coupling, was proposed. Among these steps, the B–H activation of o-carborane was located as rate-determining step (RDS). With assistance of Cs2CO3 additive (replaced by K2CO3 in simulation), the RDS free-energy barrier at PCM-LC-ωPBE/DZVP level was calculated to be 23.1–23.9 kcal·mol−1, transferring to a half-life of 3.9–15.1 h at 298 K. The predicted half-life coincides well with 80% experimental yields of C,C,B-substituted carborane-fused tricyclics after 12 h. Kinetic data obtained by employing LC-ωPBE method also reproduced the experimental diastereoselective ratio well. Various B–H activation pathways with and without Cs2CO3 additive were taken into consideration, which illustrates Cs2CO3 as an essential guarantee for smooth occurrence of this reaction at room temperature. Full article
(This article belongs to the Special Issue Ni-Containing Catalysts)
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21 pages, 3592 KiB  
Article
Nickel Supported on AlCeO3 as a Highly Selective and Stable Catalyst for Hydrogen Production via the Glycerol Steam Reforming Reaction
by Nikolaos D. Charisiou, Georgios I. Siakavelas, Binlin Dou, Victor Sebastian, Steven J. Hinder, Mark A. Baker, Kyriaki Polychronopoulou and Maria A. Goula
Catalysts 2019, 9(5), 411; https://doi.org/10.3390/catal9050411 - 1 May 2019
Cited by 41 | Viewed by 4372
Abstract
In this study, a critical comparison between two low metal (Ni) loading catalysts is presented, namely Ni/Al2O3 and Ni/AlCeO3 for the glycerol steam reforming (GSR) reaction. The surface and bulk properties of the catalysts were evaluated using a plethora [...] Read more.
In this study, a critical comparison between two low metal (Ni) loading catalysts is presented, namely Ni/Al2O3 and Ni/AlCeO3 for the glycerol steam reforming (GSR) reaction. The surface and bulk properties of the catalysts were evaluated using a plethora of techniques, such as N2 adsorption/desorption, Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP–AES), X-ray Diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS), Scanning Electron Microscopy / Energy Dispersive X-Ray Spectroscopy (SEM/EDX, Transmission Electron Microscopy (TEM), CO2 and NH3– Temperature Programmed Desorption (TPD), and Temperature Programmed Reduction (H2–TPR). Carbon deposited on the catalyst’s surfaces was probed using Temperature Programmed Oxidation (TPO), SEM, and TEM. It is demonstrated that Ce-modification of Al2O3 induces an increase of the surface basicity and Ni dispersion. These features lead to a higher conversion of glycerol to gaseous products (60% to 80%), particularly H2 and CO2, enhancement of WGS reaction, and a higher resistance to coke deposition. Allyl alcohol was found to be the main liquid product for the Ni/AlCeO3 catalyst, the production of which ceases over 700 °C. It is also highly significant that the Ni/AlCeO3 catalyst demonstrated stable values for H2 yield (2.9–2.3) and selectivity (89–81%), in addition to CO2 (75–67%) and CO (23–29%) selectivity during a (20 h) long time-on-stream study. Following the reaction, SEM/EDX and TEM analysis showed heavy coke deposition over the Ni/Al2O3 catalyst, whereas for the Ni/AlCeO3 catalyst TPO studies showed the formation of more defective coke, the latter being more easily oxidized. Full article
(This article belongs to the Special Issue Ni-Containing Catalysts)
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15 pages, 9692 KiB  
Article
Highly Dispersed Ni Nanocatalysts Derived from NiMnAl-Hydrotalcites as High-Performing Catalyst for Low-Temperature Syngas Methanation
by Bin Lu, Jiahao Zhuang, Jinping Du, Fangna Gu, Guangwen Xu, Ziyi Zhong, Qing Liu and Fabing Su
Catalysts 2019, 9(3), 282; https://doi.org/10.3390/catal9030282 - 19 Mar 2019
Cited by 16 | Viewed by 4070
Abstract
Increasing the low-temperature performance of nickel-based catalysts in syngas methanation is critical but very challenging, because at low temperatures there is high concentration of CO on the catalyst surface, causing formation of nickel carbonyl with metallic Ni and further catalyst deactivation. Herein, we [...] Read more.
Increasing the low-temperature performance of nickel-based catalysts in syngas methanation is critical but very challenging, because at low temperatures there is high concentration of CO on the catalyst surface, causing formation of nickel carbonyl with metallic Ni and further catalyst deactivation. Herein, we have prepared highly dispersed Ni nanocatalysts by in situ reduction of NiMnAl-layered double hydroxides (NiMnAl-LDHs) and applied them to syngas methanation. The synthesized Ni nanocatalysts maintained the nanosheet structure of the LDHs, in which Ni particles were decorated with MnOy species and embedded in the AlOx nanosheets. It was observed that the Ni nanocatalysts exhibited markedly better low-temperature performance than commercial catalysts in the syngas methanation. At 250 °C, 3.0 MPa and a high weight hourly space velocity (WHSV) of 30,000 mL·g−1·h−1, both the CO conversion and the CH4 selectivity reached 100% over the former, while those over the commercial catalyst were only 14% and 76%, respectively. Furthermore, this NiMnAl catalyst exhibited strong anti-carbon and anti-sintering properties at high temperatures. The enhanced low-temperature performance and high-temperature stability originated from the promotion effect of MnOy and the embedding effect of AlOx in the catalyst. Full article
(This article belongs to the Special Issue Ni-Containing Catalysts)
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12 pages, 3154 KiB  
Article
The Role of NiO in Reactive Adsorption Desulfurization Over NiO/ZnO-Al2O3-SiO2 Adsorbent
by Feng Ju, Miao Wang, Tian Wu and Hao Ling
Catalysts 2019, 9(1), 79; https://doi.org/10.3390/catal9010079 - 14 Jan 2019
Cited by 15 | Viewed by 4219
Abstract
The reactive adsorption desulfurization (RADS) of a model gasoline n-hexane containing thiophene was carried out with a NiO/ZnO-Al2O3-SiO2 adsorbent in N2 and H2, respectively. A declining RADS trend has been observed in N2 [...] Read more.
The reactive adsorption desulfurization (RADS) of a model gasoline n-hexane containing thiophene was carried out with a NiO/ZnO-Al2O3-SiO2 adsorbent in N2 and H2, respectively. A declining RADS trend has been observed in N2, without the presence of H2, indicating that NiO is sulfurized and exhibits activity for RADS. TPR and XPS results presented NiO in the adsorbent is hard to be reduced because of the powerful interaction between NiO and the support. The sulfurization of NiO into NiSx is a primary condition for the RADS process, the same as the presulfurization of hydrotreating catalyst, while metallic Ni is an intermediate reduction product of NiSx. Results of a low RADS temperature at 300 °C, much lower than the reduction temperature of NiO, suggest that NiO plays an important role. Based on assumption of NiO as the main active component, the RADS could reduce the reaction temperature and energy consumption significantly. The participation of hydrogen and n-hexane in pretreatment conducted at 420 °C contributes to the activation of adsorbent. Also, these methods of pretreatment improved the desulfurization performance under the reaction temperature of 300 °C. Full article
(This article belongs to the Special Issue Ni-Containing Catalysts)
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7 pages, 816 KiB  
Article
Prominent Conductor Mechanism-Induced Electron Transfer of Biochar Produced by Pyrolysis of Nickel-Enriched Biomass
by Wenbing Tan, Renfei Li, Hanxia Yu, Xinyu Zhao, Qiuling Dang, Jie Jiang, Lei Wang and Beidou Xi
Catalysts 2018, 8(12), 573; https://doi.org/10.3390/catal8120573 - 22 Nov 2018
Cited by 4 | Viewed by 2774
Abstract
Biochar is redox-active and can function as a sustainable electron shuttle in catalyzing relevant redox reactions. It plays a crucial role in environmental remediation. In this work, we used different-nickel (Ni)-level biochars produced by the pyrolysis of plant biomass with correspondingly different Ni [...] Read more.
Biochar is redox-active and can function as a sustainable electron shuttle in catalyzing relevant redox reactions. It plays a crucial role in environmental remediation. In this work, we used different-nickel (Ni)-level biochars produced by the pyrolysis of plant biomass with correspondingly different Ni levels as extracellular electron shuttles for microbial reduction of ferrihydrite by Shewanella oneidensis MR-1. A high Ni level of the precursor considerably enhanced the conductor mechanism of the produced biochar and thus enabled the biochar to catalyze increased microbial reductions of the Fe(III) mineral, but it did not promote the charging and discharging capacities of the produced biochar. This study can aid in the search for natural biomass with high Ni content to establish low-cost biochars with wide-ranging applications in catalyzing the redox-mediated reactions of pollutants. Full article
(This article belongs to the Special Issue Ni-Containing Catalysts)
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10 pages, 8911 KiB  
Article
Application of POCOP Pincer Nickel Complexes to the Catalytic Hydroboration of Carbon Dioxide
by Jie Zhang, Jiarui Chang, Ting Liu, Bula Cao, Yazhou Ding and Xuenian Chen
Catalysts 2018, 8(11), 508; https://doi.org/10.3390/catal8110508 - 1 Nov 2018
Cited by 23 | Viewed by 3748
Abstract
The reduction of CO2 is of great importance. In this paper, different types of bis(phosphinite) (POCOP) pincer nickel complexes, [2,6-(R2PO)2C6H3]NiX (R = tBu, iPr, Ph; X = SH, N3, NCS), [...] Read more.
The reduction of CO2 is of great importance. In this paper, different types of bis(phosphinite) (POCOP) pincer nickel complexes, [2,6-(R2PO)2C6H3]NiX (R = tBu, iPr, Ph; X = SH, N3, NCS), were applied to the catalytic hydroboration of CO2 with catecholborane (HBcat). It was found that pincer complexes with tBu2P or iPr2P phosphine arms are active catalysts for this reaction in which CO2 was successfully reduced to a methanol derivative (CH3OBcat) with a maximum turnover frequency of 1908 h−1 at room temperature under an atmospheric pressure of CO2. However, complexes with phenyl-substituted phosphine arms failed to catalyze this reaction—the catalysts decomposed under the catalytic conditions. Complexes with iPr2P phosphine arms are more active catalysts compared with the corresponding complexes with tBu2P phosphine arms. For complexes with the same phosphine arms, the catalytic activity follows the series of mercapto complex (X = SH) ≈ azido complex (X = N3) >> isothiocyanato complex (X = NCS). It is believed that all of these catalytic active complexes are catalyst precursors which generate the nickel hydride complex [2,6-(R2PO)2C6H3]NiH in situ, and the nickel hydride complex is the active species to catalyze this reaction. Full article
(This article belongs to the Special Issue Ni-Containing Catalysts)
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9 pages, 4343 KiB  
Article
Study of Chemical and Morphological Transformations during Ni2Mo3N Synthesis via an Oxide Precursor Nitration Route
by Denis V. Leybo, Dmitry I. Arkhipov, Konstantin L. Firestein and Denis V. Kuznetsov
Catalysts 2018, 8(10), 436; https://doi.org/10.3390/catal8100436 - 3 Oct 2018
Cited by 3 | Viewed by 2449
Abstract
Chemical and morphological transformations during Ni2Mo3N synthesis were studied in this work. Nitride samples were synthesized from oxide precursors in H2/N2 flow and were analyzed by thermogravimetry, X-ray diffraction analysis, scanning electron microscopy, and energy dispersive [...] Read more.
Chemical and morphological transformations during Ni2Mo3N synthesis were studied in this work. Nitride samples were synthesized from oxide precursors in H2/N2 flow and were analyzed by thermogravimetry, X-ray diffraction analysis, scanning electron microscopy, and energy dispersive X-ray spectroscopy methods. In addition, physical and chemical adsorption properties were studied using low-temperature N2 physisorption and NH3 temperature-programmed desorption. It was shown that nitride formation proceeds through a sequence of phase transformations: NiMoO4 + MoO3 → Ni + NiMo + MoO2 → Ni + NiMo + Mo2N → Ni2Mo3N. The weight changes that were calculated from the proposed reactions were in agreement with the experimental data from thermogravimetry. The morphology of the powder changed from platelets and spheres for the oxide sample, to aggregates of needle-like particles for the intermediate product, to porous particles with an extended surface area for the nitride final product. The obtained results should prove useful for subsequent Ni2Mo3N based catalysts production process optimization. Full article
(This article belongs to the Special Issue Ni-Containing Catalysts)
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12 pages, 4825 KiB  
Article
NOx Removal by Selective Catalytic Reduction with Ammonia over a Hydrotalcite-Derived NiFe Mixed Oxide
by Ruonan Wang, Xu Wu, Chunlei Zou, Xiaojian Li and Yali Du
Catalysts 2018, 8(9), 384; https://doi.org/10.3390/catal8090384 - 8 Sep 2018
Cited by 38 | Viewed by 4585
Abstract
A series of NiFe mixed oxide catalysts were prepared via calcining hydrotalcite-like precursors for the selective catalytic reduction of nitrogen oxides (NOx) with NH3 (NH3-SCR). Multiple characterizations revealed that catalytic performance was highly dependent on the phase composition, [...] Read more.
A series of NiFe mixed oxide catalysts were prepared via calcining hydrotalcite-like precursors for the selective catalytic reduction of nitrogen oxides (NOx) with NH3 (NH3-SCR). Multiple characterizations revealed that catalytic performance was highly dependent on the phase composition, which was vulnerable to the calcination temperature. The MOx phase (M = Ni or Fe) formed at a lower calcination temperature would induce more favorable contents of Fe2+ and Ni3+ and as a result contribute to the better redox capacity and low-temperature activity. In comparison, NiFe2O4 phase emerged at a higher calcination temperature, which was expected to generate more Fe species on the surface and lead to a stable structure, better high-temperature activity, preferable SO2 resistance, and catalytic stability. The optimum NiFe-500 catalyst incorporated the above virtues and afforded excellent denitration (DeNOx) activity (over 85% NOx conversion with nearly 98% N2 selectivity in the region of 210–360 °C), superior SO2 resistance, and catalytic stability. Full article
(This article belongs to the Special Issue Ni-Containing Catalysts)
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12 pages, 4718 KiB  
Article
Highly Loaded and Dispersed Ni2P/Al2O3 Catalyst with High Selectivity for Hydrogenation of Acetophenone
by Junen Wang, Yanling Wang, Gaoli Chen and Zhanjun He
Catalysts 2018, 8(8), 309; https://doi.org/10.3390/catal8080309 - 30 Jul 2018
Cited by 12 | Viewed by 4222
Abstract
Highly loaded and dispersed Ni2P/Al2O3 catalyst was prepared by the phosphidation of Ni/Al2O3 catalyst with Ni loading of 80 wt.% in liquid phase and compared with the Ni/Al2O3 catalyst for the hydrogenation [...] Read more.
Highly loaded and dispersed Ni2P/Al2O3 catalyst was prepared by the phosphidation of Ni/Al2O3 catalyst with Ni loading of 80 wt.% in liquid phase and compared with the Ni/Al2O3 catalyst for the hydrogenation of acetophenone. X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) etc. were used to characterize the textural and structural properties of the prepared catalysts. It was found that the Ni/Al2O3 and Ni2P/Al2O3 catalyst possessed high surface area, loading and dispersion. The Ni/Al2O3 catalyst had higher apparent activity while the Ni2P/Al2O3 catalyst had higher intrinsic activity for the hydrogenation of acetophenone (AP). Remarkably, the Ni2P/Al2O3 catalyst exhibited high selectivity to 1-phenylethanol, due to repulsion of the phosphorous (Pδ) for phenyl group and attraction of the nickel (Niδ+) for oxygen atom of carbonyl group, leading to preferential hydrogenation of carbonyl group in acetophenone. The effect of the particle size of the catalyst on the chemical selectivity might be another reason for high selectivity on the Ni2P/Al2O3 catalyst. Full article
(This article belongs to the Special Issue Ni-Containing Catalysts)
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Review

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39 pages, 6965 KiB  
Review
Lignin Valorizations with Ni Catalysts for Renewable Chemicals and Fuels Productions
by Xiao Chen, Weixiang Guan, Chi-Wing Tsang, Haoquan Hu and Changhai Liang
Catalysts 2019, 9(6), 488; https://doi.org/10.3390/catal9060488 - 28 May 2019
Cited by 35 | Viewed by 7230
Abstract
Energy and fuels derived from biomass pose lesser impact on the environmental carbon footprint than those derived from fossil fuels. In order for the biomass-to-energy and biomass-to-chemicals processes to play their important role in the loop of the circular economy, highly active, selective, [...] Read more.
Energy and fuels derived from biomass pose lesser impact on the environmental carbon footprint than those derived from fossil fuels. In order for the biomass-to-energy and biomass-to-chemicals processes to play their important role in the loop of the circular economy, highly active, selective, and stable catalysts and the related efficient chemical processes are urgently needed. Lignin is the most thermal stable fraction of biomass and a particularly important resource for the production of chemicals and fuels. This mini review mainly focuses on lignin valorizations for renewable chemicals and fuels production and summarizes the recent interest in the lignin valorization over Ni and relevant bimetallic metal catalysts on various supports. Particular attention will be paid to those strategies to convert lignin to chemicals and fuels components, such as pyrolysis, hydrodeoxygenation, and hydrogenolysis. The review is written in a simple and elaborated way in order to draw chemists and engineers’ attention to Ni-based catalysts in lignin valorizations and guide them in designing innovative catalytic materials based on the lignin conversion reaction. Full article
(This article belongs to the Special Issue Ni-Containing Catalysts)
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27 pages, 10813 KiB  
Review
Ni Promotion by Fe: What Benefits for Catalytic Hydrogenation?
by Dichao Shi, Robert Wojcieszak, Sébastien Paul and Eric Marceau
Catalysts 2019, 9(5), 451; https://doi.org/10.3390/catal9050451 - 15 May 2019
Cited by 46 | Viewed by 9559
Abstract
Metallic nickel is known to efficiently catalyze hydrogenation reactions, but one of its major drawbacks lies in its lack of selectivity, linked to side-reactions of hydrogenolysis and over-hydrogenation. More selective hydrogenations can be obtained upon the introduction of a second metal in combination [...] Read more.
Metallic nickel is known to efficiently catalyze hydrogenation reactions, but one of its major drawbacks lies in its lack of selectivity, linked to side-reactions of hydrogenolysis and over-hydrogenation. More selective hydrogenations can be obtained upon the introduction of a second metal in combination with Ni. Fe is an interesting choice, as it is a cheap and abundant metal. This review aims at discussing the advantages and constraints brought by the preparation procedures of bimetallic supported Ni–Fe nanoparticles, and at analyzing the benefits one can draw by substituting Ni–Fe supported catalysts for Ni monometallic systems for the catalytic hydrogenation of organic molecules. Specific formulations, such as Ni75Fe25, will be singled out for their high activity or selectivity, and the various hypotheses behind the roles played by Fe will be summarized. Full article
(This article belongs to the Special Issue Ni-Containing Catalysts)
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