Intermetallic nickel silicide nanocatalyst—A non-noble metal–based general hydrogenation catalyst

Ryabchuk, Pavel; Agostini, Giovanni; Pohl, Marga‐Martina; Lund, Henrik; Agapova, Anastasiya; Junge, Henrik; Junge, Kathrin; Beller, Matthias

doi:10.1126/sciadv.aat0761

Cited by 123 publications

(135 citation statements)

References 37 publications

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“…[12,13,18,23,25,29] For the metal incorporated ceramics, the active metal ions (Ni or Co) helps the thermal reduction process of SiÀ O bonds, which results in a diffusion of Si atoms into the metal lattice and forms intermetallic nickel/cobalt silicide nanoparticles upon the ceramic matrix. [12,13,[29][30][31] The XRD pattern (Figure 1 a) of Co/SiOC after pyrolysis at 1200°C shows a high-intensity diffraction peak at 26°indexed to (002) plane indicating the presence of low ordered turbostratic graphitic carbon phase. [13,25] This confirms that the presence of metal ions has significantly involved as a catalyst in the promotion of CÀ C bond leading to the formation of turbostratic carbon.…”

Section: Resultsmentioning

confidence: 99%

Metal Silicide Nanosphere Decorated Carbon‐Rich Polymer‐Derived Ceramics: Bifunctional Electrocatalysts towards Oxygen and their Application in Anion Exchange Membrane Fuel Cells

et al. 2019

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The current hindrance in the commercialization of electrochemical devices such as fuel cells and metal–air batteries is the high cost and poor stability of widely employed noble‐metal‐based electrocatalysts. In this report, a new intermetallic nickel/cobalt silicide‐decorated carbon‐rich silica‐based ceramic composites (Co/SiOC or Ni/SiOC) were successfully synthesized as alternative bifunctional electrocatalysts. The oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) kinetics of the prepared composite materials were evaluated by electrochemical characterization. Co/SiOC exhibited more positive ORR kinetics with the onset potential of 0.87 V vs. RHE compared to that of Ni/SiOC, which is slightly lower compared to Pt/C. Conversely, Ni/SiOC exhibits a 50 mV more positive OER onset potential compared to Co/SiOC with almost similar OER kinetics to RuO2. The bifunctional ability concluded that Ni/SiOC was a good bifunctional catalyst with an oxygen electrode potential 0.89 V. As Co/SiOC performs as a better ORR catalyst, it was utilized as a cathode catalyst for the construction of anion exchange membrane fuel cell and its fuel cell performance was evaluated. The Co/SiOC composites produce a peak power density of 54 mW/cm2, representing a satisfactory result when compared with Pt/C. The results reveal that the intermetallic nickel/cobalt silicide nanosphere decorated ceramic materials can have a promising future as efficient alternative electrocatalysts in electrochemical devices.

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Section: Resultsmentioning

confidence: 99%

Metal Silicide Nanosphere Decorated Carbon‐Rich Polymer‐Derived Ceramics: Bifunctional Electrocatalysts towards Oxygen and their Application in Anion Exchange Membrane Fuel Cells

et al. 2019

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“…Over the past few years, non-noble metal catalysts have attracted much attention due to their comparable properties with noble metal catalysts in both homogeneous and heterogeneous catalysis [113][114][115][116][117]. In particular, furfural hydrogenation has been widely tested while using various non-noble metal catalysts, such as Cu, Co, Ni, and Zr, among others.…”

Section: Non-noble Metal Catalystsmentioning

confidence: 99%

Recent Advances in Catalytic Hydrogenation of Furfural

et al. 2019

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Furfural has been considered as one of the most promising platform molecules directly derived from biomass. The hydrogenation of furfural is one of the most versatile reactions to upgrade furanic components to biofuels. For instance, it can lead to plenty of downstream products, such as (tetrahydro)furfuryl alcohol, 2-methyl(tetrahydro)furan, lactones, levulinates, cyclopentanone(l), or diols, etc. The aim of this review is to discuss recent advances in the catalytic hydrogenation of furfural towards (tetrahydro)furfuryl alcohol and 2-methyl(tetrahydro)furan in terms of different non-noble metal and noble metal catalytic systems. Reaction mechanisms that are related to the different catalytic materials and reaction conditions are properly discussed. Selective hydrogenation of furfural could be modified not only by varying the types of catalyst (nature of metal, support, and preparation method) and reaction conditions, but also by altering the reaction regime, namely from batch to continuous flow. In any case, furfural catalytic hydrogenation is an open research line, which represents an attractive option for biomass valorization towards valuable chemicals and fuels.FA is a very important monomer for the synthesis of furan resins, which are widely used in thermoset polymer matrix composites, cements, adhesives, coatings, and casting/foundry resins. This molecule is also used as a non-reactive diluent for epoxy resin, a modifier for phenolic and urea resins, an oil well, and a carbon binder. Furthermore, the salt of FA is used in the synthesis of lysine, vitamin C, lubricants, and plasticizers [22,23]. Moreover, it should be highlighted that FA is also an important intermediate for the production of further hydrogenation products (as shown in Scheme 1), such as 2-methylfuran (MF), a potential alternative fuel with better combustion performance and higher Research Octane Number (RON = 103) than that of gasoline (RON = 96.8) [24]. In other applications, MF is used in perfume intermediates, chloroquine lateral chains in medical intermediates, and as a raw material for the production of chrysanthemate pesticides [25].Moreover, tetrahydrofurfuryl alcohol (THFA) can be used as a green solvent in the pharmaceutical industry and, in addition, it constitutes an outstanding intermediate to produce dihydropyran [26], pyridine [27], tetrahydrofuran, and pentan-1,5-diol [28][29][30]. Particularly, the latest molecule is an important monomer in the plastics industry. Furthermore, 2-methyltetrahydrofuran (MTHF) is quite engaging for its possible applications in organometallic chemistry, as well as in organic reactions that are related to organocatalysis, biotransformations, and biomass processing [31]. Catalysts 2019, 9, 796 3 of 33 Catalysts 2018, 8, x FOR PEER REVIEW 3 of 36 Scheme 1. Illustrative representation of reaction pathways in furfural hydrogenation.Other downstream products of furfural hydrogenation, such as (tetrahydro)furan [32], tetrahydrofurfural [33], lactones [34][35][36][37], levulinates [38,39], cyclopentanone...

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“…Nickel silicides have also received attention, for example Ni31Si12, Ni2Si, NiSi2, and NiSi in hydrogenation reactions. 41,42,43,44,45 Ni2Si and Pd2Si were investigated for HER, 46 and for selective phenylacetylene hydrogenation. 47 Recently, ternary silicide intermetallics such as LaScSi, LaCoSi, and LnNiSi (Ln = La-Nb) have gathered attention due to their ability to act as electrides-compounds which have anionic-like electrons localized in interstitial sites-which renders them useful in hydrogen storage as well as in catalytic ammonia synthesis at moderate temperature (400 °C) and pressure (1 atm).…”

Section: Introductionmentioning

confidence: 99%

Intermetallic Nanocatalysts from Heterobimetallic Group 10–14 Pyridine-2-thiolate Precursors

et al. 2020

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Intermetallic compounds are atomically ordered inorganic materials containing two or more transition metals and main-group elements in unique crystal structures. Intermetallics based on group 10 and group 14 metals have shown enhanced activity, selectivity, and durability in comparison to simple metals and alloys in many catalytic reactions. While high-temperature solid-state methods to prepare intermetallic compounds exist, softer synthetic methods can provide key advantages, such as enabling the preparation of metastable phases or of smaller particles with increased surface areas for catalysis. Here, we study a generalized family of heterobimetallic precursors to binary intermetallics, each containing a group 10 metal and a group 14 tetrel bonded together and supported by pincer-like pyridine-2-thiolate ligands. Upon thermal decomposition, these heterobimetallic complexes form 10-14 binary intermetallic nanocrystals. Experiments and density functional theory (DFT) computations help in better understanding the reactivity of these precursors toward the synthesis of specific intermetallic binary phases. Using Pd2Sn as an example, we demonstrate that nanoparticles made in this way can act as uniquely selective catalysts for the reduction of nitroarenes to azoxyarenes, which highlights the utility of the intermetallics made by our method. Employing heterobimetallic pincer complexes as precursors toward binary nanocrystals and other metal-rich intermetallics provides opportunities to explore the fundamental chemistry and applications of these materials.

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Intermetallic nickel silicide nanocatalyst—A non-noble metal–based general hydrogenation catalyst

Abstract: Incorporation of silicon atoms into nickel nanoparticles boosts the catalytic activity for (de)hydrogenation reactions.

Cited by 123 publications

References 37 publications

Metal Silicide Nanosphere Decorated Carbon‐Rich Polymer‐Derived Ceramics: Bifunctional Electrocatalysts towards Oxygen and their Application in Anion Exchange Membrane Fuel Cells

Metal Silicide Nanosphere Decorated Carbon‐Rich Polymer‐Derived Ceramics: Bifunctional Electrocatalysts towards Oxygen and their Application in Anion Exchange Membrane Fuel Cells

Recent Advances in Catalytic Hydrogenation of Furfural

Intermetallic Nanocatalysts from Heterobimetallic Group 10–14 Pyridine-2-thiolate Precursors

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