Selective Hydrogenation Reactions Research Articles

Expedited Synthesis of Metal Phosphides Maximizes Dispersion, Air Stability, and Catalytic Performance in Selective Hydrogenation.

Metal phosphides have been hailed as potential replacements for scarce noble metal catalysts in many aspects of the hydrogen economy from hydrogen evolution to selective hydrogenation reactions. But the need for dangerous and costly phosphorus precursors, limited support dispersion, and low stability of the metal phosphide surface toward oxidation substantially lower the appeal and performance of metal phosphides in catalysis. We show here that a 1-step procedure that relies on safe and cheap precursors can furnish an air-stable Ni2P/Al2O3 catalyst containing 3.2 nm nanoparticles. Ni2P/Al2O3 1-step is kinetically competitive with the palladium-based Lindlar catalyst in selective hydrogenation catalysis, and a loading corresponding to 4 ppm Ni was sufficient to convert 0.1 mol alkyne. The 1-step synthetic procedure alters the surface ligand speciation of Ni2P/Al2O3, which protects the nanoparticle surface from oxidation, and ensures that 85 % of the initial catalytic activity was retained after the catalyst was stored under air for 1.5 years. Preparation of Ni2P on a variety of supports (silica, TiO2, SBA-15, ZrO2, C and HAP) as well as Co2P/Al2O3, Co2P/TiO2 and bimetallic NiCoP/TiO2 demonstrates the generality with which supported metal phosphides can be accessed in a safe and straightforward fashion with small sizes and high dispersion.

Tuning the Electronic Structures of Anchor Sites to Achieve Zero‐Valence Single‐Atom Catalysts for Advanced Hydrogenation

Single‐atom catalysts (SACs) have recently become highly attractive for selective hydrogenation reactions owing to their remarkably high selectivity. However, compared to their nanoparticle counterparts, atomically dispersed metal atoms in SACs often show inferior activity and are prone to aggregate under reaction conditions. Here, by theoretical calculations, we show that tuning the local electronic structures of metal anchor sites on g‐C3N4 by doping B atoms (BCN) with relatively lower electronegativity allows achieving zero‐valence Pd SACs with reinforced metal‐support orbital hybridizations for high stability and upshifted Pd 4d orbitals for high activity in H2 activation. The precise synthesis of Pd SACs on BCN supports with varied B contents substantiated the theoretical prediction. A zero‐valence Pd1/BCN SAC was achieved on a BCN support with a relatively low B content. It exhibited much higher stability in a H2 reducing environment, and more strikingly, a hydrogenation activity, approximately 10 and 34 times greater than those high‐valence Pd1/g‐C3N4 and Pd1/BCN with a high B content, respectively.

Tuning the Electronic Structures of Anchor Sites to Achieve Zero-Valence Single-Atom Catalysts for Advanced Hydrogenation.

Single-atom catalysts (SACs) have recently become highly attractive for selective hydrogenation reactions owing to their remarkably high selectivity. However, compared to their nanoparticle counterparts, atomically dispersed metal atoms in SACs often show inferior activity and are prone to aggregate under reaction conditions. Here, by theoretical calculations, we show that tuning the local electronic structures of metal anchor sites on g-C3N4 by doping B atoms (BCN) with relatively lower electronegativity allows achieving zero-valence Pd SACs with reinforced metal-support orbital hybridizations for high stability and upshifted Pd 4d orbitals for high activity in H2 activation. The precise synthesis of Pd SACs on BCN supports with varied B contents substantiated the theoretical prediction. A zero-valence Pd1/BCN SAC was achieved on a BCN support with a relatively low B content. It exhibited much higher stability in a H2 reducing environment, and more strikingly, a hydrogenation activity, approximately 10 and 34 times greater than those high-valence Pd1/g-C3N4 and Pd1/BCN with a high B content, respectively.

Selective hydrogenation of furfural to furfuryl alcohol over copper-cobalt bimetallic catalyst

Cu-based catalysts have been widely studied as selectively hydrogenated furfural. However, due to the weak hydrogenation activity of the mono-metal copper-based catalyst, the interaction with furfural is usually weak, and the accessibility of the active site is severely limited. A micro-doping strategy was proposed in this study to solve these problems. Trace amounts of cobalt metal are doped into copper using equal volume impregnation. Compared with the Cu/MgO catalyst, the bimetallic CuCo/MgO-0.04 catalyst changes metal particles' size and valence and regulates the catalyst surface's electronic environment. Electron transfer occurs between Co and Cu, and many active sites are generated for adsorption and activation of CO double bonds, and hydrogenation reactions occur with adjacent H protons to improve the selectivity of furfuryl alcohol. CuCo/MgO-0.04 catalyst has excellent catalytic performance of 100 % furfural conversion and 99.4 % furfural alcohol selectivity. Combined with experimental data, kinetic studies, and theoretical calculations, it was confirmed that the d-band center shifted up in the catalyst doped with trace metal cobalt, which optimized the adsorption energy and configuration of furfural and reduced the reaction barrier more effectively. This study provides a strategy to support the partial doping of highly dispersed Cu nanoparticles with a small amount of Co metal. It achieves excellent catalytic properties and chemical selectivity in selective hydrogenation reactions.

Rational Design and Precise Synthesis of Single-Atom Alloy Catalysts for the Selective Hydrogenation of Nitroarenes.

Single-atom alloys (SAAs) have gained increasing prominence in the field of selective hydrogenation reactions due to their uniform distribution of active sites and the unique host-guest metal interactions. Herein, 15 SAAs are constructed to comprehensively elucidate the relationship between host-guest metal interaction and catalytic performance in the selective hydrogenation of 4-nitrostyrene (4-NS) by density functional theory (DFT) calculations. The results demonstrate that the SAAs with strong host-guest metal interactions exhibit a preference for N─O bond cleavage, and the reaction energy barrier of the hydrogenation process is primarily influenced by the host metal. Among them, Ir1Ni SAA stands out as the prime catalyst candidate, showcasing exceptional activity and selectivity. Furthermore, the Ir1Ni SAA is subsequently prepared through precise synthesis techniques and evaluated in the selective hydrogenation of 4-NS to 4-aminostyrene (4-AS). As anticipated, the Ir1Ni SAA demonstrates extraordinary catalytic performance (yield>96%). In situ FT-IR experiments and DFT calculations further confirmed that the unique host-guest metal interaction at the Ir-Ni interface site of Ir1Ni SAA endows it with excellent 4-NS selective hydrogenation ability. This work provides valuable insights into enhancing the performance of SAAs catalysts in selective hydrogenation reactions by modulating the host-guest metal interactions.

Water-promoted selective hydrogenation of cinnamaldehyde over hydrotalcite-derived Co catalysts

Non-noble metal-catalyzed selective CO hydrogenation of α,β-unsaturated aldehydes to corresponding alcohols is chemically atom economic and practically feasible. This work reports hydrotalcite-derived Co-based catalysts for catalyzing aqueous phase selective hydrogenation reaction of cinnamaldehyde to cinnamyl alcohol. The structure characterizations demonstrate the phase transition from hydrotalcite to co-existed CoOx and metallic Co0 in the optimal Co2Al-H2-400 catalyst. It exhibits superior catalytic activity and selectivity relative to other as-obtained Co catalysts, because of the synergy effect of Co2+ sites to promote the adsorptive activation of CO group and small-size Co0 sites to facilitate the activating dissociation of hydrogen. Furthermore, the catalytic role of water has also been explored. Adopting water as pure solvent and partially adding water into organic solvent can both effectively enhance the activity and selectivity. Such reaction environment may induce creation of more intermolecular hydrogen bonds for promoting the hydrogen transfer and thus boosting the hydrogenation reaction.

Strategies to improve hydrogen activation on gold catalysts.

Catalytic reactions involving molecular hydrogen are at the heart of many transformations in the chemical industry. Classically, hydrogenations are carried out on Pd, Pt, Ru or Ni catalysts. However, the use of supported Au catalysts has garnered attention in recent years owing to their exceptional selectivity in hydrogenation reactions. This is despite the limited understanding of the physicochemical aspects of hydrogen activation and reaction on Au surfaces. A rational design of new improved catalysts relies on making better use of the hydrogenating properties of Au. This Review analyses the strategies utilized to improve hydrogen-Au interactions, from addressing the importance of the Au particle size to exploring alternative mechanisms for H2 dissociation on Au cations and Au-ligand interfaces. These insights hold the potential to drive future applications of Au catalysis.

Liquid organic hydrogen carriers: Process design and economic analysis for manufacturing N‐ethylcarbazole

AbstractThis paper revisits the economics of manufacturing N‐ethylcarbazole (NEC), a strong candidate for large‐scale liquid organic hydrogen carrier (LOHC) supply chains, because of its high H2 storage capacity (6 wt%), selective hydrogenation and dehydrogenation reactions, and favorable reaction enthalpy and reaction temperatures compared to other LOHC systems. Two different process routes for producing NEC from industrial chemicals are selected out of 10 possible options: one using aniline and the other using cyclohexanone and nitrobenzene as feedstock. The required capital and operational costs are estimated to determine a NEC break‐even cost for a capacity of 225 ktpa. NEC break‐even costs of $3.0 and $2.6 per kg LOHC are found for the routes. This is significantly less than the $40/kg cost that has generally been reported in literature for NEC, thus improving the economic viability of using NEC as LOHC. The total fixed capital costs are estimated to be $200 MM and $250 MM. Furthermore, the prices of the feedstock show the largest influence (76% and 72%) on the final NEC break‐even costs. The overall LOHC price contribution to the levelized H2 cost is estimated to be $0.77–$0.90 per kg H2 for a 60‐day roundtrip and $0.09–$0.10 per kg H2 for a 7‐day roundtrip. It is important to note that both routes rely heavily on laboratory scale data and the corresponding assumptions that stem from this limitation. Therefore, this research can serve as a guide to future experimental studies into validating the key assumptions made for this analysis.

Constructing fully exposed Pt atomically dispersed catalysts for enhanced multifunctional selective hydrogenation reactions

Constructing highly efficient and low-cost catalysts is essential for the selective hydrogenation reaction. Herein, we developed fully exposed Pt atomically dispersed catalysts (PtAD/C-Al2O3) by a simple carbon modified strategy. Importantly, the co-existence of Pt-O1C2 single atoms and Pt nanoclusters in the PtAD/C-Al2O3 system could exhibit excellent catalytic activity in the selective hydrogenation of quinoline and p-nitrophenol. Notably, the quinoline conversion and the corresponding selectivity of 1,2,3,4-tetrahydroquinoline is 99.6 % and 99.3 %, respectively. Meanwhile, the turnover frequency of PtAD/C-Al2O3 (1081 h−1) is 3.8 and 5.7 times higher than that of Pt single-atom catalysts (PtSA/C-Al2O3) and Pt nanoparticles (PtNPs/C-Al2O3), respectively, during quinoline hydrogenation. Besides, the rate constant of PtAD/C-Al2O3 could reach 192.5 min-1mgPt-1 for p-nitrophenol hydrogenation, which is much better than most of the reported catalysts. Mechanism studies revealed the synergistic effect between Pt-O1C2 single atoms and Pt nanoclusters acts as the main role in enhancing the hydrogenation activity. Specifically, Pt single atoms sites mainly adsorb and activate quinoline molecules, while Pt nanoclusters boost the dissociation of H2 molecules to H atoms. This work paves an origin carbon modified method to construct Pt atomically dispersed catalysts for efficient multifunctional hydrogenation.

Linkage-Editing Pseudo-Glycans: A Reductive α-Fluorovinyl-C-Glycosylation Strategy to Create Glycan Analogs with Altered Biological Activities.

The acetal (O-glycoside) bonds of glycans and glycoconjugates are chemically and biologically vulnerable, and therefore C-glycosides are of interest as more stable analogs. We hypothesized that, if the O-glycoside linkage plays a vital role in glycan function, the biological activities of C-glycoside analogs would vary depending on their substituents. Based on this idea, we adopted a "linkage-editing strategy" for the creation of glycan analogs (pseudo-glycans). We designed three types of pseudo-glycans with CH2 and CHF linkages, which resemble the O-glycoside linkage in terms of bond lengths, angles, and bulkiness, and synthesized them efficiently by means of fluorovinyl C-glycosylation and selective hydrogenation reactions. Application of this strategy to isomaltose (IM), an inducer of amylase expression, and α-GalCer, which activates iNKT cells, resulted in the discovery of CH2-IM, which shows increased amylase production ability, and CHF-α-GalCer, which shows activity opposite that of native α-GalCer, serving as an antagonist of iNKT cells.

The effect of MgO in Pd/Al2O3–MgO catalyst on a selective hydrogenation reaction

In this work, we modified the electronic structure of Pd by coating with MgO on the surface of Al2O3. Through in-depth research, we revealed the mechanism of MgO modification on the dispersion and stability of Pd active centers.

Mass transport effects in gas-phase selective hydrogenation of 1,3-butadiene over supported Pd

The performance of selective hydrogenation reactions is affected by mass transfer limitations, induced by higher local metal loading and larger catalyst grain size.

The role of surface chemistry in the synthesis of supported CuPd bimetallic/intermetallic catalysts for selective hydrogenation reactions

Understanding and controlling the structure of supported bimetallic/intermetallic catalysts are crucial for many heterogeneous catalytic reactions. However, commonly used synthesis techniques such as coimpregnation and coadsorption often yield nonuniform alloying and phase segregation, largely owing to the lack of interactions between different metal precursors. Here we show that by adopting sequential adsorption of complex metal cations and anions with the assistance of a proper ligand, the interaction between different metal precursors is enhanced, thus resulting in uniformly alloyed intermetallic catalysts. The supported CuPd intermetallic catalyst exhibits greatly improved selectivity towards monoolefins in the semihydrogenation of acetylene and butadiene compared to those random CuPd alloys synthesized via coimpregnation and coadsorption methods.

Carbon-Based Electrode Materials for Electrocatalytic Transformations

Industrial processes for the synthesis of chemicals and fuels utilise selective hydrogenation reactions. The need for high temperatures and high pressure of H2 makes these reactions energy intensive and only viable on a large scale, requiring expensive transport of materials. Electrocatalytic hydrogenation (ECH) could potentially bypass these limitations, running at ambient conditions and generating the adsorbed hydrogen in-situ. The interest in new electrocatalyst materials increased in recent years, as ECH offers a synthetic route for fuels and value-added chemicals with a reduced carbon footprint. The development of new low-cost catalyst materials will be paramount for the integration of ECH into economic activities.In this work we focus on heteroatom-modified carbon based electrode materials for the ECH. Carbon materials possess a list of beneficial properties for electrochemical applications: they are widely available, environmentally benign, stable at cathodic potentials and can be tailored towards specific applications. One way of tailoring is to dope the carbon with heteroatoms like nitrogen.Nitrogen-doped carbon thin films have been synthesised using sputter deposition followed by an annealing process, to control graphitisation and nitrogen distribution of the carbon material. These model electrodes were investigated by themselves and as supports for thin nanoparticle films of MoS2 in the ECH and the hydrogen evolution reaction (HER), as the Volmer step of the HER is needed in the ECH. This allowed us to understand the influence of nitrogen moieties on reduction rates in the absence of morphological effects. The results suggest possible strategies for developing electrocatalysts for the ECH based on functional carbons.[1] Orella, M.J.; Román-Leshkov, Y.; Brushett, F.R., Emerging opportunities for electrochemical processing to enable sustainable chemical manufacturing. Current Opinion in Chemical Engineering 2018, 20, 159–167.[2] Behan, J. A.; Stamatin, S. N.; Hoque, M. K.; Ciapetti, G.; Zen, F.; Esteban-Tejeda, L.; Colavita, P. E., Combined Optoelectronic and Electrochemical Study of Nitrogenated Carbon Electrodes. The Journal of Physical Chemistry C 2017, 121 (12), 6596-6604.[3] Nolan, H.; Schröder, C.; Brunet-Cabré, M.; Pota, F.; McEvoy, N.; McKelvey, K.; Perova, T. S.; Colavita, P. E., MoS2/carbon heterostructured catalysts for the hydrogen evolution reaction: N-doping modulation of substrate effects in acid and alkaline electrolytes. Carbon 2023, 202, 70-80.

New core-shell catalyst for catalyzing hydrogenation of α-pinene to cis-pinane

Improving the selectivity of catalytic hydrogenation by designing new catalysts is an effective strategy for preparing cis-pinane. However, the stability of the reported catalyst is generally poor, and one of the main reasons is that metal active site is easy to drop. To address the issues, a new type of core–shell catalyst SiO2@Pd-Ni@mSiO2 is designed. The active metals can sandwich between the core and the shell, effectively preventing the dropping to enhance the related stability. The SiO2@Pd-Ni@mSiO2 shows outstanding stereoselectivity for the desired product, owing to its adsorption characteristics of shell pores, which can effectively promote α-pinene molecules directional adsorption, consequently enhancing the directional selective hydrogenation reaction of α-pinene with active metals and active hydrogen occurs in the interlayer. The conversion of α-pinene and the selectivity for cis-pinane are 99.4% and 93.3% under mild reaction conditions, respectively. Meanwhile, the catalyst SiO2@Pd-Ni@mSiO2 also has outstanding reusability. The preparation strategy of the new catalyst provides a new path for preparing efficient and stable catalysts for the hydrogenation of α-pinene.

Fabrication of stable and selective non‐noble metal catalysts for selective alkyne hydrogenation

AbstractModification of Ni/Al2O3 catalysts with Sn is appealing for tuning catalyst activity and selectivity for hydrogenation reactions. However, a strong interaction between the Al2O3 and Sn ions can lead to problems when a traditional impregnation strategy is employed. For example, tin aluminate complexes can form and uneven distribution of the metals can occur. In this work, a support coordination induction strategy is developed, in which the use of a rod‐shaped Al2O3 with a high number penta‐coordinated Al3+ surface species prepared from a rotating liquid film reactor was used. The unsaturated Al3+ coordination sites on this support induce the formation of a stable and uniform Ni‐Sn intermetallic phase without the appearance of either monometallic Ni or SnO2 particles. This uniform Ni‐Sn intermetallic phase was then shown to be responsible for enhanced activity, selectivity, and stability for alkyne hydrogenation relative to samples which lacked the same level of Ni‐Sn uniformity.

A general and robust Ni-based nanocatalyst for selective hydrogenation reactions at low temperature and pressure.

Catalytic hydrogenations are important and widely applied processes for the reduction of organic compounds both in academic laboratories and in industry. To perform these reactions in sustainable and practical manner, the development and applicability of non-noble metal-based heterogeneous catalysts is crucial. Here, we report highly active and air-stable nickel nanoparticles supported on mesoporous silica (MCM-41) as a general and selective hydrogenation catalyst. This catalytic system allows for the hydrogenation of carbonyl compounds, nitroarenes, N-heterocycles, and unsaturated carbon─carbon bonds in good to excellent selectivity under very mild conditions (room temperature to 80°C, 2 to 10 bar H2). Furthermore, the optimal nickel/meso-silicon dioxide catalyst is reusable (4 cycles) without loss of its catalytic activity.

Pd-doped Ni nanocatalyst with high Pd utilization for semi-hydrogenation of phenylacetylene at ambient conditions

Semi-hydrogenation of phenylacetylene to styrene is an essential process in the expanding polystyrene industry. Despite Pd-based catalysts have been widely used, challenges like styrene over-hydrogenation and high cost remain to be addressed. Herein, a Pd-doped Ni nanocatalyst (Pd0.1/Ni1/Al2O3) with excellent Pd utilization was successfully developed for semi-hydrogenation of phenylacetylene, delivering a high conversion of >99 % with 95 % selectivity to styrene at ambient temperature and pressure (25 °C, 1 atm H2). The boosted catalytic activity might be ascribed to the mesoporous Al2O3 with large surface area, and the enhanced selectivity is due to the reduced electron density and improved dispersion of Pd derived from Ni-Pd interaction. Furthermore, the catalyst exhibits excellent stability for enduring 6 cycles. This work provides an efficient and practical strategy to develop cost-effective, high-performance and recyclable catalysts for various selective hydrogenation reactions in fundamental and applied research.

Thiophene Modification of the Pt/SOD Catalyst to Enhance Catalytic Selectivity in Hydrogenation Reactions

Thiophene Modification of the Pt/SOD Catalyst to Enhance Catalytic Selectivity in Hydrogenation Reactions

Visible-Light-Driven Selective Hydrogenation of Nitrostyrene over Layered Ternary Sulfide Nanostructures.

Selective hydrogenation of nitrostyrenes is a great challenge due to the competitive activation of the nitro groups (─NO2 ) and carbon-carbon (C═C) double bonds. Photocatalysis has emerged as an alternative to thermocatalysis for the selective hydrogenation reaction, bypassing the precious metal costs and harsh conditions. Herein, two crystalline phases of layered ternary sulfide Cu2 WS4 , that is, body-centered tetragonal I-Cu2 WS4 nanosheets and primitive tetragonal P-Cu2 WS4 nanoflowers, are controlled synthesized by adjusting the capping agents. Remarkably, these nanostructures show visible-light-driven photocatalytic performance for selective hydrogenation of 3-nitrostyrene under mild conditions. In detail, the I-Cu2 WS4 nanosheets show excellent conversion of 3-nitrostyrene (99.9%) and high selectivity for 3-vinylaniline (98.7%) with the assistance of Na2 S as a hole scavenger. They also can achieve good hydrogenation selectivity to 3-ethylnitrobenzene (88.5%) with conversion as high as 96.3% by using N2 H4 as a proton source. Mechanism studies reveal that the photogenerated electrons and in situ generated protons from water participate in the former hydrogenation pathway, while the latter requires the photogenerated holes and in situ generated reactive oxygen species to activate the N2 H4 to form cis-N2 H2 for further reduction. The present work expands the rational synthesis of ternary sulfide nanostructures and their potential application for solar-energy-driven organic transformations.