Semihydrogenation Of Alkynes Research Articles

Efficient catalysis of acetylene semi-hydrogenation through synergistic action of supported ionic liquid-nickel catalyst

In the semi-hydrogenation of acetylene, nickel-based catalysts offer a promising alternative to precious metal palladium catalysts. Despite the positive hydrogenation activity of nickel-based catalysts, there is still room for improvement in terms of their selectivity and stability. In this study, a simple incipient wetness impregnation method was employed to prepare Ni(OAC)2-IL/Al2O3 catalyst and its performance in the selective hydrogenation of acetylene was investigated. It was found that under the conditions of 170 °C and a space velocity of 600 h−1, the 3 % Ni(OAC)2-IL/Al2O3 catalyst achieved a 95.3 % acetylene conversion with an 85.6 % ethylene selectivity. Furthermore, the catalyst exhibited outstanding stability over a 100 hour test. TEM, XPS and C2H4-TPD experiments showed that the Ni species were encapsulated in the ionic liquids (ILs), and the interaction between the metal ions, nickel, and the ILs ensured a high dispersion and stability of the actives on the carriers, and the electronic effect between the ionic nickel and the ionic liquids increased the electron cloud density of the Ni, which improved the catalyst selectivity, which is the main reason for its excellent catalytic performance.

Fine tuning the dynamic PdCx formation for enhanced acetylene semi-hydrogenation: The role of gas environment and ZnO addition

Palladium carbide (PdCx) has been extensively reported as active phase in acetylene semi-hydrogenation that can be dynamically formed during reaction. However, fine tuning of dynamic PdCx formation towards enhanced acetylene semi-hydrogenation is of great challenge and the dynamic insights remain elusive. In this paper, the state-of-the-art in situ characterizations have been adopted to elucidate the dynamic PdCx formation for acetylene semi-hydrogenation. The role of hydrogen atmosphere and ZnO addition in tuning the carburization process were clearly identified by in situ spectroscopies. The hydrogen in the gas environment assisted the carbon infiltration via PdHx hydrides, while the addition of ZnO suppress the carburization by the surface Zn alloy. As a result, the carbon content in PdCx can be precisely modulated by altering the hydrogen atmosphere and ZnO additives, and exhibits a linear correlation with the activity of acetylene semi-hydrogenation. The carbon insertion enriched the electron state of Pd sites in PdCx that favors the activation of hydrogen for acetylene semi-hydrogenation. This work thus provides a new route for the design of Pd catalyst for high-performance acetylene semi-hydrogenation by fine tuning the reaction environment and the degree of carburization during dynamic PdCx formation.

Bimetallic [Ge-Rh] complex catalyzed alkyne semihydrogenation: Theoretical investigations on the germanium promoted mechanism and selectivity

Transitional metal catalyzed alkynes functionalization is a very important method to obtain the organic intermediates. In this work, the mechanism of PhCCPh hydrogenation catalyzed by [Ge-Rh] bimetallic catalyst has been studied by means of density functional theory. The whole reaction consists of two cycles, cis-semihydrogenation of alkyne to give Z-alkene and trans-isomerization to get E-alkene. The rate-determining step is the hydrogen complexation in cis-semihydrogenation. Because the isomerization from Z-alkene to E-alkene is easy, while the reverse transformation is difficult, E-alkene is main product of alkyne semihydrogenation. The semihydrogenation would be facilitated by replacing the terphenyl ligands in the [Ge-Rh] bimetallic catalyst with the polar N-heterocyclic ligands. The addition of H2 is crucial in controlling the chemoselectivity of the reaction. The Ge acts as the Lewis acid to reduce the electron density on Rh, making Rh center becomes more electropositive than that in the monorhodium catalysts, thus increasing the selectivity of the [Ge-Rh] bimetallic catalyst. Our work elucidates the detailed mechanism of PhCCPh semihydrogenation catalyzed by the [Ge-Rh] catalyst and provides explanations for the experimental results.

Efficient electrocatalytic alkyne Semi-Hydrogenation and deuteration using Pd/PANI catalysts supported on nickel foam

In this study, we synthesized Pd/PANI catalysts anchored on nickel foam (NF) via a single-step CV electrodeposition process. The resulting Pd0.3/PANI-NF materials exhibited outstanding selectivity and activity for electrocatalytic alkyne semi-hydrogenation and deuteration under ambient conditions. Characterization of Pd/PANI and control experiment revealed that the combination of PANI and Pd had a synergistic effect on the catalytic performance of Pd/PANI-NF for alkyne semi-hydrogenation. Optimized conditions in H-cells allowed efficient conversion of various terminal and internal alkynes into their corresponding alkenes with remarkable yields up to 92 % and a Faradaic efficiency of 88 %, even at low Pd loading (0.4 mol%). The Pd0.3/PANI-NF showed sustained catalytic activity for gram-scale alkene synthesis through five usage cycles under continuous flow conditions, marked by a high TOF (up to 230 h−1) and combined TONs of 2151, establishing its practical viability for electrocatalytic hydrogenation.

Boron-Nitrogen-Embedded Polycyclic Aromatic Hydrocarbon-Based Controllable Hierarchical Self-Assemblies through Synergistic Cation-π and C-H···π Interactions for Bifunctional Photo- and Electro-Catalysis.

Boron-Nitrogen-embedded polycyclic aromatic hydrocarbons (BN-PAHs) as novel π-conjugated systems have attracted immense attention owing to their superior optoelectronic properties. However, constructing long-range ordered supramolecular assemblies based on BN-PAHs remains conspicuously scarce, primarily attributed to the constraints arising from coordinating multiple noncovalent interactions and the intrinsic characteristics of BN-PAHs, which hinder precise control over delicate self-assembly processes. Herein, we achieve the successful formation of BN-PAH-based controllable hierarchical assemblies through synergistically leveraged cation-π and C-H···π interactions. By carefully adjusting the solvent conditions in two progressive assembly hierarchies, the one-dimensional (1D) supramolecular assemblies with "rigid yet flexible" assembled units are first formed by cation-π interactions, and then they can be gradually fused into two-dimensional (2D) structures under specific C-H···π interactions, thus realizing the precise control of the transformation process from BN-PAH-based 1D primary structures to 2D higher-order assemblies. The resulting 2D-BNSA, characterized by enhanced electrical conductivity and ordered 2D layered structure, provides anchoring and dispersion sites for loading two appropriate nanocatalysts, thus facilitating the efficient photocatalytic CO2 reduction (with a remarkable CH4 evolution rate of 938.7 μmol g-1 h-1) and electrocatalytic acetylene semihydrogenation (reaching a Faradaic efficiency for ethylene up to 98.5%).

Highly Selective Acetylene-to-Ethylene Electroreduction Over Cd-Decorated Cu Catalyst with Efficiently Inhibited Carbon-Carbon Coupling.

Electrochemical acetylene reduction (EAR) employing Cu catalysts represents an environmentally friendly and cost-effective method for ethylene production and purification. However, Cu-based catalysts encounter product selectivity issues stemming from carbon-carbon coupling and other side reactions. We explored the use of secondary metals to modify Cu-based catalysts and identified Cd decoration as particular effective. Cd decoration demonstrated a high ethylene Faradaic efficiency (FE) of 98.38 % with well-inhibited carbon-carbon coupling reactions (0.06 % for butadiene FE at -0.5 V versus reversible hydrogen electrode) in a 5 vol % acetylene gas feed. Notably, ethylene selectivity of 99.99 % was achieved in the crude ethylene feed during prolonged stability tests. Theoretical calculations revealed that Cd metal accelerates the water dissociation on neighboring Cu surfaces allowing more H* to participate in the acetylene semi-hydrogenation, while increasing the energy barrier for carbon-carbon coupling, thereby contributing to a high ethylene semi-hydrogenation efficiency and significant inhibition of carbon-carbon coupling. This study provides a paradigm for a deeper understanding of secondary metals in regulating the product selectivity of EAR electrocatalysts.

Hydrophobic Surface Modification of Cu-Based Catalysts for Enhanced Semihydrogenation of Acetylene in Excess Ethylene

Hydrophobic Surface Modification of Cu-Based Catalysts for Enhanced Semihydrogenation of Acetylene in Excess Ethylene

A MOF-supported Pd1–Au1 dimer catalyses the semihydrogenation reaction of acetylene in ethylene with a nearly barrierless activation energy

The removal of acetylene from ethylene streams is key in industry for manufacturing polyethylene. Here we show that a well-defined Pd1–Au1 dimer, anchored to the walls of a metal–organic framework (MOF), catalyses the selective semihydrogenation of acetylene to ethylene with ≥99.99% conversion (≤1 ppm of acetylene) and >90% selectivity in extremely rich ethylene streams (1% acetylene, 89% ethylene, 10% H2, simulated industrial front-end reaction conditions). The reaction proceeds with an apparent activation energy of ∼1 kcal mol–1, working even at 35 °C, and with operational windows (>100 °C) and weight hourly space velocities (66,000mlgcat−1h−1\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$66{,}000\\,{\\mathrm{ml}}\\,{\\mathrm{g}}^{-1}_{\\mathrm{cat}}\\,{\\mathrm{h}}^{-1}$$\\end{document}) within industrial specifications. A combined experimental and computational mechanistic study shows the cooperativity between both atoms, and between atoms and support, to enable the barrierless semihydrogenation of acetylene.

Membrane-Free Selective Semi-Hydrogenation of Alkynes Over an In Situ Formed Copper Nanoparticle Electrode.

Selective semi-hydrogenation of alkynes is a significant reaction for preparing functionalized alkenes. Electrochemical semi-hydrogenation presents a sustainable alternative to the traditional thermal process. In this research, affordable copper acetylacetonate is employed as a catalyst precursor for the electrocatalytic hydrogenation of alkynes, using MeOH as the hydrogen source in an undivided cell. Good to excellent yields for both aromatic and aliphatic internal/terminal alkynes are obtained under constant current conditions. Notably, up to 99% Z selectivity is achieved for various internal alkynes. Mechanistic investigations revealed the formation of copper nanoparticles (NPs) at the cathode during electrolysis, acting as the catalyst for the selective semireduction of alkynes. The copper NPs deposited cathode demonstrated reusable for further hydrogenation.

Spectroscopic visualization of reversible hydrogen spillover between palladium and metal–organic frameworks toward catalytic semihydrogenation

Hydrogen spillover widely occurs in a variety of hydrogen-involved chemical and physical processes. Recently, metal–organic frameworks have been extensively explored for their integration with noble metals toward various hydrogen-related applications, however, the hydrogen spillover in metal/MOF composite structures remains largely elusive given the challenges of collecting direct evidence due to system complexity. Here we show an elaborate strategy of modular signal amplification to decouple the behavior of hydrogen spillover in each functional regime, enabling spectroscopic visualization for interfacial dynamic processes. Remarkably, we successfully depict a full picture for dynamic replenishment of surface hydrogen atoms under interfacial hydrogen spillover by quick-scanning extended X-ray absorption fine structure, in situ surface-enhanced Raman spectroscopy and ab initio molecular dynamics calculation. With interfacial hydrogen spillover, Pd/ZIF-8 catalyst shows unique alkyne semihydrogenation activity and selectivity for alkynes molecules. The methodology demonstrated in this study also provides a basis for further exploration of interfacial species migration.

Efficient Alkyne Semihydrogenation Catalysis Enabled by Synergistic Chemical and Thermal Modifications of a PdIn MOF.

Recently, there has been a growing interest in using MOF templating to synthesize heterogeneous catalysts based on metal nanoparticles on carbonaceous supports. Unlike the common approach of direct pyrolysis of PdIn-MOFs at high temperatures, this work proposes a reductive chemical treatment under mild conditions before pyrolysis (resulting in PdIn-QT). The resulting material (PdIn-QT) underwent comprehensive characterization via state-of-the-art aberration-corrected electron microscopy, N2 physisorption, X-ray absorption spectroscopy, Raman, X-ray photoelectron spectroscopy, and X-ray diffraction. These analyses have proven the existence of PdIn bimetallic nanoparticles supported on N-doped carbon. In situ DRIFT spectroscopy reveals the advantageous role of indium (In) in regulating Pd activity in alkyne semihydrogenation. Notably, incorporating a soft nucleation step before pyrolysis enhances surface area, porosity, and nitrogen content compared to direct MOF pyrolysis. The optimized material exhibits outstanding catalytic performance with 96% phenylacetylene conversion and 96% selectivity to phenylethylene in the fifth cycle under mild conditions (5 mmol phenylacetylene, 7 mg cat, 5 mL EtOH, R.T., 1 H2 bar).

Semihydrogenation of Alkynes with a Pd-Carbide Composite Encapsulated in an MFI Zeolite

Semihydrogenation of Alkynes with a Pd-Carbide Composite Encapsulated in an MFI Zeolite

Selective hydrogenation of acetylene over Pd/In2O3@SiO2: The effect of the catalyst reduction temperature

Tuning the hydrogenation activity of Pd is an effective method to achieve selective hydrogenation of acetylene. The previous study shows that Pd has a strong interaction with In2O3, causing a significant change in the electronic structure of the palladium catalyst. Herein, Pd/In2O3@SiO2 was prepared by a deposition-precipitation method for selective hydrogenation of acetylene. After the reduction by flowing hydrogen, Pd-In intermetallic compounds can be formed. The concentration of the formed intermetallic compounds is closely associated with the reduction temperature. The Pd-In intermetallic compounds suppress the hydrogen activation ability of Pd and significantly weaken the adsorption of ethylene. Especially, a weak adsorption of di-σ-bonded ethylene is observed, which facilitates the desorption of ethylene and promotes the ethylene selectivity in the semi-hydrogenation of acetylene. The experimental study confirms that there exists an optimum reduction temperature (250 °C) for the formation of the Pd-In intermetallic compounds, with which ∼ 80 % ethylene selectivity and 100 % acetylene conversion have been achieved at 140 °C.

Unlocking enhanced selectivity of Pd/Al2O3 in semihydrogenation of alkynes by in situ ligand‐reduction strategy

AbstractThe partial hydrogenation of alkynes into alkenes constitutes a pivotal chemical transformation in the synthesis of fine chemicals, pharmaceuticals, and polymers. Nevertheless, the extant industrial catalyst falls short of achieving a felicitous equilibrium between its catalytic potency and selectivity. Herein, triphenylphosphine (PPh3) modified Pd/Al2O3 catalysts are fabricated through a “one‐pot” process, which achieve highly selective hydrogenation of alkynes at room temperature. PPh3 plays a dual role—as a reducing agent and a ligand. Kinetic and characterization studies reveal PPh3 alters H2 activation from homolytic to heterolytic cleavage, which facilitate the formation of alkene. Moreover, PPh3 can also optimize the reaction microenvironment, achieving the reduced self‐poisoning of alkyne and promoted desorption of alkene. In the realm of alkyne hydrogenation, our philosophy encompasses a global optimization of active sites, ligand systems, and reaction microenvironmental. This method steers the course of catalyst development for other reactions beyond the field of alkyne hydrogenation.

In situ cell for grazing-incidence x-ray diffraction on thin films in thermal catalysis.

A cell for synchrotron-based grazing-incidence x-ray diffraction at ambient pressures and moderate temperatures in a controlled gas atmosphere is presented. The cell is suited for the in situ study of thin film samples under catalytically relevant conditions. To some extent, in addition to diffraction, the cell can be simultaneously applied for x-ray reflectometry and fluorescence studies. Different domes enclosing the sample have been studied and selected to ensure minimum contribution to the diffraction patterns. The applicability of the cell is demonstrated using synchrotron radiation by monitoring structural changes of a 3nm Pd thin film upon interaction with gas-phase hydrogen and during acetylene semihydrogenation at 150 °C. The cell allows investigation of very thin films under catalytically relevant conditions.

Tandem Electrocatalytic Alkyne Semihydrogenation over Bicomponent Catalysts through Hydrogen Spillover

AbstractElectrocatalytic alkyne semihydrogenation under mild conditions is a more attractive approach for alkene production than industrial routes but suffers from either low production efficiency or high energy consumption. Here, we describe a tandem catalytic concept that overcomes these challenges. Component (i), which can trap hydrogen effectively, is partnered with component (ii), which can readily release hydrogen for hydrogenation, to enable efficient generation of active hydrogen on component (i) at low overpotentials and timely (i)‐to‐(ii) hydrogen spillover and facile desorptive hydrogenation on component (ii). We examine this concept over bicomponent palladium‐copper catalysts for the production of representative 2‐methyl‐3‐butene‐2‐ol (MBE) from 2‐methyl‐3‐butyne‐2‐ol (MBY) and achieve a record high MBE production rate of 1.44 mmol h−1 cm−2 and a Faraday efficiency of ~88.8 % at a low energy consumption of 1.26 kWh kgMBE−1. With these catalysts, we further achieve 60 h continuous production of MBE with record high profit space.

Tandem Electrocatalytic Alkyne Semihydrogenation over Bicomponent Catalysts through Hydrogen Spillover.

Electrocatalytic alkyne semihydrogenation under mild conditions is a more attractive approach for alkene production than industrial routes but suffers from either low production efficiency or high energy consumption. Here, we describe a tandem catalytic concept that overcomes these challenges. Component (i), which can trap hydrogen effectively, is partnered with component (ii), which can readily release hydrogen for hydrogenation, to enable efficient generation of active hydrogen on component (i) at low overpotentials and timely (i)-to-(ii) hydrogen spillover and facile desorptive hydrogenation on component (ii). We examine this concept over bicomponent palladium-copper catalysts for the production of representative 2-methyl-3-butene-2-ol (MBE) from 2-methyl-3-butyne-2-ol (MBY) and achieve a record high MBE production rate of 1.44 mmol h-1 cm-2 and a Faraday efficiency of ~88.8 % at a low energy consumption of 1.26 kWh kgMBE -1. With these catalysts, we further achieve 60 h continuous production of MBE with record high profit space.

Hydrogen Spillover Accelerates Electrocatalytic Semi-hydrogenation of Acetylene in Membrane Electrode Assembly Reactor.

Electrocatalytic acetylene semi-hydrogenation (EASH) offers a promising and environmentally friendly pathway for the production of C2H4, a widely used petrochemical feedstock. While the economic feasibility of this route has been demonstrated in three-electrode systems, its viability in practical device remains unverified. In this study, we designed a highly efficient electrocatalyst based on a PdCu alloy system utilizing the hydrogen spillover mechanism. The catalyst achieved an operational current density of 600 mA cm-2 in a zero-gap membrane electrode assembly (MEA) reactor, with the C2H4 selectivity exceeding 85%. This data confirms the economic feasibility of EASH in real-world applications. Furthermore, through in situ Raman spectroscopy and theoretical calculations, we elucidated the catalytic mechanism involving interfacial hydrogen spillover. Our findings underscore the economic viability and potential of EASH as a greener and scalable approach for C2H4 production, thus advancing the field of electrocatalysis in sustainable chemical synthesis.

Mediating trade-off between activity and selectivity in alkynes semi-hydrogenation via a hydrophilic polar layer

As a crucial industrial process for the production of bulk and fine chemicals, semi-hydrogenation of alkynes faces the trade-off between activity and selectivity due to undesirable over-hydrogenation. By breaking the energy linear scaling relationships, we report an efficient additive-free WO3-based single-atom Pd catalytic system with a vertical size effect of hydrogen spillover. Hydrogen spillover induced hydrophilic polar layer (HPL) with limited thickness on WO3-based support exhibits unconventional size effect to Pd site, in which over-hydrogenation is greatly suppressed on Pd1 site due to the polar repulsive interaction between HPL and nonpolar C=C bonds, whereas this is invalid for Pd nanoparticles with higher altitudes. By further enhancing the HPL through Mo doping, activated Pd1/MoWO3 achieves recorded performance of 98.4% selectivity and 10200 h−1 activity for semi-hydrogenation of 2-methyl-3-butyn-2-ol, 26-fold increase in activity of Lindlar catalyst. This observed vertical size effect of hydrogen spillover offers broad potential in catalytic performance regulation.

Atomic Design of Alkyne Semihydrogenation Catalysts via Active Learning.

Alkyne hydrogenation on palladium-based catalysts modified with silver is currently used in industry to eliminate trace amounts of alkynes in alkenes produced from steam cracking and alkane dehydrogenation processes. Intensive efforts have been devoted to designing an alternative catalyst for improvement, especially in terms of selectivity and catalyst cost, which is still far away from that as expected. Here, we describe an atomic design of a high-performance Ni-based intermetallic catalyst aided by active machine learning combined with density functional theory calculations. The engineered NiIn catalyst exhibits >97% selectivity to ethylene and propylene at the full conversion of acetylene and propyne at mild temperature, outperforming the reported Ni-based catalysts and even noble Pd-based ones. Detailed mechanistic studies using theoretical calculations and advanced characterizations elucidate that the atomic-level defined coordination environment of Ni sites and well-designed hybridization of Ni 3d with In 5p orbital determine the semihydrogenation pathway.