Selective Hydrogenation Of Acetylene Research Articles

Au Nanoparticles Supported on Hydrotalcite-Based MMgAlOx (M=Cu, Ni, and Co) Composite: Influence of Dopants on the Catalytic Activity for Semi-Hydrogenation of C2H2

Semi-hydrogenation of acetylene to ethylene over metal oxide-supported Au nanoparticles is an interesting topic. Here, a hydrotalcite-based MMgAlOx (M=Cu, Ni, and Co) composite oxide was exploited by introducing different Cu, Ni, and Co dopants with unique properties, and then used as support to obtain Au/MMgAlOx catalysts via a modified deposition–precipitation method. XRD, BET, ICP-OES, TEM, Raman, XPS, and TPD were employed to investigate their physic-chemical properties and catalytic performances for the semi-hydrogenation of acetylene to ethylene. Generally, the catalytic activity of the Cu-modified Au/CuMgAlOx catalyst was higher than that of the other modified catalysts. The TOR for Au/CuMgAlOx was 0.0598 h−1, which was 30 times higher than that of Au/MgAl2O4. The SEM and XRD results showed no significant difference in structure or morphology after introducing the dopants. These dopants had an unfavorable effect on the Au particle size, as confirmed by the TEM studies. Accordingly, the effects on catalytic performance of the M dopant of the obtained Au/MMgAlOx catalyst were improved. Results of Raman, NH3-TPD, and CO2-TPD confirmed that the Au/CuMgAlOx catalyst had more basic sites, which is beneficial for less coking on the catalyst surface after the reaction. XPS analysis showed that gold nanoparticles exhibited a partially oxidized state at the edges and surfaces of CuMgAlOx. Besides an increased proportion of basic sites on Au/CuMgAlOx catalysts, the charge transfer from nanogold to the Cu-doped matrix support probably played a positive role in the selective hydrogenation of acetylene. The stability and deactivation of Au/CuMgAlOx catalysts were also discussed and a possible reaction mechanism was proposed.

Lattice Strain and Mott-Schottky Effect of the Charge-Asymmetry Pd1Fe Single-Atom Alloy Catalyst for Semi-Hydrogenation of Alkynes with High Efficiency.

The ideal interface design between the metal and substrate is crucial in determining the overall performance of the alkyne semihydrogenation reaction. Single-atom alloys (SAAs) with isolated dispersed active centers are ideal media for the study of reaction effects. Herein, a charge-asymmetry "armor" SAA (named Pd1Fe SAA@PC), which consists of a Pd1Fe alloy core and a semiconducting P-doped C (PC) shell, is rationally designed as an ideal catalyst for the selective hydrogenation of alkynes with high efficiency. Multiple spectroscopic analyses and density functional theory calculations have demonstrated that Pd1Fe SAA@PC is dual-regulated by lattice tensile and Schottky effects, which govern the selectivity and activity of hydrogenation, respectively. (1) The PC shell layer applied an external traction force causing a 1.2% tensile strain inside the Pd1Fe alloy to increase the reaction selectivity. (2) P doping into the C-shell layer realized a transition from a p-type semiconductor to an n-type semiconductor, thereby forming a unique Schottky junction for advancing alkyne semihydrogenation activity. The dual regulation of lattice strain and the Schottky effect ensures the excellent performance of Pd1Fe SAA@PC in the semihydrogenation reaction of phenylethylene, achieving a conversion rate of 99.9% and a selectivity of 98.9% at 4 min. These well-defined interface modulation strategies offer a practical approach for the rational design and performance optimization of semihydrogenation catalysts.

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.

Unraveling the Role of Single-Atom Catalysts Immobilized onto Metal–Organic Frameworks in Selective Acetylene Hydrogenation: An Implementation of the Active Site Isolation Strategy

Unraveling the Role of Single-Atom Catalysts Immobilized onto Metal–Organic Frameworks in Selective Acetylene Hydrogenation: An Implementation of the Active Site Isolation Strategy

Al2O3-Flower Anchoring Pd Catalyst for Acetylene Selective Hydrogenation: A Compartmentalizing Strategy Promotes Metal Dispersion and Maintains Stability

Al2O3-Flower Anchoring Pd Catalyst for Acetylene Selective Hydrogenation: A Compartmentalizing Strategy Promotes Metal Dispersion and Maintains Stability

Deprotonated 2-thiolimidazole serves as a metal-free electrocatalyst for selective acetylene hydrogenation.

Metal-free catalysts offer a desirable alternative to traditional metal-based electrocatalysts. However, metal-free catalysts, featuring defined active sites, rarely show activities as promising as metal-based materials. Here we report 2-thiolimidazole as an efficient metal-free catalyst for selective electrocatalytic hydrogenation of acetylene into ethylene. Under alkaline conditions, the sulfhydryl and imino groups of 2-thiolimidazole are spontaneously deprotonated into dianions. Deprotonation thus enriches the negative charges of pyridinic N sites in 2-thiolimidazole to enhance the adsorption of electrophilic acetylene through the σ-configuration. Ethylene partial current densities show a volcano relationship with the negative charges of the pyridinic N sites in various imidazole derivatives. Consequently, the deprotonated 2-thiolimidazole exhibits an ethylene partial current density and faradaic efficiency competitive with metal-based catalysts like Cu and Pd. This work highlights the tunability and promising potential of metal-free molecules in electrocatalysis.

Effect of preparation conditions of nanocrystalline Pd/MgO catalysts on their performance in selective hydrogenation of acetylene

In the present work, an alkoxide sol-gel method was applied to prepare Pd/MgO catalysts. The sol-gel procedure was followed by supercritical drying (aerogels) or conventional drying (xerogels) in a furnace. These materials were compared with the impregnated samples. The Pd loading was 1 wt% in all the cases. The as-prepared catalysts were characterized by a set of physicochemical methods. Both the type of the Pd precursor and the preparation route were found to affect the porous structure of the materials as well as the dispersion of the palladium particles and their localization over the MgO support. Both the xerogel and incipient wetness impregnation methods lead to a narrower pore size distribution in comparison to the aerogel technique. The most dispersed particles with an average size of ∼ 2.0–2.2 nm were observed for the samples prepared by xerogel and impregnation methods. In the case of aerogel-prepared samples, metallic palladium particles possess bimodal distribution with average diameters of 4.3 and 8.4 nm. The best catalytic performance in acetylene hydrogenation to ethylene (50 % acetylene conversion at 37 °C with selectivity ∼60 %) was observed for the Pd/MgO catalyst prepared via the aerogel route using [Pd(NH3)4](NO3)2. Compared to other samples, this material is characterized by relatively weak metal-support interactions and the availability of active sites for reactants, which ensures the kinetic mode of the hydrogenation reaction (Ea = 74.9 kJ/mol).

Functionalized ionic liquid coatings in the Pd-catalyzed selective hydrogenation of acetylene in ethylene-rich feeds

This study explores the tuning of a Pd/Al2O3 hydrogenation catalyst for the selective removal of trace acetylene from ethylene-rich feeds by coating the catalyst with non-functionalized and functionalized ionic liquids (denoted as SCILL and Advanced SCILL materials, respectively). These materials were tested in an automated continuous hydrogenation rig converting 3300 ppm of acetylene in excess ethylene, a gas mixture mimicking a technical front-end steam cracker feed composition. While the sulfonic-acid-functionalized IL coating resulted in a highly active but very unselective catalyst converting mainly ethylene to ethane, an Advanced SCILL catalyst prepared from a nitrile-functionalized IL reduced the acetylene concentration down to less than 1 ppm, while leaving over 99% of the ethylene untouched. We also examined the potential transformations of the IL layer under reaction conditions by means of 1H NMR. Except for a ketone-functionalized IL, which was inherently labile, all tested ILs primarily underwent C2-ethylation or remained unaltered. Our findings highlight the great potential of functionalized ILs in modifying heterogeneous hydrogenation catalysts.

Insights into reaction–diffusion behaviors of acetylene selective hydrogenation on pellet catalysts

AbstractIn this work, a particle‐resolved computational fluid dynamics model of the acetylene hydrogenation process is developed to investigate the effects of catalyst particle structures on the reaction–diffusion behaviors aiming to improve selectivity toward target ethylene. The effects of packing structures on mass and heat transfer are explored by employing particles with varying shapes, wall thicknesses, and external diameters. The simulation results reveal that decreasing diffusion paths and elevating reactor bed temperature will enhance ethylene selectivity, and cylinder and Raschig ring packing structures exhibit the lowest and highest ethylene selectivity of 35.6% and 48.9% at 70% of acetylene conversion, respectively. Reducing wall thicknesses of Raschig ring particles facilitates the diffusion of generated ethylene from the interior zone of catalysts but concurrently inhibits the conversion of acetylene to ethylene. The Raschig ring catalyst particle with 1.9 mm of wall thickness and 3.5 mm of external diameter is finally revealed to exhibit the highest ethylene selectivity.

Experimental study and modeling of the liquid phase hydrogenation of acetylene

Selective hydrogenation of acetylene is an important process for both ethylene purification and ethylene production from acetylene in the industry. Herein, we proposed liquid phase acetylene hydrogenation for high feed concentrations of C2H2 (8 %) and CO (20 %), which is used to produce ethylene as a subsequent process of partial oxidation of natural gas. The experiments were carried out in a stirred tank reactor using N-methylpyrrolidone (NMP) as solvent and PdAg/SiO2 as catalyst. The liquid phase process obtained a much higher selectivity to ethylene (92 %) with only 8 % selectivity to green oil (GO) and C4, compared to 71 % ethylene selectivity in gas phase hydrogenation. Furthermore, in the liquid phase ethylene selectivity increased with increasing acetylene conversion, especially in the conversion range of 80–100 %. We developed a model incorporating reaction kinetics, mass transfer and reactor model to predict the acetylene conversion and ethylene selectivity in liquid phase hydrogenation. The calculation results indicated that hydrogenation in the liquid phase operated at a lower acetylene concentration and a higher H2/C2H2 ratio, especially under high acetylene conversions. This explains why the liquid phase hydrogenation of acetylene has a much higher selectivity to ethylene than the gas phase process.

Metal-organic framework/polyurea composite microreactors prepared in oil-in-oil emulsions

A new technique was developed to create composite microcapsules consisting of metal–organic framework (MOF) and polyurea. This method employs oil-in-oil (O/O) emulsion as a template for forming these microcapsules. It involves emulsifying a polar solvent containing MOF reagents within a nonpolar phase containing a suitable surfactant and an isocyanate monomer. Subsequently, the addition of the amine monomer initiates two simultaneous processes: the formation of MOF crystals in the core of polar droplets and the interfacial polymerization to create polyurea shell. Optimization of the method involved adjusting various parameters affecting the composite microcapsules' structure and morphology. These parameters include the surfactant’s type and concentration, the emulsion phases’ type and concentration, and quantity of the MOF component.This method was applied to create palladium-based MOF/polyurea microreactors by encapsulating sodium tetrachloropalladate and then reducing the palladium salt with hydrogen to generate reactive palladium species. The produced catalysts were utilized in the selective hydrogenation of terminal alkynes. It was observed that the selectivity of the catalyst is influenced by the quantity of encapsulated MOF, the amount of encapsulated palladium, and the solvent type used for the reaction.

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.

Design of efficient supported Pd-Co catalysts for selective hydrogenation of acetylene

The research is devoted to the study of active component formation in the novel Pd-Co catalysts supported on carbon material Sibunit. It was shown that 0.5 %Pd–0.5 %Co/C samples exhibit high ethylene yield in the acetylene hydrogenation process due to the presence of fcc PdxCo(1-x) particles. According to in situ XRD-TPR analysis, solid solution formation begins during the reduction of samples in H2 at T ≥ 500 °C. Using the EXAFS, XRD and EDX it was established that H2-treatment at 500 °C leads to the formation of ∼Pd0.6Co0.4 particles and an increase in the reduction temperature to 600 and 700 °C is accompanied by the enrichment of the Pd-Co-phase with cobalt to ∼Pd0.5Co0.5 and ∼Pd0.45Co0.55 compositions, respectively. The ethylene yield on Pd-Co/C catalysts reduced at 500, 600 and 700 °C is 56, 66 and 68 %, respectively, which significantly exceeds the ethylene quantity obtained on monometallic Pd/C samples (∼52 %). It is assumed that the excellent selectivity of Pd-Co/C samples treated in H2 at 600 and 700 °C is due to an increase in the amount of palladium atoms surrounded by cobalt and a change in the palladium electronic state (XPS).

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.

Kinetic Analysis of the Non‐Monotonic Response of Ethene Hydrogenation Rates to Ceria Surface Reduction

The precise effect of oxide understoichiometry on bulk oxide catalytic properties continues to remain a subject of intense investigation. Of specific interest in this regard is the role of oxygen vacancies present on bulk ceria catalysts that have recently been reported to represent a more cost‐effective alternative to the more toxic and expensive catalysts used industrially for the selective hydrogenation of acetylene to ethylene. Contrasting claims as to the effect of surface reduction on hydrogenation rates exist in the open literature, with vacancy formation attributed, in separate studies, either a favorable or a deleterious role in effecting hydrogenation turnovers. We report here the non‐monotonic behavior of ethene hydrogenation rates that subsumes both of these trends as a function of degree of surface reduction over a sufficiently large range of pre‐reduction temperatures. Steady state transient kinetic and isotopic exchange data combined with in‐situ titration experiments suggest that this non‐monotonic trend can be attributed not to a change in either the kinetic relevance of specific elementary steps or the hydrogenation mechanism, but rather to site requirements that stipulate the need for two distinct, proximal sites.

Selective Hydrogenation of Alkyne by Atomically Precise Pd6 Nanocluster Catalysts: Accurate Construction of the Coplanar and Specific Active Sites

Selective Hydrogenation of Alkyne by Atomically Precise Pd₆ Nanocluster Catalysts: Accurate Construction of the Coplanar and Specific Active Sites

Partial carbon encapsulation synthesis of separated Ni-Ag catalyst for efficient selective hydrogenation of acetylene: Synergizing hydrogen spillover and steric hindrance

The selective hydrogenation of acetylene is a vital process to for the purification of crude ethylene in petroleum industry. Achieving high activity and selectivity simultaneously over Ni-based catalysts is still challenging. Herein, a partial encapsulation strategy is proposed by fabricating carbon-encapsulated Ag nanoparticles and un-encapsulated Ni nanoparticles on Al2O3 surface (Ni-Ag@C/Al2O3) toward the enhanced selectivity without loss of activity. In particular, the Ni-Ag@C/Al2O3 exhibits higher ethylene selectivity of 81% at the complete acetylene conversion along with excellent stability for 30-h, in sharp with the Ni/Al2O3 (6%) and Ni-Ag/Al2O3 (54%) catalyst. The enhanced selectivity is attributed to the promotion of hydrogen spillover by the carbon species on Al2O3 surface and the inhibition of oligomer formation by a steric hindrance formed by the carbon layer on the Ag surface. This study provides a new structural design avenue of bifunctional bimetallic catalyst for selective hydrogenation reaction.

Fabrication of a PdCu@SiO2@Cu core-shell-satellite catalyst for the selective hydrogenation of acetylene.

Pd25Cu75@SiO2 core-shell and PdCu@SiO2@Cu core-shell-satellite architectures were fabricated by silica-coating of Pd25Cu75 colloids in a reverse microemulsion. Hydrolysis of tetraethylorthosilicate in the reverse microemulsion containing hydrazine and ammonia yielded a core-shell structure, while the use of ammonia only, instead of a mixture of hydrazine and ammonia, formed a core-shell-satellite structure. The ammonia-leached copper species migrated onto the developing silica shell and formed smaller Cu clusters. Air-calcination at 673 K followed by H2-reduction at 773 K of the as-synthesized samples removed the organic surfactants and generated the permeable porous silica shells. The core-shell catalyst consisted of a metal core (8.5 nm) and a silica shell (7.8 nm), while the core-shell-satellite catalyst was composed by a metal core (7.0 nm), a silica shell (8.0 nm), and satellite Cu clusters (1.4 nm) on the silica shell. When used to catalyze the selective hydrogenation of acetylene to ethylene, the core-shell-satellite catalyst showed substantially enhanced activity and stability because of the synergetic catalysis between the metal core and the surrounding Cu clusters.

Same size, same support, same spectator? Selective acetylene hydrogenation on supported Pd nanoparticles.

The selective hydrogenation of acetylene catalyzed by Pd nanoparticles is industrially used to increase the purity of ethylene. Despite the implementation of Pd based catalysts on an industrial scale, little is known about metal-support interactions on a fundamental level due to the complexity of these systems. In this study, the influence of metal-support interactions between Pd nanoparticles and two electronically modified a-SiO2 thin films on acetylene hydrogenation is investigated under ultra-high vacuum (UHV) conditions. The hydrogenation is performed under isothermal reaction conditions using a pulsed molecular beam reactive scattering (pMBRS) technique. Besides the activity and selectivity of clean Pd particles also the impact of dehydrogenated species intentionally introduced a priori is elucidated, whereas the active phase of the catalyst is additionally characterized by CO infrared reflection-absorption spectroscopy (IRRAS) and post-mortem temperature-programmed reaction (TPR). Metal-support interactions are found to influence the catalytic properties of Pd particles by charge-transfer, where positive charging leads to increased activity for acetylene hydrogenation. However, the increased activity is accompanied by formation of undesired byproducts. The active sites for acetylene and ethylene hydrogenation are shown to be different as previously proposed by the A and E model. The availability of the two different active sites on the Pd nanoparticles is determined by dehydrogenated species, whose nature and stability can be tuned by metal-support interactions. Based on these findings an electronic model is proposed how selectivity for acetylene hydrogenation can be steered solely by metal-support interactions leading to blocking of unselective sites in situ.

Thermally induced intermetallic Rh1Zn1 nanoparticles with high phase-purity for highly selective hydrogenation of acetylene.

Ordered M1Zn1 intermetallic phases with structurally isolated atom sites offer unique electronic and geometric structures for catalytic applications, but lack reliable industrial synthesis methods that avoid forming a disordered alloy with ill-defined composition. We developed a facile strategy for preparing well-defined M1Zn1 intermetallic nanoparticle (i-NP) catalysts from physical mixtures of monometallic M/SiO2 (M = Rh, Pd, Pt) and ZnO. The Rh1Zn1 i-NPs with structurally isolated Rh atom sites had a high intrinsic selectivity to ethylene (91%) with extremely low C4 and oligomer formation, outperforming the reported intermetallic and alloy catalysts in acetylene semihydrogenation. Further studies revealed that the M1Zn1 phases were formed in situ in a reducing atmosphere at 400 °C by a Zn atom emitting-trapping-ordering (Zn-ETO) mechanism, which ensures the high phase-purity of i-NPs. This study provides a scalable and practical solution for further exploration of Zn-based intermetallic phases and a new strategy for designing Zn-containing catalysts.