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The selective hydrogenation of acetylene is of industrially indispensable in the production of polymer-grade ethylene. The design of non-precious metal catalysts with outstanding performance is of pivotal importance in order to replace the supported Pd–Ag catalysts. Our previous work showed that a copper carbide (CuxC)-containing catalyst exhibited high hydrogenation activity and selectivity under mild conditions. In the present work, Mg(OH)2 was used to modify the CuxC-containing catalyst in order to improve its catalytic performance. Mg(OH)2-modified CuxC-containing catalyst was prepared from a coprecipitate of Cu(OH)2 and Mg(OH)2, which was obtained by precipitation of Cu(NO3)2 and Mg(NO3)2 solution with dropwise addition of NaOH solution, by thermal treatment in C2H2/Ar (0.5%) at 120 ℃ followed by H2 reduction at 150 ℃. The introduction of Mg(OH)2 led to reduced CuxC crystalline size and to increased amount of CuxC crystallites. In addition, the basic nature of Mg(OH)2 is favorable to suppress the undesired oligomerization. The prepared catalyst showed excellent catalytic performance with complete acetylene conversion, low selectivity to unwanted ethane (24%), and high stability at 100 °C and atmospheric pressure in the presence of large excess ethylene in 100 h. [ABSTRACT FROM AUTHOR]

Objective In the sulfuric acid alkylation unit, the main causes and solutions to the deactivation of the hydrogenation catalyst were found by analyzing the running status of the selective hydrogenation reactor of 1,3-butadiene. Methods By analyzing the feedstock properties before and after catalyst deactivation, the effect of feedstock properties changes on the 1,3-butadiene removal rate was investigated. Results For the selective hydrogenation of the 1,3-butadiene catalyst, a high level of pH, caustic sodium and total sulfur contents in feedstock will inhibit the active centers of the catalyst. Conclusion The harmful impurities in feedstock were removed by optimizing operation. Additionally, the deactivated catalysts were re-activated by on-line treatment with pure hydrogen, the catalyst activity was significantly restored and maintained long-cycle running after re-starting up. [ABSTRACT FROM AUTHOR]

This work demonstrates that supported ruthenium phosphides (RuP2) are attractive catalysts for selective production of alditols by sugar hydrogenation. In our studies, carbon supported RuP2 with a ruthenium content of 5 wt.– % led to the highest activity in xylose hydrogenation and to nearly 100 % yield for xylitol. ICP‐OES and XRD measurements revealed the stability of this novel RuP2/C catalyst under typical hydrogenation conditions (50 barH2, 120 °C) in aqueous phase. Furthermore, STEM‐EDX illustrated the close proximity of ruthenium and phosphorous on the catalyst site and the formation of nanoparticles in the size of 2–4 nm. The catalyst system was successfully applied for the selective hydrogenation of further sugar substrates, including glucose, fructose, and disaccharides, such as cellobiose and sucrose. Here, the RuP2/C revealed its bifunctional acidic/metallic character, enabling in a tandem reaction the hydrolysis of disaccharides, directly followed by a selective hydrogenation to form sugar alcohols in high yield. [ABSTRACT FROM AUTHOR]

Catalyst preparation, reaction process conditions and kinetics of the selective hydrogenation of fatty acid methyl esters (FAME) over a noble metal catalyst were studied. Two catalysts were prepared by impregnation of γ-Al2O3 with Ru (1% mass content) as active metal and Sn and B as modifiers (2% mass content), and with different Sn/Ru ratios of 2 and 4. FAME derived from biomass, an environment friendly raw material, was used for the preparation of fatty alcohols by selective hydrogenolysis of the ester group to an alcohol group. The results were analyzed with a simple kinetic model using lumped pseudocomponents. When comparing the two catalysts it was found that the most effective catalyst for producing oleyl alcohol was the one with a Sn/Ru ratio of 2, RuSn2–B. The maximum production of alcohols and alkanes was achieved with this catalyst at 290 °C. At 270 °C a lower production of alkanes was obtained but with a similar yield of alcohols. Both reaction conditions and catalyst composition were found to be important factors influencing alcohol production. Two types of active sites were identified on the studied catalysts: the unmodified Ru0 metal for dissociating hydrogen and the modified metal, (Ru0–(SnOx)2, for adsorbing the C=C carbons. RuSn2–B seemingly exhibited an appropriate balance of these sites. The kinetic model included the reactions of esters, hydrogen, alcohols and deoxygenated hydrocarbons. These were studied with lumped variables with no distinction of individual specific molecules. In spite of this, the model provided a very good fit of the experimental data indicating that the reaction is rather insensitive to secondary features like carbon chain length or group positions. [ABSTRACT FROM AUTHOR]

A sample of a catalytic system based on nickel and a carbon-containing material, microcellulose, was obtained using a hydrothermal synthesis method. A catalytic study of the synthesized system in the process of selective hydrogenation of carbon monoxide and carbon dioxide was carried out with calculation of the apparent activation energy. The sample was demonstrated to be highly active in the selective hydrogenation reactions of carbon oxides. A 100% conversion of carbon monoxide and carbon dioxide and selectivity for methane of 90 and 80%, respectively, were obtained. [ABSTRACT FROM AUTHOR]

Metal‐Organic Frameworks (MOFs) represent a highly promising class of materials with diverse applications, particularly as catalytic materials. However, their synthesis typically yields powders available only at laboratory‐scale quantities, usually in the gram range or less. This study addresses the challenge of testing limited amounts of MOF catalysts for demanding applications, such as multiphase gas‐liquid‐solid reactions in flow, utilizing a packed‐bed microreactor. Specifically, we investigate the performance of a nanoparticle (NP) ‐immobilized Pd@UiO‐66 MOF catalyst in the selective semi‐hydrogenation of phenylacetylene to styrene, serving as a model reaction. Maintaining the Taylor flow regime upstream of the catalyst bed was crucial to ensure reproducible and reliable experimental results. We conducted 88 experiments at varying liquid flow rates, temperatures ranging from 15 to 45 °C, and relative pressures spanning 0.28 to 8 bar. Styrene selectivity within the range of 80–92.3 % was achieved at phenylacetylene conversions below 20 %. Notably, the optimal condition for styrene selectivity (70 %) was attained at 98.9 % phenylacetylene conversion under the lowest H2 pressure and highest temperature, demonstrating the significance of low H2 concentration for achieving optimal styrene selectivity. Remarkably, the catalyst exhibited stable activity and selectivity over a 20 h testing period, indicating its robust performance under prolonged reaction conditions. This study demonstrates the potential of the proposed catalyst testing system as a rapid and efficient approach for early‐stage exploration studies, particularly when limited quantities of catalyst, typically in the gram scale or less, are available. [ABSTRACT FROM AUTHOR]

Solvent effects add a new dimension for tuning the activity and selectivity of heterogeneous catalytic reactions, which is extensively employed in the hydrogenation of unsaturated compounds with multiple functional groups. In this concept, we briefly summarize recent developments on how the solvent effects affect the catalytic performance from the following aspects: 1) the polarity of the solvent can influence the interaction between the solvent and the reactant or intermediate; 2) the composition of mixed solvent can influence the reactivity of the reactant or intermediate; 3) solvent effect varies with the metal identity and support; 4) the solvent can induce surface modification of the supported catalysts. This summarization will provide insights into the rational development of efficient and selective heterogeneous hydrogenation catalytic system to realize the precise synthesis of desired chemicals. [ABSTRACT FROM AUTHOR]

While supported metal nanoparticles (NPs) have shown significant promise in heterogeneous catalysis, precise control over their interaction with the support, which profoundly impacts their catalytic performance, remains a significant challenge. In this study, Pt NPs are incorporated into thioether‐functionalized covalent organic frameworks (denoted COF‐Sx), enabling precise control over the size and electronic state of Pt NPs by adjusting the thioether density dangling on the COF pore walls. Notably, the resulting Pt@COF‐Sx demonstrate exceptional selectivity (> 99 %) in catalytic hydrogenation of p‐chloronitrobenzene to p‐chloroaniline, in sharp contrast to the poor selectivity of Pt NPs embedded in thioether‐free COFs. Furthermore, the conversion over Pt@COF‐Sx exhibits a volcano‐type curve as the thioether density increases, due to the corresponding change of accessible Pt sites. This work provides an effective approach to regulating the catalysis of metal NPs via their microenvironment modulation, with the aid of rational design and precise tailoring of support structure. [ABSTRACT FROM AUTHOR]

We successfully constructed an ultrathin Ti3C2Tx supported Pt nanocluster catalyst for highly selective and efficient hydrogenation of p-chloronitrobenzene (p-CNB) to p-chloroaniline (p-CAN) under mild conditions (30 °C, 0.1 MPa H2). The Pt/Ti3C2Tx catalyst displayed a very high conversion (>99%) and selectivity (>99%). In addition, a higher reaction rate (41 mol h–1 g–1) was obtained in comparison with the previously reported catalysts. The excellent catalytic activity of Pt/Ti3C2Tx was attributed to the strong metal–support interactions between Pt nanoclusters and the support, in which the electrons were transferred from Ti3C2Tx to Pt sites, affording a high electron density of Pt active sites. Moreover, the electrostatic repulsion between C–Cl moiety and Pt sites inhibited the dechlorination process. In addition, the Pt/Ti3C2Tx catalyst also exhibited excellent performance in substrate scope (reducible heterocyclics such as pyridine and phthalimide), stability (10th cycles, conversion >99% and selectivity 98%), and gram-scale reaction (99% yield, 1.89 g). This work will promote the research in constructing efficient and highly selective noble metal-based catalysts for hydrogenation of halogenated nitroarenes. [ABSTRACT FROM AUTHOR]

Mixed metal oxides with perovskite ABO3 or spinel AB2O4 structure can provide uniformly and highly dispersed metal oxides, which can be adopted as catalyst supports, as catalysts directly or as catalysts after reduction. When they are used as catalyst supports, the spatial isolation of A‐site ions with B‐site ions not only makes these ions highly dispersed, but also enhances the intimate contact with the active components supported on them, leading to electron transfer or synergistic effect to promote the catalytic ability. After reduction, highly dispersed A/B nanoparticles supported on BOx/AOx can be achieved for the relevant applications. Herein, recent developments in the liquid–phase selective hydrogenation of α,β‐unsaturated aldehydes, with metal oxides derived from perovskite or spinel as supports or catalyst precursors, were summarized. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

The selective hydrogenation of the biomass platform molecule furfural (FAL) to produce furfuryl alcohol (FA) is of great significance to alleviate the energy crisis. Cu-based catalysts are the most commonly used catalysts, and their catalytic performance can be optimized by changing the preparation method. This paper emphasized the effect of calcination atmosphere on the performance of a Cu/Al2O3 catalyst for the selective hydrogenation of FAL. The precursor of the Cu/Al2O3 catalyst prepared by the ammonia evaporation method was treated with different calcination atmospheres (N2 and air). On the basis of the combined results from the characterizations using in situ XRD, TEM, N2O titration, H2-TPR and XPS, the Cu/Al2O3 catalyst calcined in the N2 atmosphere was more favorable for the dispersion and reduction of Cu species and the reduction process could produce more Cu+ and Cu0 species, which facilitated the selective hydrogenation of FAL to FA. The experimental results showed that the N2 calcination atmosphere improved the FAL conversion and FA selectivity, and the FAL conversion was further increased after reduction. Cu/Al2O3-N2-R exhibited the outstanding performance, with a high yield of 99.9% of FA after 2 h at 120 °C and an H2 pressure of 1 MPa. This work provides a simple, efficient and economic method to improve the C=O hydrogenation performance of Cu-based catalysts. [ABSTRACT FROM AUTHOR]

Cu catalysts with different compositions and different Cu and promoter contents were prepared by precipitation‐gel method and studied for the selective hydrogenation of syngas or biomass‐based diethyl malonate (DEM) to valuable 1,3‐propanediol (1,3‐PDO). The Ga‐promoted 70Cu6Ga/SiO2 catalyst was found to exhibit the highest catalytic performance, achieving 100 % DEM conversion and 76.6 % 1,3‐PDO selectivity under reaction conditions of 160 °C and 8 MPa H2. The 70Cu6Ga/SiO2 bimetallic catalyst also presented obviously better stability than that of the monometallic 70Cu/SiO2 catalyst in a continuous flow reactor over 180 h time‐on stream. Characterization results showed that the incorporation of Ga increased the interaction between Cu and Ga species, hindered the full reduction of Cu2+ species, and thus increased the proportion of Cu+ and the number of Lewis acidic sites on the catalyst surface. The synergistic effect between Cu0 and Cu+ enhanced the adsorption and activation of ester carbonyl groups and their subsequent hydrogenation, eventually contributed to the outstanding performances of the CuGa/SiO2 bimetallic catalysts. [ABSTRACT FROM AUTHOR]

The selective hydrogenation has attracted increasing attention to chemists for the production of value‐added products in chemical industry. Over the past several decades, substantial effort has been devoted to the design of catalyst for the selective hydrogenation of light alkynes and α, β‐unsaturated aldehydes, two classic cases for selective hydrogenation in chemical industry. Despite the great progress, it remains great challenges to achieve the selective hydrogenation because the desired products are generally thermodynamically unfavored. Here, we summarize the recent advances on selective hydrogenation using noble metal nanocrystals, with an emphasis on the surface engineering of noble metal nanocrystals for the selective hydrogenation of light alkynes and α, β‐unsaturated aldehydes. We will highlight the strategies for surface engineering, the advanced techniques for characterizations, as well as mechanism studies. We hope this review will promote chemists to develop efficient and robust catalysts for selective hydrogenation. [ABSTRACT FROM AUTHOR]

Nanosized copper is an interesting alternative to noble metal‐based catalysts in gas phase selective hydrogenation, but little is known about its performance in liquid phase catalysis. We investigated the activity and selectivity of 2 and 7 nm Cu on SiO2 catalysts for the three‐phase partial hydrogenation of 2‐methyl‐3‐butyn‐2‐ol, a highly relevant reaction for fine chemical synthesis. Next to the desired 2‐methyl‐3‐buten‐2‐ol, also 2‐methyl‐2‐butanol was formed as a result of over‐hydrogenation. The 7 nm Cu nanoparticles were intrinsically 2.5 times more active than 2 nm Cu (in terms of turnover frequency), and they were also more selective. At 180 °C the selectivity was only 15 % at 50 % conversion, but lowering the reaction temperature to 160 and 140 °C led to 80 % and even ~100 % selectivity (at 50 % conversion). The unselective step was around two times faster than the selective one, hence the high selectivity is due the stronger adsorption of the reactant than of the desired product, which limits over‐hydrogenation. [ABSTRACT FROM AUTHOR]

The selective hydrogenation of α,β-unsaturated aldehydes using unsupported nanoporous platinum–iron–aluminum (PtFeAlNPore) as a heterogeneous catalyst was investigated in depth. A PtFeAlNPore trimetallic catalyst with a highly bicontinuous nanostructure was synthesized by a two-step chemical dealloying method. The catalyst exhibited a good yield with high selectivity for the hydrogenation of α,β-unsaturated aldehydes into allyl alcohols under mild reaction conditions. A series of characterizations revealed that a decrease in the Pt electronic density (exhibiting superior hydrogen-activation ability), a nanoporous structure (providing increased reaction active sites), Lewis acidity (promoting the adsorption and activation of the carbonyl group in α,β-unsaturated aldehydes), and intimate PtFe–Fe3O4 heterointerfaces (facilitating the selective hydrogenation of α,β-unsaturated aldehydes into allyl alcohols) led to the excellent catalytic performance. [ABSTRACT FROM AUTHOR]

The selective conversion of levulinic acid (LA) obtained from lignocellulosic biomass represents a crucial pathway for producing the key value‐added chemical compound γ‐valerolactone (GVL). Herein, we constructed a series of Pt‐based titanium‐silicalite‐1 (TS‐1) bifunctional catalysts modified with rare earth metal Ce through a simple spin‐coating impregnation method, and the catalytic performance was significantly improved compared to the unmodified Pt1.2/TS‐1. Pt0.7‐Ce0.5/TS‐1 exhibited the best aqueous‐phase catalytic activity (with a GVL yield of 99.4%). The introduction of CeOx can reduce the particle size of Pt nanoparticles and promote the formation of electron‐rich Pt species while delivering abundant oxygen vacancies (OV) for the catalysts. The characterization and testing results highlight the synergistic effect of OV and electron‐rich Pt sites on the oriented adsorption and selective hydrogenation of LA, providing new insights into constructing more efficient noble metal‐based zeolite catalysts for biomass conversion. [ABSTRACT FROM AUTHOR]

A series of inexpensive electroplating sludge-derived magnetic copper-containing catalysts were developed for the selective hydrogenation of biomass-based furfural (FFR) into furfuryl alcohol (FA) and 2-methylfuran (MF). The specific structural characteristics of as-prepared magnetic copper-containing samples were clearly identified through various techniques, including XRD, XPS, N2 adsorption–desorption, NH3-TPD, SEM and so on. The characterizations revealed that the hydrogen pre-activated magnetic catalysts supplied metallic Cu species, medium acidity and porosity for the catalytic upgrading of FFR in hydrogen atmosphere. As for FFR-to-FA as well as FFR-to-MF transformations, the magnetic copper-containing catalyst with calcination temperature of 800 °C exhibited excellent performance towards the formation of FA and MF, wherein desirable FA yield of 98.5 mol% and MF yield of 71.3 mol% were achieved at reaction temperatures of 160 °C and 240 °C, respectively. The reuse experiments indicated that the recycled catalysts still maintained excellent activity and stability even after four-time recycling. The present study thus highlights a new approach for the resource utilization of electroplating sludge, which also supplies low-cost and efficient catalytic materials for the selective upgrading of various biomass-derived platform molecules. [ABSTRACT FROM AUTHOR]

The hydrogenation of nitrogen-containing heterocyclic compounds and their derivatives to obtain the corresponding valuable products is of great practical significance. In this work, a highly active and selective Ni/NC hydrogenation catalyst was developed by utilizing melamine-modified high-specific surface carbon (NC) as a carrier for nickel nanoparticles (NPs), which showed excellent catalytic activity in the selective hydrogenation of methyl nicotinate, where the Ni/NC catalyst was first used for this reaction (selective hydrogenation of methyl nicotinate). It was found that nitrogen species on the surface of NC significantly promoted the decomposition of the nickel precursor and the high dispersion of nano-Ni, which effectively affected the agglomeration of the nickel metal, resulting in the distribution of nickel metal with a smaller particle size. In the selective hydrogenation of methyl nicotinate under mild conditions (130 °C, 3 h), the conversion of methyl nicotinate reached the optimal catalytic activity over the catalyst of 10% Ni/NC-1-M-I-300, in which the conversion of methyl nicotinate was 98.5% and the selectivity of methylpiperidine-3-carboxylate was 97.2%. After 5 recycles, the catalyst maintained a conversion of 95.4% for methyl nicotinate. The Ni/NC catalyst has good substrate adaptability in the selective hydrogenation of N-heterocyclic carboxylate, O-heterocyclic carboxylate, and aromatic carboxylate. [ABSTRACT FROM AUTHOR]

A new hybrid catalyst consisting of cobalt nanoparticles immobilized onto cellulose was developed. The cellulosic matrix is derived from date palm biomass waste, which was oxidized by sodium periodate to yield dialdehyde and was further derivatized by grafting orthoaminophenol as a metal ion complexing agent. The new hybrid catalyst was characterized by FT-IR, solid-state NMR, XRD, SEM, TEM, ICP, and XPS. The catalytic potential of the nanocatalyst was then evaluated in the catalytic hydrogenation of 4-nitrophenol to 4-aminophenol under mild experimental conditions in aqueous medium in the presence of NaBH4 at room temperature. The reaction achieved complete conversion within a short period of 7 min. The rate constant was calculated to be K = 8.7 × 10−3 s−1. The catalyst was recycled for eight cycles. Furthermore, we explored the application of the same catalyst for the hydrogenation of cinnamaldehyde using dihydrogen under different reaction conditions. The results obtained were highly promising, exhibiting both high conversion and excellent selectivity in cinnamyl alcohol. [ABSTRACT FROM AUTHOR]

Cost‐effective non‐noble metal‐based catalysts for selective hydrogenation with excellent activity, selectivity, and durability are still the holy grail. Herein, an oxygen‐doped carbon (OC) chainmail encapsulated dilute Cu–Ni alloy is developed by simple pyrolysis of Cu/Ni‐metal–organic framework. The CuNi0.05@OC catalyst displays superior performance for atmospheric pressure transfer hydrogenation of p‐chloronitrobenzene and p‐nitrophenol, and for hydrogenation of furfural, all in water and with exceptional durability. Comprehensive characterizations confirm the close interactions between the diluted Ni sites, the base Cu, and optimized three‐layered graphene chainmail. Theoretical calculations demonstrate that the properly tuned lattice strain and Schottky junction can adjust electron density to facilitate specific adsorption on the active centers, thus enhancing the catalytic activity and selectivity, while the OC shell also offers robust protection. This work provides a simple and environmentally friendly strategy for developing practical heterogeneous catalysts that bring the synergistic effect into play between dilute alloy and functional carbon wrapping. [ABSTRACT FROM AUTHOR]

Changes in the composition of immobilized [M(COD)Cl]2–NH2–C3H6–SiO2 and [M(COD)Cl]2–P(Ph)2–C2H4–SiO2 (where M = Ir, Rh) catalysts in the gas-phase selective hydrogenation of propylene, propyne, and 1,3-butadiene with parahydrogen (p-H2) have been studied by the XPS method. It has been proposed that the M/Cl atomic ratio should be used as an indicator of the structural stability of the anchored complex both at the sample synthesis stage and in the reaction. Based on comparison of XPS data and results of catalytic tests using parahydrogen-induced nuclear polarization, it has been shown that the stability of the anchored {[M(COD)Cl]2–Linker–SiO2} complex during hydrogen activation is a key factor in the catalytic behavior of the systems. The stability of the complex is affected not only by the chosen metal and linker, but also by the nature of the substrate subjected to hydrogenation. [ABSTRACT FROM AUTHOR]

The catalytic conversion of naturally rich and renewable biomass into high-value chemicals is of great significance for pursuing a sustainable future and a green economy. The preparation of pentanediol from furfuryl alcohol is an important means of high-value conversion of biomass. The Pt-based catalyst supported on MgO was applied to the selective hydrogenation of biomass furfuryl alcohol to prepare pentanediol. By adjusting parameters such as catalyst loading, reduction temperature, reaction temperature, and pressure, a highly active catalyst was designed and the optimal catalytic hydrogenation conditions were determined. The hydrogenation experiment results showed that the selectivity of the 2Pt/MgO-200 catalyst for 1,2-pentanediol and 1,5-pentanediol reached 59.4% and 15.2%, respectively, under 160 °C and 1 MPa hydrogen pressure. The catalyst was characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectrometer (XPS), CO2-temperature programmed desorption (CO2-TPD), and other methods. The characterization results indicate that the reduction temperature has a significant impact on the metal Pt, and an appropriate reduction temperature is beneficial for the hydrogenation performance of the catalyst. In addition, the basic sites on the carrier are also another important factor affecting the activity of the catalyst. In addition, stability tests were conducted on the catalyst, and the reasons for catalyst deactivation were studied using methods such as thermogravimetric analysis (TGA) and Fourier transform infrared spectroscopy (FT-IR). The results showed that the activity of the catalyst decreased after five cycles, and the deactivation was due to the hydrolysis of the carrier, the increase in metal particle size, and the surface adsorption of organic matter. [ABSTRACT FROM AUTHOR]

Mesoporous silica gel doped with dysprosium, lanthanum and modified with silver (Dy-Ag/MPS, La-Ag/MPS) was obtained by the template method. The physicochemical characteristics of the obtained catalyst were studied by scanning electron microscopy, X-ray fluorescence and X-ray diffraction analysis, inductively coupled plasma mass spectrometry and temperature-programmed reduction. In addition, the possibility of using obtained materials as an efficient and selective catalysts in the hydrogenation of a 1-heptyne/1-heptene mixture (with 30% of alkyne content) in a temperature range of 140–160 °C and a hydrogen pressure of 3 atm was studied. It was found that after 15 min from the start of the hydrogenation reaction at 140 °C on the La-Ag/MPS catalyst, total conversion of 1-heptyne was observed and selectivity for 1-heptene was 84%. Moreover, it was shown that on a Dy-Ag/MPS at 150 °C 1-heptyne conversion was 84%, the selectivity for alkene was 79%. Furthermore, with an increase in temperature to 160 °C, the conversion of 1-heptyne reaches 95%, the selectivity for 1-heptene—84%. [ABSTRACT FROM AUTHOR]

Rationally designed polymers can function as supports or promoters for metal catalysts, imparting distinct catalytic properties in selective hydrogenation. With strongly metal–ligating functional groups, mobile polymer chains can spontaneously decorate the metal catalyst surfaces under mild conditions, forming stable metal–polymer interfaces. We have termed this phenomenon 'dynamic metal–polymer interaction (DMPI),' which can be roughly considered as an organic version of the strong metal–support interaction (SMSI) concept. The polymer chains that dynamically interact with the metal surface can control the adsorption of reactants and products through competitive adsorption, significantly improving selectivity and catalyst stability. One of the remarkable advantages of using polymers as catalytic materials is that their molecular structures, such as molecular weight, crystallinity, and chemical functionality, can be tailored using rich organic chemistry. This, in turn, allows us to precisely tune the metal–polymer interactions and catalytic properties. In this Concept, we will discuss how metal–polymer interfaces can be designed and utilized for selective hydrogenation, with a particular emphasis on the industrially relevant acetylene partial hydrogenation reaction. [ABSTRACT FROM AUTHOR]

Upgrading of polyethylene terephthalate (PET) waste into valuable oxygenated molecules is a fascinating process, yet it remains challenging. Herein, we developed a two‐step strategy involving methanolysis of PET to dimethyl terephthalate (DMT), followed by hydrogenation of DMT to produce the high‐valued chemical methyl p‐methyl benzoate (MMB) using a fixed‐bed reactor and a Cu/ZrO2 catalyst. Interestingly, we discovered the phase structure of ZrO2 significantly regulates the selectivity of products. Cu supported on monoclinic ZrO2 (5 %Cu/m‐ZrO2) exhibits an exceptional selectivity of 86 % for conversion of DMT to MMB, while Cu supported on tetragonal ZrO2 (5 %Cu/t‐ZrO2) predominantly produces p‐xylene (PX) with selectivity of 75 %. The superior selectivity of MMB over Cu/m‐ZrO2 can be attributed to the weaker acid sites present on m‐ZrO2 compared to t‐ZrO2. This weak acidity of m‐ZrO2 leads to a moderate adsorption capability of MMB, and facilitating its desorption. Furthermore, DFT calculations reveal Cu/m‐ZrO2 catalyst shows a higher effective energy barrier for cleavage of second C−O bond compared to Cu/t‐ZrO2 catalyst; this distinction ensures the high selectivity of MMB. This catalyst not only presents an approach for upgrading of PET waste into fine chemicals but also offers a strategy for controlling the primary product in a multistep hydrogenation reaction. [ABSTRACT FROM AUTHOR]

A Ru-decorated porous melamine polymer is found to be an active catalyst upon selective hydrogenation of aqueous 5-hydroxymethylfurfural to 2,5-bis-(hydroxymethyl)furan (yield > 99%) under mild (20 bar H2, 30–90 °C), base/additive free conditions. Owing to its porous structure and unique surface chemistry presenting abundant weakly basic N-sites (amine and triazine), the polymeric catalyst could outperform various benchmark Ru catalysts (viz. Ru/AC, Ru/SBA-15, Ru/Nb2O5, Ru/NbOPO4, Ru/NC, and Ru/g-C3N4) in terms of activity and desired product selectivity. The catalytic material was also found to be reusable and maintained good performance during multiple recycles under kinetic regime in batch mode. Furthermore, the polymeric catalyst also showed good performance for selective HMF hydrogenation under intensified conditions in a fixed-bed reactor achieving constant BHMF yield during 20-h steady-state operation under relatively mild conditions (70 °C, 20 bar, WHSV 0.2 h−1). [ABSTRACT FROM AUTHOR]

Modification 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. [ABSTRACT FROM AUTHOR]

Zinc-included intermetallic compound catalysts of RhZn, PtZn, and PdZn with a molar ration of Zn/metal = 1/1, which are generally prepared using a hydrogen reduction approach, are known to show excellent catalytic performance in some selective hydrogenations of organic compounds. In this study, in order to reduce the incorporated mounts of the expensive noble metals, we attempted to prepare zinc-rich intermetallic compounds via a CaH2-assisted molten salt synthesis method with a stronger reduction capacity than the common hydrogen reduction method. X-ray diffraction results indicated the formation of RhZn13 and Pt3Zn10 in the samples prepared by the reduction of ZnO-supported metal precursors. In a hydrogenation reaction of p-nitrophenol to p-aminophenol, the ZnO-supported RhZn13 and Pt3Zn10 catalysts showed a higher selectivity than the RhZn/ZnO and PtZn/ZnO catalysts with the almost similar conversions. Thus, it was demonstrated that the zinc-rich intermetallic compounds of RhZn13 and Pt3Zn10 could be superior selective hydrogenation catalysts compared to the conventional intermetallic compound catalysts of RhZn and PtZn. [ABSTRACT FROM AUTHOR]

Achieving atomic‐level control over local environment of metal oxide to boost catalytic activity is challenging yet significant for heterogeneous hydrogenations. Herein, we propose anchoring atomically dispersed Pt species onto indium oxide using a precisely conditioned atomic layer deposition (ALD) technology to manipulate the local electronic properties of In2O3 toward enhanced hydrogenation of 2,6‐diamino‐3,5‐dinitropyridine (DADNP) to 2,3,5,6‐tetraaminopyridine (TAP). Experimental and theoretical studies unravel that the isolated Pt atoms localize the electron density surrounding them and thus activate the adjacent frustrated Lewis pair for hydrogen activation. In addition, the adsorption of DADNP is enhanced by such regulation, while that of TAP is suppressed on the Pt1‐In2O3 catalyst. The as‐synthesized Pt1‐In2O3 catalyst thus exhibits 91.7% of TAP selectivity at 100% conversion of DADNP, demonstrating remarkably improved catalytic performances as compared with the In2O3 catalyst for DADNP hydrogenation. [ABSTRACT FROM AUTHOR]

Aqueous phase selective hydrogenation of cinnamaldehyde (CALD), as a representative α,β-unsaturated aldehyde, into cinnamyl alcohol (CALA) has been investigated over monometallic Ru and bimetallic RuCo catalysts on pristine h-BN support. Using water as the solvent, the optimal 0.5%Ru-1.1%Co/h-BN catalyst exhibits 510 h−1 specific reaction rate and 78.9 % CALA selectivity as well as good recycling stability at 100 °C. Based on the structure characterizations of catalysts, metal nanoparticles consisting of metallic Ru0 and partially oxidized Ruδ+ sites are uniformly dispersed on h-BN thin sheets. In comparison to monometallic catalysts, additive Co metals in bimetallic RuCo/h-BN catalysts play significant geometric and electronic modification roles on Ru active sites depending on the Ru/Co ratio, and therefore remarkably enhances the preferential activation of CALD C O bond and selectivity of CALA product as well as accelerates the catalytic reaction. Furthermore, the hydrogen dissociative activation ability of various Ru and RuCo catalysts was evaluated, while the superior catalytic performance in water than other commonly used solvents was also clarified and discussed. [Display omitted] • h-BN-supported bimetallic RuCo catalyst exhibits high activity and selectivity in cinnamaldehyde C O hydrogenation. • Co additive metal plays geometric and electronic modification roles on Ru active site. • Partially oxidized Ruδ+ and decorated CoO x serve as Lewis acid sites for enhancing C O activation. • Hydrogen dissociative activation ability can be promoted by bimetallic RuCo catalyst. • Water as the solvent plays multiple positive roles of polarizing C O bond and hydrogen transfer. [ABSTRACT FROM AUTHOR]

Biomass derivatives are renewable and oxygen-rich organic feedstocks, which can be partially or completely hydrogenated to various value-added molecules with a prerequisite of expensive and tailored metal catalysts. Here, waste chicken eggshell was valorized by calcination and glycerol treatment to prepare basicity- and hydrophobicity-enhanced catalyst (CaO-G), which exhibited high efficiency (apparent activation energy 11.5 kJ mol−1) for selective hydrogenation of bio-based veratraldehyde (VE) to high-value veratryl alcohol (VA) (up to 99.7% yield, TOF: 166.7 h−1) at room temperature in only 10 min. The involved reaction path was explicitly uncovered by in-situ surface-enhanced Raman. Theoretical calculations were adopted to elucidate the remarkably promotional role of CaO-G in the activation of Si–H for the expedited hydrogenation process. The waste-derived catalyst could be recycled at least five times with no evident decline in catalytic activity and was highly selective for reduction of different unsaturated bio-based aldehydes to alcohols (> 90% yields) at room temperature. An eggshell-derived catalyst prepared by facile calcination and treatment with glycerol shows enhanced basicity and hydrophobicity, which is highly selective for hydrogenation of various bio-based aromatic aldehydes to relevant aromatic alcohols (> 90% yields) at room temperature. [ABSTRACT FROM AUTHOR]

The development of low‐cost nickel‐based catalysts for direct and selective hydrogenation of 2‐butyne‐1,4‐diol (BYD) to butane‐1,4‐diol (BAD) under mild conditions is an important and attractive target both in fundamental research and industrialization but remains a formidable challenge. The primary industrial production method for BAD synthesis is a two‐step reaction route, which suffers from complicated catalysis conditions and high equipment costs. Herein, we develop a high‐performance catalyst via a facile alcohol‐treated strategy for highly selective BAD synthesis at moderate operation conditions. The as‐synthesized NA‐80E catalyst exhibits outstanding BAD selectivity of 98.82 % and BYD conversion of 100 % at 60 °C and 4 MPa, outperforming most reported results for BAD formation in a one‐step process and even being comparable to those obtained by the two‐step hydrogenation reaction route under much high temperatures and pressures. Crucially, we found that after facile alcohol (ethanol) treatment, an intriguing phenomenon of suppression of adjacent acid‐assisted hydrogenolysis via extra acidic Al species at the NiO‐Al2O3 interface is observed, contributing to the precise enhancement of BAD selectivity by inhibiting the production of butanol (BOL). This facile alcohol‐treated method along with the revealed mechanism of blocked hydrogenolysis opens vast possibilities for designing high‐performance and highly‐selective hydrogenation catalysts. [ABSTRACT FROM AUTHOR]

The catalytic hydrogenation of dinitroaromatic compounds is an important reaction for the production of phenylenediamine derivatives, which are widely used in industry. In this work, the catalytic properties of a Cu–Al mixed oxide obtained from double layered hydroxide have been investigated in liquid-phase hydrogenation of 1,3-dinitrobenzenes under continuous-flow conditions. The reaction was carried out at temperature of 120 °C, total pressure of 30 bar, using methanol or methanol/isopropanol mixture as a solvent. It was found that hydrogenation of 1,3-dinitrobenzene, 2,4-dinitrotoluene, 2,4-dinitroanisole and 2,4-dinitromesitylene provides the selective formation of the corresponding diamines, which were isolated in the form of salts with sulfuric acid stable in storage. The effect of the reaction temperature, pressure, H2 flow rate, and solvent nature on the catalyst performance was studied. [ABSTRACT FROM AUTHOR]

A novel photocatalytic strategy was proposed for selectively reducing alkynols to corresponding alkenols under ambient temperature and pressure. Carbon nitride nanosheets with Pd nanoparticles as cocatalysts exhibit high alkynol conversion and alkenol selectivity, which potentially replaces the current thermocatalysis and electrocatalysis. [Display omitted] Selective hydrogenation of alkynols to alkenols is an essential process for producing fine and intermediate chemicals. Currently, thermocatalytic alkynol hydrogenation faces several challenges, e.g., the safety of high-pressure hydrogen (H 2) gas and the need for elevated temperature, and unavoidable side reactions, e.g., overhydrogenation. Here, a novel photocatalytic strategy is proposed for selectively reducing alkynols to alkenols with water as a hydrogen source under ambient temperature and pressure. Under the irradiation of simulated solar light, carbon nitride (C 3 N 4) nanosheets with palladium (Pd) nanoparticles as cocatalysts (Pd–C 3 N 4 NSs) exhibit a 2-methyl-3-butyn-2-ol (MBY) conversion of 98% and 2-methyl-3-buten-2-ol (MBE) selectivity of 95%, outperforming state-of-the-art thermocatalysts and electrocatalysts. After natural-sunlight irradiation (average light intensity of 25.13 mW cm−2) for 36 h, a MBY conversion of 98% and MBE selectivity of 92% was achieved in a large-scale photocatalytic system (2500 cm2). Experimental and theoretical investigations reveal that Pd cocatalysts on C 3 N 4 facilitate the adsorption and hydrogenation of MBY as well as the formation of active hydrogen species, which promote the selective semihydrogenation of alkynols. Moreover, the proposed strategy is applicable to various water-soluble alkynols. This work paves the way for photocatalytic strategies to replace thermocatalytic hydrogenation processes using pressurized hydrogen. [ABSTRACT FROM AUTHOR]

The passivation of hydrogen atoms and the conformation of textured surfaces under oil-lubricated conditions are effective strategies to obtain amorphous carbon (a-C) films with extremely low friction. It is critical to understanding the influence mechanism of selective surface hydrogenation on the tribological behaviors of textured a-C film under oil-lubricated conditions. In particular, the interactions of hydrogen atoms and lubricants are confusing, which is enslaved to the in situ characterization technique. The reactive molecular dynamics (RMD) simulations were conducted to analyze the friction response of textured a-C films with selective hydrogenation surfaces under oil-lubricated conditions. The results indicate that the existence of hydrogen atoms on specific bump sites significantly decreases the friction coefficient (μ) of textured a-C film, which is highly dependent on the surface hydrogen content. The repulsion between hydrogen atoms and lubricant molecules prompts the formation of a dense lubricant film on the surface of the mating material. Interestingly, with the enhancement of the surface hydrogen content, the passivation of the friction interface and the repulsion between hydrogen atoms and lubricants play dominant roles in reducing the friction coefficient instead of hydrodynamic lubrication. [ABSTRACT FROM AUTHOR]

The selective hydrogenation of biomass‐derived benzoic acid (BA) to cyclohexane carboxylic acid (CCA) is vital to producing fine chemicals from renewable sources. Herein, a novel nitrogen‐doped carbon supported bimetallic catalyst (Ni1Co1/NC) was synthesized via a PVP‐assisted method to catalyze the selective hydrogenation of BA to CCA. Compared with the non‐doped Ni1Co1/C and single counterparts, Ni1Co1/NC exhibited a substantially enhanced activity, with 98.1% yield of CCA. The excellent performance was attributed to the NiCo synergistic effect and N‐doped thin carbon layer, which could increase the total proportion of Ni0 and Co0 species via donating electrons to Co and thus improve the H2 adsorption capacity, the hydrogenation activity of aromatic rings in BA and the stability. This work demonstrates a synergetic effect between NiCo bimetal and N‐doped thin carbon layer. This would pave the way for the rational design and synthesis of high‐performance non‐noble catalysts used in BA hydrogenation. [ABSTRACT FROM AUTHOR]

Abstract 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.

Abstract Cost‐effective non‐noble metal‐based catalysts for selective hydrogenation with excellent activity, selectivity, and durability are still the holy grail. Herein, an oxygen‐doped carbon (OC) chainmail encapsulated dilute Cu–Ni alloy is developed by simple pyrolysis of Cu/Ni‐metal–organic framework. The CuNi0.05@OC catalyst displays superior performance for atmospheric pressure transfer hydrogenation of p‐chloronitrobenzene and p‐nitrophenol, and for hydrogenation of furfural, all in water and with exceptional durability. Comprehensive characterizations confirm the close interactions between the diluted Ni sites, the base Cu, and optimized three‐layered graphene chainmail. Theoretical calculations demonstrate that the properly tuned lattice strain and Schottky junction can adjust electron density to facilitate specific adsorption on the active centers, thus enhancing the catalytic activity and selectivity, while the OC shell also offers robust protection. This work provides a simple and environmentally friendly strategy for developing practical heterogeneous catalysts that bring the synergistic effect into play between dilute alloy and functional carbon wrapping.

An NiZr/N‐doped TiO2/Ti3C2 catalyst was prepared by KBH4 reduction for cinnamaldehyde hydrogenation. Characterization results showed that the synthesis of N‐doped TiO2 on Ti3C2 and the uniform dispersion of TiO2 on the Ti3C2 surface increased the specific surface area of NiZr/Ti3C2 by 164.4 m2/g. N‐doping at a level of 19.03 % was used to replace O in the TiO2 lattice; the Ti−O−Ti peak in the XPS spectrum of the undoped catalyst was shifted by 0.3 eV in the spectrum of the doped catalyst; as a result, there was a 15.40 % increase in the number of surface oxygen vacancies of the NiZr/Ti3C2 catalyst. The synthesis of N‐doped TiO2 on Ti3C2 converted the moderately acidic sites of NiZr/Ti3C2 to strong Lewis acid sites and increased the total number of acid sites by approximately 0.8‐fold. The active Lewis acid sites on the surface of NiZr/N‐doped TiO2/Ti3C2 adsorbed only C=O bonds and inhibited the adsorption of C=C bonds, resulting in a high cinnamaldehyde conversion of 90.69 % and a cinnamyl alcohol selectivity of 91.87 %. [ABSTRACT FROM AUTHOR]

An NiZr/N‐doped TiO2/Ti3C2 catalyst was prepared by KBH4 reduction for cinnamaldehyde hydrogenation. Characterization results showed that the synthesis of N‐doped TiO2 on Ti3C2 and the uniform dispersion of TiO2 on the Ti3C2 surface increased the specific surface area of NiZr/Ti3C2 by 164.4 m2/g. N‐doping at a level of 19.03 % was used to replace O in the TiO2 lattice; the Ti−O−Ti peak in the XPS spectrum of the undoped catalyst was shifted by 0.3 eV in the spectrum of the doped catalyst; as a result, there was a 15.40 % increase in the number of surface oxygen vacancies of the NiZr/Ti3C2 catalyst. The synthesis of N‐doped TiO2 on Ti3C2 converted the moderately acidic sites of NiZr/Ti3C2 to strong Lewis acid sites and increased the total number of acid sites by approximately 0.8‐fold. The active Lewis acid sites on the surface of NiZr/N‐doped TiO2/Ti3C2 adsorbed only C=O bonds and inhibited the adsorption of C=C bonds, resulting in a high cinnamaldehyde conversion of 90.69 % and a cinnamyl alcohol selectivity of 91.87 %. [ABSTRACT FROM AUTHOR]

Herein, we reported that the platinum (Pt) clusters encapsulated into sodalite (SOD) zeolite as catalyst exhibited 100 % selectivity at 100 % conversion in the selective hydrogenation of p‐chloronitrobenzene to p‐chloroaniline via hydrogen spillover. The direct interaction between p‐chloronitrobenzene and encapsulated Pt was prevented by the shape selectivity of SOD zeolite, reactants were thereby adsorbed onto zeolite outer surface to facilitate the hydrogenation proceeding by hydrogen spillover process. The further kinetic study and DFT calculation showed the excellent catalytic selectivity was ascribed to the much faster rate of hydrogenation of adsorbed nitro group than that of adsorbed C−Cl group. [ABSTRACT FROM AUTHOR]

Multimetallic catalysis generally involves synergistic effects in chemical transformations that can significantly improve catalytic performance, and the loading of metal nanoparticles (MNPs) onto porous materials contributes to increase the number of active sites. Herein, we investigated the selective hydrogenation of methyl palmitate (MP) using a series of transition MNPs Pd–Ni–Fe with varying molar ratios supported on UiO-66. The catalysts were synthesized through a straightforward liquid-phase impregnation-reduction method. Compared with Pd–Ni/UiO-66, the addition of Fe into Pd–Ni/UiO-66 was found to significantly enhance the selectivity of the desired product, alcohols. This improvement could be attributed to the oxophilic nature of Fe, which weakens the adsorption strength of carbon, thereby increasing the cleavage of the C–O bond rather than the C–C bond. The optimal combination was determined to be Pd1Ni2Fe6/UiO-66, resulting in a 99% conversion of MP and exhibiting 96% selectivity toward 1-hexadecanol. Notably, the catalyst exhibited versatility and stability in the hydrogenation process of fatty acid methyl esters while also offering the advantage of easy separation and reusability. Finally, the reaction mechanism and pathway were proposed based on the product distribution and the properties of the transition MNPs. [ABSTRACT FROM AUTHOR]

Small Pt–Co bimetallic nanoparticles were prepared on ionic liquid-functionalized SBA-15. The prepared 2Pt–2Co/IL@SBA-15 showed high activity and selectivity in cinnamaldehyde hydrogenation to form cinnamyl alcohol under solvent-free conditions. The reaction proceeded efficiently without any addition of solvent with simple product recovery. 2Pt–2Co/IL@SBA-15 exhibited superior activity compared to the monometallic catalysts and Pt–Co on unmodified SBA-15, with 97.1% conversion and 96.2% selectivity to cinnamyl alcohol. The formation of small Pt–Co bimetallic nanoparticles and the presence of an ionic liquid are the keys to its high activity. XAFS analysis and STEM EDS mapping revealed that Pt–Co bimetallic nanoparticles were formed with both Pt and Co exposed on the surface of the nanoparticles. The charge transfer from Co to Pt on the surface of bimetallic nanoparticles results in a high selectivity for cinnamyl alcohol formation. The ionic liquid assisted the formation of small Pt–Co nanoparticles inside the pores of SBA-15 and acted as an "immobilized solvent" allowing the hydrogenation reaction to proceed efficiently without the need for an additional solvent. Moreover, the ionic liquid is strongly bonded to SBA-15, preventing aggregation of bimetallic nanoparticles, resulting in high durability and stability that allows the catalyst to be used six times without significant activity loss. [ABSTRACT FROM AUTHOR]

The selective reduction of functionalized nitroarenes to aniline is a promising strategy to produce industrially vital aniline intermediates, while achieving high selectivity is challenging. Here, we reported the synthesis of structurally ordered Rh3Sn2 intermetallic catalysts that exhibited a high selectivity of 95.1 % in the hydrogenation of 4‐nitrostyrene to 4‐aminostyrene. Density functional theory calculation reveals that the adsorption of nitrostyrene through the nitro group on Rh3Sn2 (110) surface are great improved with the addition of the Sn atom. In addition, a significant electronic effect is formed between Rh and Sn by charge transfer that makes the Rh3Sn2 intermetallic compound more favorable for the hydrogenation of nitro group. [ABSTRACT FROM AUTHOR]