Catalysts For Hydrogenation Research Articles

Cation rearrangement at tetrahedral sites in the Cu/ZnAl2O4 spinel enhancing CO2 hydrogenation to methanol

Cu/ZnAl2O4 spinel is a promising catalyst for CO2-to-methanol due to its dual-site H2 activation. However, controlling surface properties and metal-support interactions (MSI) through the coordination environment of spinel cations remains underexplored. Herein, the occupancy of Zn2+ and Al3+ cations in Cu/ZnAl2O4 spinel is fine-tuned by manipulating the calcination atmosphere. More disordered structures (AlO4 and ZnO6) observed on the CZA-Ar catalyst benefit the creation of oxygen vacancies and surface hydroxyl groups, which facilitate the formation of highly dispersed small-sized Cu species. This enhances MSI and hydrogen spillover effects, thereby boosting CO2 conversion and the space-time yield (STY) of methanol. High-pressure in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) results reveal that the crucial formate intermediates form at tetrahedral sites in ZnAl2O4 spinel, with more Al-HCOO- species observed on the CZA-Ar catalyst due to the formation of AlO4. This work advances the understanding of spinel catalysts in CO2 hydrogenation to methanol.

Embedding Single Pd Atoms on NiGa Intermetallic Surfaces for Efficient and Selective Alkyne Hydrogenation.

Catalytic removal of alkynes is essential in industry for producing polymer-grade alkenes from steam cracking processes. Non-noble Ni-based catalysts hold promise as effective alternatives to industrial Pd-based catalysts but suffer from low activity. Here we report embedding of single-atom Pd onto the NiGa intermetallic surface with replacing Ga atoms via a well-defined synthesis strategy to design Pd1-NiGa catalyst for alkyne semi-hydrogenation. The fabricated Pd1Ni2Ga1 ensemble sites deliver remarkably higher specific mass activity under superb alkene selectivity of >96 % than the state-of-the-art catalysts under industry-relevant conditions. Integrated experimental and computational studies reveal that the single-atom Pd synergizes with the neighbouring Ni sites to facilitate the σ-adsorption of alkyne and dissociation of hydrogen while suppress the alkene adsorption. Such synergistic effects confer the single-atom Pd on the NiGa intermetallic with a Midas touch for alkyne semi-hydrogenation, providing an effective strategy for stimulating low active Ni-based catalysts for other selective hydrogenations in industry.

Waste-Derived Caffeine for Green Synthesis of Rhenium Nanoparticles with Enhanced Catalytic Activity in the Hydrogenation of 4-Nitrophenol

Yearly, thousands of tons of wasted coffee grounds are produced according to high coffee consumption. Still, after the coffee brewing, wasted coffee grounds contain some amounts of caffeine (CAF). CAF, in turn, contains multiple O and N chelating atoms in its structure. These have a potential to be reductors for complexes of metals. In this context, within the present study, a set of CAF extracts derived from coffee beans and coffee grounds were obtained and then used for the one-step reduction of ReO4− ions with no additional toxic chemicals. Within this approach, CAF was applied as a secondary, green resource for the synthesis of unique rhenium nanoparticles (ReNPs) containing Re species at 0 and +6 oxidation states. The obtained ReNPs were identified and characterized with the use of X-ray powder diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM). Further, the capping and stabilization of ReNPs by CAF were verified with the aid of Fourier transformation infrared spectroscopy (FT-IR). The so-obtained “green” ReNPs were then used as a homogenous catalyst in the catalytic hydrogenation of 4-nitrophenol (4-NP). This new nanomaterial revealed a superior catalytic activity, leading to the complete reduction of 4-NP to 4-aminophenol within 40–60 min with a first-order rate constant of 0.255 min−1.

Constructing efficient Pd/Al2O3 catalyst for reverse water-gas shift via alkali-modification

The intrinsic nature of irreducible oxides (e.g. Al2O3) makes it hard to tune the charge state of supported late-transition metals, then difficult to adjust the selectivity of catalysts in CO2 hydrogenation. Herein, we find that modifying the Pd/Al2O3 catalyst with alkali metals (especially potassium) is efficient to boost the CO formation in CO2 hydrogenation. In comparison to Pd/Al2O3, approximately twenty-fold promotion in reverse water–gas shift (RWGS) rate was achieved on K-modified catalysts with proper K/Pd proportions. Combined structural characterizations demonstrate that the enhanced Pd-O interactions through K mediation stabilize the ca. 2 nm sized Pd particles as well as the electron-deficient state of Pd, which are robust enough during long-termed evaluation with undamped performance. In situ spectroscopy unveils a bi-dentate *HCOO associated reaction mechanism taking effect on alkali-modified catalysts, which contributes to ∼ 100 % of CO selectivity and 3318.1 mmol∙gPd-1∙h−1 of CO formation rate at 340°C.

Ru nanoparticles on mesostructured carbon for glucose hydrogenation; catalysts synthesis and characterization

Ru-containing hydrogenation catalysts based on functionalized carbon material CMK-3 (Carbon Mesostructured by KAIST) were developed. Mesostructured silicate SBA-15 with enlarged wall channels was used as a template for the carbon replica synthesis. The effect of carbon material functionalization via moist air oxidation and sulfonation on the morphology, physicochemical properties and activity of the catalyst was studied. The dispersion, localization, and electronic state of supported ruthenium were determined depending on the support functionalization method. The initial support structure preservation after Ru deposition was confirmed by a set of physicochemical methods. Metal particles are finely distributed with no agglomerated present, providing a high active site accessibility and ensures a superb catalyst activity. The catalysts were tested in glucose to sorbitol hydrogenation. The results showed that pore morphology and carbon support initial structure preservation account for the catalytic activity of Ru nanoparticles.

Liquid Organic Hydrogen Carrier Concepts and Catalysts for Hydrogenation and Dehydrogenation Reactions.

The issue of renewable energy (RE) source intermittency, such as wind and solar, along with the geographically uneven distribution of the global RE potential, makes it imperative to establish an energy transport medium to balance the energy demand and supply areas. A promising energy vector to address this situation is hydrogen, which is considered a clean energy carrier for various mobile and portable applications. Unfortunately, at standard pressure and temperature, its energy content per volume is very low (0.01 kJ/L). This necessitates alternative storage technologies to achieve reasonable capacities and enable economically viable long-distance transportation. Among the hydrogen storage technologies using chemical methods, liquid organic hydrogen carrier (LOHC) systems are considered a promising solution. They can be easily managed under ambient conditions, the H2 storage/release processes are carbon-free, and the carrier liquid is reusable. However, the evolution of the proposals from the carrier liquid type and catalyst elemental composition point of view is scarcely studied, considering that both are critical in the performance of the system (operational parameters, kinetic of the reactions, gravimetric hydrogen content, and others) and impact in the final cost of the technology deployed. The latter is due to the use of the Pt group elements (PGEs) in the catalyst that, for example, have a high demand in the hydrogen production sector, particularly for polymer electrolyte membrane (PEM) water electrolysis. With that in mind, our objective was to examine the evolution and the focus of the research in recent years related to proposals of LOHCs and catalysts for hydrogenation and dehydrogenation reactions in LOHC systems which can be useful in defining routes/strategies for new participants interested in becoming involved in the development of this technology. For this systematic review, we searched the SCOPUS database and forward and backward citations for studies published in the database between January 2011 and December 2022. The criteria include articles which assessed or studied the effect of the type of catalyst, type of organic liquid, reactor design(s)/configuration(s), and modification of the reactor operational parameters, among others, over the performance of the LOHC system (de/hydrogenation reaction(s)). The relevant data from each reviewed study were collected and organized into a pre-designed table on an Excel spreadsheet, categorized by reference, year, carrier organic liquid, reaction (hydrogenation and/or dehydrogenation), investigated catalyst, and primary catalyst element. For processing the data obtained from the selected scientific publications, the data analysis software Orbit Intellixir was employed. For the study, 233 studies were included. For the liquid carrier side, benzyltoluene and carbazole dominate the research strategies. Meanwhile, platinum (Pt) and palladium (Pd) are the most employed catalysts for dehydrogenation reactions, while ruthenium (Ru) is preferred for hydrogenation reactions. From the investigated liquid carrier, those based on benzyltoluene and carbazole together account for over 50% of the total scientific publications. Proposals based on indole, biphenyl, cyclohexane, and cyclohexyl could be considered to be emerging within the time considered in this review, and, therefore, should be monitored for their evolution. A great activity was detected in the development of catalysts oriented toward the dehydrogenation reaction, because this reaction requires high temperatures and presents slow H2 release kinetics, conditioning the success of the implementation of the technology. Finally, from the perspective of the catalyst composition (monometallic and/or bimetallic), it was identified that, for the dehydrogenation reaction, the most used elements are platinum (Pt) and palladium (Pd), while, for the hydrogenation reaction, ruthenium (Ru) widely leads its use in the different catalyst designs. Therefore, the near-term initiatives driving progress in this field are expected to focus on the development of new or improved catalysts for the dehydrogenation reaction of organic liquids based on benzyltoluene and carbazole.

Foam Ti Supported Pd Catalysts for the Selective Hydrogenation of Nitroaromatics.

The selective hydrogenation of nitroaromatics plays an essential role in the chemical industry for the synthesis of anilines and their derivatives, which are known as crucial fine chemicals and pharmaceuticals. In this study, we demonstrate the preparation of Pd/Ti monolith catalyst containing well-isolated metallic Pd sites on Ti substrate through a simple impregnation method, showing remarkable catalytic properties in the selective hydrogenation of nitroaromatics containing various functional groups. Kinetic analyses reveal an apparent activation energy of 61 kJ/mol and the kinetic isotope effect (KH2/KD2) of ~1.7 in the hydrogenation of 3-chloronitrobenzene over Pd/Ti-200 ppm catalyst, indicating the facile dissociation of dihydrogen and the subsequent efficient hydrogenation. The Pd/Ti-200 ppm catalyst also demonstrates good stability and recyclability, maintaining its performance over multiple cycles. This simple but innovative approach not only enhances the efficiency of Pd catalysts in the selective hydrogenation of nitroaromatics but also offers significant potential for industrial applications in aniline production.

Homogeneous Integration of Polyoxometalates and Titania into Crumpled Layers.

The crumpling and buckling in nanosheets are anticipated to provide new characteristics that could not be observed in ideal flat layers. However, the rigid lattice structure of inorganic metal oxides limits their assembly into well-defined crumpled layers. Here, this study demonstrates that at the sub-nm scale, polyoxometalates (POMs) clusters having well-defined structures can intercede during the nucleation process of titania and co-assemble with nuclei to form uniform, large-sized crumpled binary 2D layers with a thickness of 2nm. The obtained crumpled layers are then used as a support material to immobilize Pd nanoclusters with an average size of 2nm. Pd-immobilized crumpled layers are employed as heterogeneous catalysts for the partial hydrogenation of acetylene. This structurally and compositionally unique heterogeneous catalyst manifests exceptional selectivity to cis-alkene with almost 100% yield as compared to commercially available titania which only exhibits 10% diphenylacetylene conversion and 42% selectivity in the given period of time.

Homogeneous Catalysts for Hydrogenative PHIP Used in Biomedical Applications

AbstractAt present, two competing hyperpolarization (HP) techniques, dissolution dynamic nuclear polarization (DNP) and parahydrogen (para‐H2) induced polarization (PHIP), can generate sufficiently high liquid state 13C signal enhancement for in vivo studies. PHIP utilizes the singlet spin state of para‐H2 to create non‐equilibrium spin populations. In hydrogenative PHIP, para‐H2 is irreversibly added to unsaturated precursors, typically in the presence of a homogeneous catalyst. The hydrogenation catalyst plays a crucial role in converting the singlet spin order of para‐H2 into detectable nuclear polarization. Currently, rhodium(I) bisphosphine complexes are the most widely employed catalysts for PHIP, capable of catalyzing the addition of para‐H2 to unsaturated precursors in organic solvents or aqueous media, depending on the ligand. Chiral catalysts enable the stereoselective production of hyperpolarized substrates. Ruthenium(II) piano stool complexes are capable of trans addition and are used to generate hyperpolarized fumarate. However, these catalysts systems are not optimal, and the greatest source of nuclear spin polarization loss is attributed to the mixing of singlet and triplet states of the protons derived from the para‐H2 during the hydrogenation process. Hence, future efforts should focus on enhancing the efficiency and kinetics of these catalysts.

Structural design and electronic regulation of atomically dispersed Mo-S4 sites by second shell N species reconfiguration for intensifying hydrogen spillover

Intensifying hydrogen spillover by regulating the atomic local structures catalysts is crucial for improving the hydrogenation performance, but still hugely challenging. Herein, we report a robust single-atom catalyst featuring Mo-S4 sites in the first shell modulated with N atoms in the second shell (Mo-S4-N/C) by an efficient cyclodextrin supramolecular self-assembly pyrolysis strategy for intensifying hydrogen spillover in slurry-phase hydrocracking of vacuum residue (VR). We discovered that the H2 is activated at the single-atom Mo-S4 sites efficiently and the spillover of active hydrogen is accelerated by the reconfiguration of N species in the second shell. Remarkably, the Mo-S4-N/C catalyst demonstrates excellent catalytic hydrogenation activity with high turnover frequency calculated for total metals up to 0.46 s−1, the VR per pass conversion of 61 wt.%, liquid product yield of 94 wt.%, and the low coke content of 0.6 wt.%, along with good stability, respectively. Theoretical calculations revealed that the N species in the second shell regulated the electronic structure of Mo-S4 sites, promoting the migration of active hydrogen species by reducing the transfer energy barrier of hydrogen spillover, thus enhancing the hydrogenation performance. This work proposed a strengthened hydrogen spillover mechanism from the atomic scale for hydrogenation reaction, offering novel concepts for designing and developing high-performance hydrogenation catalysts.

Ir(III) Diamine Transfer Hydrogenation Catalysts in Cancer Cells

AbstractThe development of catalytic metallodrugs is an emerging field that may offer new approaches to cancer chemotherapeutic design. By exploiting the unique properties of transition metal complexes, in‐cell catalysis can be applied to modulate the cellular redox balance as part of a multi‐targeting mechanism of action. We describe the synthesis and characterization of six coordinatively unsaturated iridium(III) diamine catalysts that are stable at physiological pH in aqueous solution. Reduction of the colorimetric substrate 2,6‐dichlorophenolindophenol by transfer hydrogenation under biologically compatible conditions achieved turnover frequencies up to 63 ± 2 h−1 and demonstrated that the source of hydride (sodium formate) is the limiting reagent, despite being in a 1000‐fold excess of the catalyst. The catalyst showed low in vivo acute toxicity in zebrafish embryos and modest in vitro potency towards cancer cells. When administered alone, the catalyst generated oxidative stress in cells (an effect that was conserved in vivo), but co‐treatment with a nontoxic dose of sodium formate negated this effect. Co‐treatment with sodium formate significantly enhanced catalyst potency in cancer cells (A2780 ovarian and MCF7 breast cancer cells) and drug‐resistant cells (A2780cis and MCF7‐TAMR1) but not in non‐tumorigenic cells (MRC5), demonstrating that a redox‐targeting mechanism may generate selectivity for cancer cells.

Carbon Materials with Different Dimensions Supported Pt Catalysts for Selective Hydrogenation of 3,4-Dichloronitrobenzene to 3,4-Dichloroaniline

In this study, carbon materials with different dimensions, including the typical one-dimensional (1D) carbon nanotube (CNT), two-dimensional (2D) graphene (GF), and three-dimensional (3D) activated carbon (AC), were investigated as a support for Pt catalysts for the selective hydrogenation of 3,4-dichloronitrobenzene (3,4-DCNB) to 3,4-dichloroaniline (3,4-DCAN). Notably, the Pt/CNT catalyst with the lowest dimension exhibited the best conversion of 3,4-DCNB under mild reaction conditions, followed by Pt/GF. Comprehensive characterizations, including XRD, TEM, XPS, and in situ CO DRIFTS, reveal that the dimension of carbon supports plays an important role in the particle size and electronic properties of Pt species, consequently affecting the catalytic performances of Pt catalysts. According to the results, electron-deficient Pt particles with small sizes are more favorable for the hydrogenation of 3,4-DCNB to 3,4-DCAN. In addition, dynamic tests and in situ DRIFTS of 3,4-DCNB indicated that the carbonaceous supports will largely influence the adsorption and activation capacity of the Pt catalysts, so that Pt loaded on CNT and GF are superior to that on the AC. We believe this study will provide good guidance for designing efficient carbon-supported metal catalysts for selective hydrogenation.

Enhanced Selectivity to Methanol in CO2 Hydrogenation on CuO/ZrO2 Catalysts by Alkali Metal Modification

AbstractIn order to alleviate the influence of greenhouse effect on global climate change, the effective utilization of CO2 to prepare fine chemicals should be paid more attention to, however, which is greatly blocked by the catalyst with low efficiency. Here, alkali metal (Li, Na, or K) are employed as a modification aid to prepare CuO/ZrO2 catalyst for CO2 hydrogenation to methanol. The effects of alkali metal on physicochemical properties and catalytic activities of CuO/ZrO2 catalyst were studied in detail by the XRD, N2‐physisorption, ICP‐OES, SEM/EDS, H2/N2O/CO2/NH3‐chemisorption, and evaluation test. The results verified that the use of complex combustion method enabled the uniform combination of all components in precursor. High‐temperature calcination (700 °C) further enhanced the strong interaction and synergistic effect between Cu and ZrO2. Most importantly, the introduction of alkali metal effectively altered the structure and catalytic activity of CuO/ZrO2 catalysts. However, the selectivity to methanol increased while the CO2 conversion decreased regardless of different kinds of alkali metal being introduced to the CuO/ZrO2 catalysts. For example, CuO/ZrO2 catalyst modified by K exhibited excellent performance for methanol production that 98.9% selectivity of methanol based on 8.8% conversion of CO2 after 48 h online reaction.

Nanoporous Carbon-Supported Bimetallic (Ni, Cu, and Fe)-Mo Catalysts for Partial Hydrogenation of Biodiesel.

Upgrading biodiesel or hydrogenated fatty acid methyl esters (H-FAMEs) by partial hydrogenation is a second-generation biofuel with high specific fuel characteristics, such as superior cold flow properties, higher oxidative stability, and lower hazardous gas emissions, allowing this biofuel to provide excellent fuel properties, over conventional biodiesel. This study assessed the potential of using nanoporous carbon produced from cattail leaves (CL) as an alternative catalyst support. We synthesized various catalysts including monometallic Mo/NPC, Ni/NPC, Ce/NPC, and Fe/NPC catalysts, as well as bimetallic molybdenum-based catalysts doped with nickel, copper, or iron for the partial hydrogenation of soybean biodiesel. The NPC support demonstrated a surface area (S BET) of approximately 1,323 m2g-1, which greatly increases the catalytic activity through the efficient dispersion of catalyst active sites. The partial hydrogenation reaction of soybean FAME over the MoNi/NPC catalyst obtained the highest catalytic activity with enhanced oxidation stability from 3 to 14 h, and the cloud point and pour point increased from 2 to 13 °C and -1 to 10 °C, respectively. Hence, the selection of catalysts is crucial due to their impact on the feasibility of the process and its economic viability. This article focuses on highlighting the effectiveness of a highly promising catalyst for partial hydrogenation as well as examining the variables that influence the primary reaction pathway.

Catalytic performance of a single atom Pd1Ag10/Al2O3 catalyst for the selective hydrogenation of acetylene: The role of CO-induced segregation

The single-atom Pd catalysts based on silver-rich bimetallic compositions are known for their extremely high ethylene selectivity in the acetylene hydrogenation reaction; however, their activity is noticeably lower than that of traditional monometallic Pd catalysts. The aim of the work was to apply a method of CO-induced segregation to increase the concentration of single atom Pd1 sites on the surface of Pd1Ag10/Al2O3 catalyst without noticeable formation of multiatomic Pdn (n ≥ 2) ensembles. It has been experimentally established by DRIFTS-CO and XPS methods that the effect of 30 vol% CO exposure temperature on the increase of surface Pd1 sites concentration in the range of 50 to 350 °C has a volcano-like dependence with a maximum at ∼ 200–250 °C. The catalytic tests show a considerable enhancement in activity for samples treated in CO at 200–250 °C (the temperature of 100 % acetylene conversion is reduced by ∼ 30 °C), while the C2H4 selectivity was similar for both freshly reduced and CO-treated catalysts. These results demonstrate the use of CO-induced segregation as a promising method for the controlled increase in the concentration of isolated Pd1 sites to improve the activity of silver-rich palladium catalyst without compromising its selectivity.

Catalytic hydrogenation of waste-derived lipids: A route to producing sustainable drop-in biofuels by using Re/TiO2 catalysts

The urgent threat of climate change compels modern society to transition to alternative energy sources swiftly. The production of sustainable liquid biofuels capable of substituting fossil-derived fuels is a topic of great interest. This study explores the effectiveness of Re/TiO2 catalysts in producing drop-in biofuels from waste-derived feedstock. Specifically, four Re-based catalysts supported on different TiO2 materials, namely TiO2 P25, TiO2 FSP, TiO2 M, TiO2 COTIOX were synthesized using the wet impregnation method, characterized and tested in the hydrodeoxygenation reaction of fatty acids, to uncover fundamental insight into this process. These catalysts exhibited varying levels of effectiveness. Apart from Re/TiO2 COTIOX, which showed the lowest conversion of fatty acids (30 %), the other three catalysts allowed over 98 % conversion of fatty acids into hydrocarbons after 6 h reaction, at 35 bar of H2, under solvent-free conditions and without pre-reduction of the catalyst. Notably, Re/TiO2 P25 was the most effective, attaining this remarkable result at 300 °C. The remaining catalysts, Re/TiO2 FSP and Re/TiO2 M, required higher temperatures (350 °C) to achieve complete hydrogenation of fatty acids into hydrocarbons. These effective catalysts also demonstrated great recoverability, reusability, and robustness, successfully converting waste-derived lipids, such as grease recovered from urban sewage sludge and waste cooking oil, into hydrocarbons. These findings underscore Re/TiO2 as a promising robust catalyst for waste-derived lipids hydrogenation, enabling the efficient production of drop-in biofuels and paving the way for innovative solutions in the renewable energy landscape.

NiO Nano- and Microparticles Prepared by Solvothermal Method—Amazing Catalysts for CO2 Methanation

Nickel oxide (NiO) is one of the most popular hydrogenation catalysts. In heterogeneous catalysis, nickel oxide is used, for example, as a suitable methanation catalyst in the Fischer–Tropsch reaction not only for CO hydrogenation but also in the modified Fischer–Tropsch reaction with CO2. However, CH4 selectivity and CO2 conversion strongly depend on NiO micro- (MPs) and nanoparticles’ (NPs) shape, size, and surface area. In this study, the synthesis of NiO micro- and nanoparticles was conducted using the simple solvothermal method. Different morphologies (microspheres, sheet clusters, hexagonal microparticles, and nanodiscs) were prepared using this method with different solvents and stabilizers. The prepared catalysts were tested in the hydrogenation of CO2 in a gas phase with excellent conversion values and high selectivity to produce CH4. The best results were obtained with the NiO with disc or sphere morphology, which produced methane with selectivity at a level near 100% and conversion close to 90%.

Synthesis and reactivity of a heteroleptic magnesium hydride on a dearomatized picolyl-based NNN-chelator.

Heteroleptic magnesium hydrides are important for their stoichiometric and catalytic reduction chemistry. Their primary nucleophilic site is typically the hydride, while the ancillary ligands commonly used are mostly spectators. Chemically non-innocent ligands in comparison are rarely applied on MgH as their reactivity can be complex. Milstein et al. have recently reported Mg-mediated alkyne hydrogenation by using their metal-ligand cooperation (MLC) concept on a dearomatized picolyl-based PNP pincer that is non-innocent with a nucleophilic nature. A '(PNP)MgH' is noted as the active catalyst in hydrogenation but without structural validation. Inspired by the same, we report herein a novel NNN-chelator (MesL) with a dearomatized picolyl moiety and its well-defined MgH. Having two prominent nucleophilic sites, the present MgH shows metal-ligand competition while reacting with certain electrophiles. It also distinguishes nonpolar alkynes and polar carbonyls by cleanly inserting itself into the former but not the latter. The nucleophilicities of the two sites are also probed by DFT methods and compared with Milstein's (PNP)MgH. Although the present system shows no MLC-type H2 activation, the addition of a CS2 molecule in that way is realized.

Covalent Organic Framework-Derived B/N Co-Doped Carbon FLPs Metal-Free Catalysts for the Selective Hydrogenation of α,β-Unsaturated Aldehydes to Unsaturated Alcohols

Covalent Organic Framework-Derived B/N Co-Doped Carbon FLPs Metal-Free Catalysts for the Selective Hydrogenation of α,β-Unsaturated Aldehydes to Unsaturated Alcohols

Laser-engraved defects in TiO2 support: Enhancing reducibility and redox capability of Pt/TiO2 catalyst for reactive and selective hydrogenation

Titanium dioxide (TiO2) has been studied as catalyst or catalyst support in catalysis. Its synthesis or modification approach controls the structural, optical, and electronic properties. Here we applied laser engraving to the anatase TiO2 and studied the consequent changes in its structure and property as well as the properties of TiO2 supported platinum (i.e., Pt/TiO2) catalyst. The laser engraving enlarged the particle size, formed rutile phase and created defects (i.e., oxygen vacancy (Ov) and Ti3+) in anatase TiO2. This induced band gap change and enhanced visible light absorption. The defects created by laser engraving are stable and more reducible than those existed in the pristine TiO2. The defective TiO2 is structurally stable and has great redox properties. The metal-support interaction in the Pt/defective TiO2 catalyst is stronger than that of the pristine Pt/TiO2 catalyst, which enabled higher reactivity and selectivity in hydrogenation of 3-nitrostyrene and furfuryl alcohol. Laser-engraved TiO2 has been rarely studied for thermal catalysis. This work provides basic understanding of material properties and catalysis application of laser-engraved catalyst supports and catalysts in field of thermal catalysis.