Deposition Precipitation Method Research Articles

Highly efficient CoAl-LDH/(110) facet-exposed BiOBr catalysts: Promotional effect of Z-type heterojunction and oxygen vacancies in photocatalytic ciprofloxacin degradation

Photocatalysis has received extensive attention as a sustainable technology. Herein, a 2D/2D CoAl-LDH/(110) facet-exposed BiOBr Z-type heterojunction photocatalyst enriched with oxygen vacancies (OVs) and Lewis acid sites was prepared by deposition-precipitation method. Results show that the removal of ciprofloxacin by the optimal heterojunction achieves 88 % within 10 min and 98.6 % within 95 min under visible light. Characterization and DFT calculation reveal that CoAl-LDH induces high-energy (110) crystal plane exposure of BiOBr, resulting in the generation of surface OVs and Lewis acid sites. OVs contribute to the adsorption of dissolved oxygen in water, thereby facilitating the generation of •O2−. And Bi(3−x)+ Lewis acid sites promote the adsorption and degradation of reactant molecules. The charge transfer recombination mechanism of the heterojunction enhances the utilization of photogenerated electrons and holes, improving the catalyst photostability. This work provides a simple method for constructing efficient and stable Z-type heterojunctions with defects for photocatalytic water treatment.

Unlocking the potential of biogenic Ag@g-C3N4 in sustainable water purification: A kinetic and photocatalytic study

This research introduces a pioneering biogenic deposition-precipitation method for synthesis of Ag@g-C3N4 nanocomposites (NCs) employing fennel seed extract (FSE). This technique involves the reduction and capping of silver nanoparticles (AgNPs) onto g-C3N4, employing polyphenolic content of FSE, consequently establishing a strong Schottky junction. The, NCs were characterized through various spectroscopic and microscopic techniques, confirming successful biogenic deposition of AgNPs and purity of prepared nanomaterials. Further, the synthesized NCs were utilized for photocatalytic degradation of various hazardous pollutants viz. Rhodamine-B (Rh-B) dye, Tetracycline (TCy) antibiotic, Imidacloprid (IMD) insecticide and deactivation of E. coli microbes. Amongst the synthesized NCs, 3 wt% Ag@g-C3N4 NCs exhibited superior photocatalytic mitigation of Rh-B (99.26%, k = 90.4 × 10−3 min−1), TCy (96.86%, k = 40.2 × 10−3 min−1), IMD (95.7%, k = 34.96 × 10−3 min−1) and E. coli deactivation (99.5%, k = 49.19 × 10−3 min−1). Moreover, the rate constants revealed many-fold increase in photocatalytic degradation of pollutants, contrary to pristine g-C3N4 (k = 11.8 × 10−3 min−1). This investigation also unveils an intricate photocatalytic mitigation pathway for the aforementioned-contaminants, elucidating key role of superoxide radical anions in photocatalytic mitigation. One of the significant highlights of this research is the sustainable and cost-effective synthesis methodology involving fennel seeds, which not only ensures the wide availability of resources but also guarantees environmental safety, in alignment with green principles.

Optimizing mass-transfer and oxygen components to enhance toluene oxidation for MnOx/SAPO-34 and revealing mechanism by in-situ DRITFS

A series of MnOx/SAPO-34 was synthesized using deposition-precipitation method with acid, alkali, saline to modify their physicochemical property enhancing the performance for toluene oxidation. The structure-activity relationship was explored in depth using variant instruments. It was found that the SAPO-34 was etched by desiliconization with oxalic acid as precipitant and converting its micropores into mesopores as well as macropores, which is not only conducive to anchoring and dispersion of more active MnOx, but also promote the mass transfer of reactants. Meanwhile, the catalyst derived from oxalic acid possesses abundant redox sites with the strongest low temperature reducibility. As the results, the Mn/S34-OA exhibits the best performance of toluene oxidation with T90=237°C and ∼100% CO2 selectivity. Besides, the catalyst maintained long-term stability even in presence of H2O at 260°C. Furthermore, the reaction mechanism is revealed by in-situ DRIFTS experiments. It is demonstrated that lattice oxygen directly participates in oxidation of toluene as the crucial active component in path of toluene to benzyl alcohol to benzaldehyde to benzoic acid to CO2 finally. In addition, the consumed lattice oxygen is replenished by adsorbed gaseous O2, which is the key to maintain continuous reaction cycle.

Selective hydrogenation of acetylene over Pd/β-Mo2C catalyst: Experimental and theoretical studies

Molybdenum carbide is a promising support to tune the metal reactivity, which originates from the interaction between metal and support. In this work, Pd/β-Mo2C was prepared using a deposition-precipitation method for selective hydrogenation of acetylene. The high temperature calcination is employed to modulate the interaction between Pd and β-Mo2C. The Pd/β-Mo2C catalyst calcined at 600 °C exhibits significant promotion in selective hydrogenation, which shows 100 % acetylene conversion and 81.4 % ethylene selectivity at 160 °C. The activity promotion originates from the enhanced electronic metal-support interaction, which induces a shift of Pd 3d to higher binding energy. Besides, the Pd species become atomically dispersed after calcination. The changes in geometric and electronic structure suppress the formation of Pd hydrides, which consequently inhibits the excessive hydrogenation capacity of Pd. The structure variation also affects the adsorption of ethylene. No strong adsorbed ethylene (di-σ bonded ethylene) can be identified, which is conducive to the improvement of ethylene selectivity. Density functional theoretical (DFT) calculations confirm that Pd on β-Mo2C is positively charged. The desorption energy of C2H4* (0.78 eV) is significantly lower than that of further hydrogenation (1.45 eV), which explains the improved ethylene selectivity of the calcinated catalyst. The present study indicates calcination is an effective method to tune the activity of Pd/β-Mo2C for reactions beyond selective hydrogenation of acetylene.

2-Methylfuran hydrogenation to 2-methyltetrahydrofuran utilizing Ni/SiO2 catalysts in vapor-phase: Excellent stability via enhanced metal-support interaction

Biomass-derived 2-methyltetrahydrofuran (2-MTHF) is a significant green solvent and a promising biomass fuel, and it is usually produced from 2-methylfuran (2-MF) hydrogenation in liquid phase. It is highly desirable and challenging to develop vapor-phase hydrogenation with such a catalyst that combines high efficiency, excellent stability, easy scale up and low cost. In the present work, we prepared three Ni/SiO2 catalysts using impregnation, urea-assisted impregnation, and deposition–precipitation methods (labeled as NS-IM, NS-UIM, and NS-DP), respectively, for the synthesis of 2-MTHF from 2-MF hydrogenation in vapor-phase. The NS-DP catalyst demonstrated the highest activity and the best stability among all catalysts. Under moderate reaction conditions, a 2-MF conversion of 99.9% with a 2-MTHF selectivity of 99% were achieved on the NS-DP catalyst over 140 h, and it showed a potential significant application prospect. N2 physisorption, ICP, XRD, H2-TPR, TG, HRTEM, and in situ XPS characterization revealed that the catalyst prepared by the deposition–precipitation method possessed the smallest Ni grain size and the strongest metal-support interaction, leading to the highest performance. It was demonstrated that reaction pressure affected the conversion of 2-MF while the reaction temperature affected the selectivity of 2-MTHF. In addition, the structures of the spent catalysts were characterized, and mechanism of deactivation have been discussed in this work.

Catalytic Activity of Incorporated Palladium Nanoparticles on Recycled Carbon Black from Scrap Tires.

A stable support substrate for catalytically active metal nanoparticles (NPs) plays an important role in various chemical transformation reactions. This study describes the effective integration of catalytically active palladium nanoparticles (PdNPs) into recycled carbon black (rCB) obtained from scrap tires. The loading efficiency and dispersion degree of PdNPs prepared via a deposition-precipitation method are thoroughly compared to those prepared with conventional Vulcan CB. As the rCB powder exhibits relatively larger surface areas and wider pore size distributions, slightly polydisperse and more PdNPs are integrated across rCB than those on CB. These composite materials are subsequently tested as catalysts in the Suzuki coupling and styrene hydrogenation reactions. For the Suzuki reaction using phenylboronic acid and bromobenzene, the PdNPs on rCB exhibit slightly higher reactivity than those on CB (TOF of ∼9/h vs ∼8/h), presumably due to the structural features of the integrated PdNPs and the relatively hydrophobic characteristics of the rCB substrate. For the hydrogenation reaction, both composite materials easily result in over 99% yield under ambient conditions with similar activation energies of ∼32 kcal/mol. These composite materials are also recyclable in both reactions without a detectable loss of the PdNP catalyst and its activity. Understanding the physicochemical properties of rCB and demonstrating their potential use as a catalyst support substrate evidently suggest the possibility of replacing conventional CB, which also provides an idea of upcycling waste tires in the development of practical and green reaction systems.

Enhanced catalytic performance for gas phase epoxidation of propylene with H2 and O2 by multiple pretreated Au/TS-1 catalysts

Direct epoxidation of propylene (C3H6) with hydrogen (H2) and oxygen (O2) over Au/TS-1 catalyst was promising way for the synthesis of propylene oxide (PO). However, high selectivity of PO (>95 %) and conversion of C3H6 (>5 %) cannot be achieved at the same time. The industrialization process was severely restricted. In this paper, Au/TS-1 catalysts were synthesized by deposition precipitation method with alkali metal promoter. And alkaline gases and silane coupling post-treatment were performed to promote the catalytic activity. The prepared samples exhibited a much better C3H6 conversion (6.5 %) and PO selectivity (95.1 %) compared with general catalyst using normal synthetic technology. Cs2CO3 was beneficial to increasing Au nanoparticles uptake efficiency. Both NH3 and triethoxyvinylsilane post-treatment were good for smaller and more uniform loading of Au nanoparticles. The decreasing in surface hydroxyl density effectively alleviated the occurrence of PO ring opening isomerization. The increased hydrophobicity of TS-1 surface was conducive to the rapid desorption of generated PO and significantly increased PO selectivity. Multiple pretreatment was also favorable for extending the lifetime of Au/TS-1 catalyst.

Influence of 0.25% Indium Addition to Ni/CeO2 Catalysts for Dry Reforming of Methane

In this study, the surface and textural properties as well as the catalytic performance of Ni/CeO2 and NiIn/CeO2 catalysts prepared by wet impregnation (WI) and deposition–precipitation (DP) are investigated. The addition of Ni (3.0 wt.%) resulted in a decrease in the specific surface area and pore volume in the case of the WI method, possibly due to a blockage of mesopores. A minimal addition of In (0.25 wt.%) caused a further decrease in the surface area in both cases. XRD analysis showed that Ni deposited on CeO2 by DP resulted in some lattice incorporation, affecting the crystallinity of the support. The H2-TPR profiles altered depending on the different ways of Ni and In introduction. STEM-EDS-derived elemental maps indicated that the Ni and NiIn particles deposited on CeO2 using the DP method were somewhat smaller than in the WI synthesis. A comprehensive CO-DRIFTS analysis proved a direct Ni-In interaction in bimetallic samples, leading to the formation of a surface NiIn alloy. Ni/CeO2 catalysts showed a higher activity in the process of dry reforming of methane (DRM) than the bimetallic counterparts at 650 °C, with the Ni_DP sample performing slightly better. However, the Ni_DP catalyst showed significant coking, which was drastically reduced by the addition of In. The agglomeration of Ni and/or NiIn particles during the 6 h DRM reaction somewhat impaired the catalyst performance. Overall, this study highlights the intricate relationship between the catalyst preparation, surface properties and catalytic performance in the DRM reaction and emphasizes the beneficial role of In addition in reducing the coking of the monometallic catalyst and the critical location and surface morphology of nickel nanoparticles decorated with indium and in contact with ceria.

Unravelling the morphology effect of Pt/In2O3 catalysts for highly efficient hydrogen production by methanol steam reforming

Methanol steam reforming (MSR) constitutes an attractive reaction for high-yield on-board hydrogen production for H2-fueled fuel cell applications. Engineering the morphology of Pt/In2O3 heterogeneous catalyst is a feasible strategy for efficient MSR catalyst design, which can construct the Pt2+-In2O3 interfacial sites by utilizing the interaction between Pt and In2O3, thereby facilitating oxygen vacancy creation and activating methanol and water molecules. In this work, three kinds of In2O3 supports with different morphologies of nanorods, nanocubes and nanoplates were synthesized, and Pt/In2O3 catalysts were prepared by deposition–precipitation method. The performance of the catalysts for MSR hydrogen production was evaluated at 250 ∼ 375 ℃. The rod-shaped Pt/In2O3 catalyst with extremely low loading of Pt (0.21 wt%) exhibited the superior catalytic activity compared to the other two counterpart catalysts, achieving the complete CH3OH conversion and the CO selectivity as low as 3.8 % at 325 ℃. Moreover, the performance of Pt/r-In2O3 catalyst remained stable during the stability test for up to 40 h. Based on XRD, BET, HRTEM, XPS, Raman, UV–vis and H2-TPR characterization methods, the observed morphology-dependent reactivity of Pt/In2O3 catalysts can be correlated to the good low-temperature reducibility, abundant surface Pt2+ and adsorbed reactive oxygen species, which was originated from the exposed (211) crystal planes. The preferential exposed (211) crystal plane enables a stronger interaction of In2O3 support with Pt species resulting in the synergistic effect of high oxygen vacancy content, high proportion of Pt2+, and the formation of Pt2+-In2O3 interface active sites, which facilitates the activation and conversion of methanol and water molecules. The developed strategy may provide insight into the development of the design principles for high-performance methanol reforming catalysts for hydrogen production.

Synthesis of Gold Nanoparticles over CoAl Mixed Oxide for Ethanol Oxidation Reaction.

Catalytic total oxidation is an effective technique for the treatment of industrial VOCs principally resulting from industrial processes using solvents and usually containing mono-aromatics (BTEX) and oxygenated compounds (acetone, ethanol, butanone). The aim of this work is to deposit gold nanoparticles on CoAl mixed oxide issued from layered double hydroxide (LDH) precursor by using the deposition precipitation (DP) method, which is applied with two modifications, labeled method (A) and method (B), in order to enhance the interaction of the HAuCl4 precursor with the support. Method (A) involves the hydrolysis of the HAuCl4 precursor after addition of the support, while in method (B), the gold precursor is hydrolyzed before adding the support. The two methods were applied using as support the CoAl mixed oxide and the LDH precursor. Samples were characterized by several physical chemical techniques and evaluated for ethanol total oxidation. Method (B) allowed the ethanol oxidation activity to be enhanced for the resulting Au/CoAlOx catalysts thanks to the high surface concentration of Co2+ and improved reducibility at low temperature. The presence of gold permits to minimize the formation of by-products, notably, methanol, allowed for a total oxidation of ethanol at lower temperature than the corresponding support.

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.

Bimetallic Ni-Co catalyst for improving selectivity in transfer hydrogenation of phenolic compounds

The study investigated the transfer hydrogenation of guaiacol, anisole, phenol, and positional isomers of dimethoxybenezene using 2-PrOH as the H-donor over Ni, Co, and Ni-Co catalysts. The catalysts, which contained 5 wt% metal, were prepared by the deposition-precipitation method. The results showed that the catalysts had developed a pore structure and fine metal particles. The Ni and Ni-Co catalysts demonstrated exceptional activity in the transfer hydrogenation of phenolic compounds with a substrate to metal molar ratio of 100 to 1. Furthermore, the addition of Co to Ni significantly impacted the selectivity of transfer hydrogenation promoting hydrodeoxygenation of anisole and guaiacol.

Preparation of Hydrophobic Au Catalyst and Application in One-Step Oxidative Esterification of Methacrolein to Methyl Methacrylate.

The water produced during the oxidative esterification reaction occupies the active sites and reduces the activity of the catalyst. In order to reduce the influence of water on the reaction system, a hydrophobic catalyst was prepared for the one-step oxidative esterification of methylacrolein (MAL) and methanol. The catalyst was synthesized by loading the active component Au onto ZnO using the deposition-precipitation method, followed by constructing the silicon shell on Au/ZnO using tetraethoxysilane (TEOS) to introduce hydrophobic groups. Trimethylchlorosilane (TMCS) was used as a hydrophobic modification reagent to prepare hydrophobic catalysts, which exhibited a water droplet contact angle of 111.2°. At a temperature of 80 °C, the hydrophobic catalyst achieved a high MMA selectivity of over 95%. The samples were characterized using XRD, N2 adsorption, ICP, SEM, TEM, UV-vis, FT-IR, XPS, and water droplet contact angle measurements. Kinetic analysis revealed an activation energy of 22.44 kJ/mol for the hydrophobic catalyst.

Fine-tuning the electronic properties of Au toward two-dimensional clusters with higher activity for ethanol conversion

Efficient Au/m-ZrO2 catalysts for the conversion of ethanol to acetaldehyde and ethyl acetate were obtained by the deposition precipitation method. The present work investigates the impact of the electronic properties of Au supports on m-ZrO2 catalysts on ethanol dehydrogenation. The Au4f7/2 binding energy (BE) and the average Au-Au nearest-neighbor distances (RAu-Au) were associated with surface defects characterized by CO adsorption. The BE and RAu-Au properties are correlated among themselves, changing by Au loading and pretreatments in an inert atmosphere at different temperatures. Although the RAu-Au unveils a boost of the reaction rates for shorter distances, the coupling of Au and m-ZrO2 produced a bifunctional catalyst. Theoretical studies indicate that molecular ethanol adsorption and formation of the ethoxy intermediate represented a feasible pathway for the activation of ethanol on the Au-ZrO2 interface. The RAu-Au toward of 2D clusters conferred high catalytic activity and low apparent activation energy for ethanol dehydrogenation.

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.

Synthesis of novel Ag/AgBr/K0.4Y0.7Sb2O6.25 nanocomposite with enhanced photocatalytic properties

Devoloping efficient wastewater treatment photocatalysts capable of improving water quality is undoubtedly one of the main problems of present society. In recent years, novel plasmonic photocatalysts have shown new possible applications in photocatalytic wastewater treatment due to their unique properties. In this work, a novel Ag/AgBr/K0.4Y0.7Sb2O6.25 composite was successfully fabricated by photo-reduction using the pre-prepared AgBr/K0.4Y0.7Sb2O6.25 and K0.4Y0.7Sb2O6.25 (KYSbO). The AgBr/KYSbO and KYSbO were synthesized by deposition-precipitation and precipitation-heating methods. The visible-light photocatalytic performance of parent KYSbO and Ag/AgBr/KYSbO composite was evaluated using methylene blue (MB) as a model organic pollutant. The effects of catalyst dosage, pH and the initial concentration of the MB dye solution on the photocatalytic activity were also investigated in this study. Remarkably, the Ag/AgBr/KYSbO composite exhibited superior visible-light photocatalytic activity for the degradation of MB than that of parent KYSbO. MB was degraded to 91.6% in the presence of parent KYSbO after visible irradiation of 180 min, while 93.2% degraded in merely 30 min in the case of Ag/AgBr/KYSbO composite. The superior improvement in the photocatalytic activity of the Ag/AgBr/KYSbO composite can be credited to the efficient separation of photoinduced electron-hole pairs and the extended visible-light response range. Superoxide radicals are crucial for MB photocatalytic degradation in the Ag/AgBr/KYSbO composite. The possible photocatalytic mechanism was proposed.

C–C bond coupling differences between β-O-4 and 4-O-5 ether bonds over hydrophobic mesoporous Ru/MY-O catalysts: from lignin model compounds to polycyclic alkanes

MY zeolites with mesopores were prepared by hydrothermal method using functionalized SiO2 (F-SiO2) as a silica source, and hydrophobic bifunctional Ru/MY-O catalysts were obtained by deposition precipitation method and silylation treatment. This work aims at obtaining polycyclic alkane (PCA) based high-density hydrocarbon fuels (HDHFs). We focused on the catalytic hydroconversion (CHC) of 2-phenoxy-1-phenylethanol (PP-ol) and oxydibenzene (ODB), two typical lignin-related model compounds (LRMCs), over Ru/MY-O. The effects of different reaction conditions and catalysts on the product distribution in PP-ol and ODB were investigated. The partial hydrogenation of ODB was found to be a necessary step before achieving C-O ether bond cleavage and C-C bond coupling. The balance of metal/acidic sites is critical for maximizing PCA yields. Changes in the metal/acid ratio had a greater effect on PCA yield in PP-ol than in ODB. Poor stability of cycloalkyl cations and partial hydrogenation of ODB hinder the generation of C-C coupling products. The incorporation of mesopores and hydrophobic treatment were found to weaken the negative effects of C-C bond coupling products and water on the catalyst. The conversion of Ru3/MY-O was improved by nearly 10% compared to Ru3/Y in the fifth cycle reaction. This work provided a theoretical basis for the generation of HDHFs from lignin.

Hydrogen Production from Hydrous Hydrazine Decomposition Using Ir Catalysts: Effect of the Preparation Method and the Support

Herein, Ir/CeO2 catalysts were prepared using the deposition–precipitation method with NaOH or urea as the precipitating agent or using sol immobilization with tetrakis(hydroxymethyl)phosphonium chloride (THPC) as the protective and reducing agent. The effect of the preparation method on Ir catalyst activity was evaluated in the liquid-phase catalytic decomposition of hydrous hydrazine to hydrogen. Ir/CeO2 prepared using sol immobilization and DP NaOH showed the best activity (1740 h−1 and 1541 h−1, respectively) and yield of hydrogen (36.6 and 38.9%). Additionally, the effect of the support was considered, using TiO2 and NiO in addition to CeO2. For this purpose, the sol immobilization of preformed nanoparticles technique was considered because it allows the same morphology of the immobilized particles to be maintained, regardless of the support. Ir deposited on NiO resulted in the most selective catalyst with a H2 yield of 83.9%, showing good stability during recycling tests. The catalysts were characterized using different techniques: X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), scanning electron microscopy (SEM) equipped with an X-ray detector (EDX) and inductively coupled plasma–mass spectroscopy (ICP-MS).

CO2 hydrogenation to methanol over the copper promoted In2O3 catalyst

The metal promoted In2O3 catalysts for CO2 hydrogenation to methanol have attracted wide attention because of their high activity with high methanol selectivity. However, there was still no experimental confirmation if copper could be a good promoter for In2O3. Herein, the Cu promoted In2O3 catalyst was prepared using a deposition-precipitation method. Such prepared Cu/In2O3 catalyst shows significantly higher CO2 conversion and space time yield (STY) of methanol, compared to the un-promoted In2O3 catalyst. The loading of Cu facilitates the activation of both H2 and CO2 with the interface between the Cu cluster and defective In2O3 as the active site. The Cu/In2O3 catalyst takes the CO hydrogenation pathway for methanol synthesis from CO2 hydrogenation. It exhibits a unique size effect on the CO adsorption. At temperatures below 250 °C, CO adsorption on Cu/In2O3 is stronger than that on In2O3, causing higher methanol selectivity. With increasing temperatures, the Cu catalyst aggregates, which leads to the formation of weak CO adsorption site and causes a decrease in the methanol selectivity. Compared with other metal promoted In2O3 catalysts, it can be concluded that the catalyst with stronger CO adsorption possesses higher methanol selectivity.

Engineering the CuO/MnO2 interface with multivalent conversion for low-temperature and efficient CO oxidation

A novel interface of MnO2 with CuO with multivalent conversion is fabricated by the deposition-precipitation method for low-temperature and efficient CO oxidation. It is found that the temperature for CO thermal-catalytic oxidation to reach a complete conversion significantly decreases to 105 °C for the CuO/MnO2. A combination of experimental and theoretical studies demonstrates the successful formation of the CuO/MnO2 interface, inducing a pronounced effect that promotes CO oxidation. The CuO/MnO2 interface leads to the formation of Cu-O-Mn, a superior redox system with multivalent conversion (Cu+ + Mn4+ ↔ Cu2+ + Mn3+, Cu+ + Mn3+ ↔ Cu2+ + Mn2+), abundant active sites, excellent ability to activate O2, the rapid oxygen transfer, and more suitable adsorption energy for O2, CO, and CO2. These characteristics are advantageous to CuxO-MnxOy for achieving a 100 % removal of CO at a lower temperature. Furthermore, the computational study reveals that the CO oxidation process follows two mechanistic pathways (Eley-Rideal (E-R) and Mars-van Krevelen (M-K)), indicating that there is no competitive adsorption of CO and O2 on the CuO/MnO2. This study shows that the interface created between suitable metal oxides can improve the catalytic performance and provides new perspective for catalyst design and performance enhancement mechanisms.