Space-time Yield Research Articles

Intensification of Enzymatic Sorbityl Laurate Production in Dissolved and Neat Systems under Conventional and Microwave Heating.

Glycolipids such as sugar alcohol esters have been demonstrated to be relevant for numerous applications across various domains of specialty. The use of organic solvents and, more recently, deep eutectic solvents (DESs) to mediate lipase-supported bioconversions is gaining potential for industrial application. However, many challenges and limitations remain such as extensive time of production and relatively low productivities among others, which must be solved to strengthen such a biocatalytic process in industry. In this context, this study focuses on the intensification of sorbityl laurate production, as a model biocatalyzed reaction using Novozym 435, investigating the relevance of temperature, heating method, and solvent system. By increasing the reaction temperature from 50 to 90 °C, the space-time yield and product yield were considerably enhanced for reactions in DES and the organic solvent 2M2B, irrespective of the heating method (conventional or microwave heating). However, positive effects in 2M2B were more pronounced with conventional heating as 98% conversion yield was reached within 90 min at 90 °C, equating thus to a nearly 4-fold increase in performance yielding 118.0 ± 3.6 g/(L·h) productivity. With DES, the overall yield and space-time yield were lower with both heating methods. However, microwave heating enabled a 2-fold increase in both performance parameters when the reaction temperature was increased from 50 to 90 °C. Compared to conventional heating, a 7-fold increase in space-time yield at 50 °C and a 16-fold increase at 90 °C were achieved in DES by microwave heating. Furthermore, microwave irradiation enabled the usage of a neat, solvent-free system, representing an initial proof of concept with productivities of up to 13.3 ± 2.3 g/(L·h).

Corrosion Engineering of Part-Per-Million Single Atom Pt1/Ni(OH)2 Electrocatalyst for PET Upcycling at Ampere-Level Current Density.

The plastic waste issue has posed a series of formidable challenges for the ecological environment and human health. While conventional recycling strategies often lead to plastic down-cycling, the electrochemical strategy of recovering valuable monomers enables an ideal, circular plastic economy. Here a corrosion synthesized single atom Pt1/Ni(OH)2 electrocatalyst with part-per-million noble Pt loading for highly efficient and selective upcycling of polyethylene terephthalate (PET) into valuable chemicals (potassium diformate and terephthalic acid) and green hydrogen is reported. Electro-oxidation of PET hydrolysate, ethylene glycol (EG), to formate is processed with high Faraday efficiency (FE) and selectivity (>90%) at the current density close to 1000mAcm-2 (1.444V vs RHE). The in situ spectroscopy and density functional theory calculations provide insights into the mechanism and the understanding of the high efficiency. Remarkably, the electro-oxidation of EG at the ampere-level current density is also successfully illustrated by using a membrane-electrode assembly with high FEs to formate integrated with hydrogen production for 500h of continuous operation. This process allows valuable chemical production at high space-time yield and is highly profitable (588-700$ton-1 PET), showing an industrial perspective on single-atom catalysis of electrochemical plastic upcycling.

Experimental and kinetic modelling studies for the design of fixed bed methanol reactor over CuZA catalyst

Direct conversion of CO2 via hydrogenation to value-added chemicals is a vital approach for utilising CO2 emitted into the atmosphere. In this paper, a critical analysis of reaction kinetic modelling studies is explored in a fixed bed reactor to improve methanol yield for different H2 to CO2 ratios by simulating a lab-scale reactor for adiabatic and isothermal conditions. The feed inlet temperature and pressure variations are applied to study the effect of both configurations on methanol production. The results show that the isothermal configuration yields 2.76% more methanol yield compared to the adiabatic reactor. The effect of H2 to CO2 molar ratios of 3, 6 and 9 on the performance of the catalyst and the influence of CO and CO2 hydrogenation is investigated with model simulations. The overall methanol yield is increased from 19.03% to 36.41% with increase in H2 to CO2 molar ratio from 3 to 9. Experiments are performed using commercial copper-based catalyst for different temperatures of 210, 230 and 250 °C at a pressure of 40 bar for H2/CO2 of 3 and GHSV of 720 h−1 as well as at optimal temperature of 250 °C and 50 bar with varying H2/CO2 of 3, 6, 9 for 3 g and 6 g catalyst. The maximum methanol yield of 2.53% and space time yield of 13.59 mg/gcat.h is obtained at H2/CO2 ratio of 9.

Gas-phase continuous synthesis of metal-organic framework-derived hybrid catalysts for combined CO2 and CO hydrogenation to methanol

Aerosol-based continuous synthesis for metal–organic framework (MOF) derived catalyst materials, in combination with real-time gas-phase electrophoresis for material characterization, is demonstrated for methanol production via combined CO2 and CO hydrogenation. Cu-based and Zn-based MOF colloids were prepared as the templates for the synthesis of Cu-ZnO catalysts supported on either Al2O3 or CeO2. The results showed the incorporation of real-time gas-phase electrophoresis enabled traceability of continuous catalyst production. Optimal selectivity of 90.52 %, and space–time yield of 7.50 mmol gcat−1h−1 were achievable in the methanol production. Interestingly, the space–time yield of methanol was shown to be linearly proportional to metal surface area of the catalyst. This study demonstrated significant advances in the continuous production of MOF-derived hybrid catalysts through aerosol-phase synthesis with real-time characterization. The high catalytic performance of the developed materials in the combined CO2 and CO hydrogenation to methanol bears promise for applications in the field of CO2 utilization.

Dilute Alloy Catalysts for the Synthesis of Isobutanol via the Guerbet Route: A Comprehensive Study

This study investigates the potential of bimetallic alloy catalysts, specifically Ni99Pt1, Cu99Ni1, Cu99Fe1, Fe99Pt1, and Fe99Pd1, for the synthesis of isobutanol via the Guerbet route. The catalysts were synthesized with a doping of 1 at% Ni, Fe, Pt, and Pd in the base metals Fe, Cu, and Ni. The catalytic properties of these bimetallic alloy catalysts were explored for their potential for promoting the Guerbet reaction. The study aims to test the usability of the theoretically predicted d-band values in the synthesized bimetallic catalysts, which were prepared by means of incipient wetness impregnation, and shows that doping amounts smaller than 1 at% already significantly improved the catalytic activity of the base metals. In particular, the doping of nickel with platinum yielded an effective catalyst for the synthesis of isobutanol via the Guerbet pathway. The Ni99Pt1/C catalyst from the presented experiments had the highest Space Time Yield (STY) and is, therefore, also a promising catalyst for the hydrogen-borrowing reactions class.

Titanium dioxide–supported mercury photocatalysts for oxidative removal of hydrogen sulfide from the air using a portable air purification unit

Photocatalytic removal of gaseous hydrogen sulfide (H2S) has been studied through the control of key process variables using a prototype air purifier (AP) fabricated with titanium dioxide (TiO2)-supported mercury. The performance of Hg/TiO2 systems, prepared with different Hg mass proportions over TiO2 (such as 0.1%, 1%, 2%, and 5%), is measured against 5 ppm H2S at 160 L min-1 under UV irradiation. Accordingly, their removal efficiency (RE) values after 360 s are 40.3%, 74.8%, 99.3%, and 99.9%, respectively (relative to 33.5% of AP (TiO2)). An AP with a 2% Hg/TiO2 unit achieves a clean air delivery rate of 32 L min-1 with kinetic reaction rate (r (at 10% RE)) of 0.774 mmol h-1 g-1, quantum yield of 2.19E-02 molecules photon-1, and space-time yield of 1.46E-04 molecules photon-1 mg-1. The superior photocatalytic performance of Hg/TiO2 is supported by superoxide anion and hydroxyl radicals formed in dry air and humid nitrogen (N2) environments, respectively. A density functional theory simulation suggests that the presence of oxygen vacancies should promote the disparities in the electronic structure to subsequently affect the reaction pathways and energetics. The presence of moisture enhances the robust formation of a mercury-OH bond to favorably yield β-mercury sulfide from H2S.

An artificial biocatalytic cascade for efficient synthesis of norepinephrine by combination of engineered L-threonine transaldolase with multi-enzyme expression fine-tuning

Norepinephrine, a kind of β-adrenergic receptor agonist, is commonly used for treating shocks and hypotension caused by a variety of symptoms. The development of a straightforward, efficient and environmentally friendly biocatalytic route for manufacturing norepinephrine remains a challenge. Here, we designed and realized an artificial biocatalytic cascade to access norepinephrine starting from 3, 4-dihydroxybenzaldehyde and L-threonine mediated by a tailored-made L-threonine transaldolase PsLTTA-Mu1 and a newly screened tyrosine decarboxylase ErTDC. To overcome the imbalance of multi-enzymes in a single cell, engineering of PsLTTA for improved activity and fine-tuning expression mode of multi-enzymes in single E.coli cells were combined, leading to a robust whole cell biocatalyst ES07 that could produce 100 mM norepinephrine with 99% conversion, delivering a highest time-space yield (3.38 g/L/h) ever reported. To summarized, the current study proposed an effective biocatalytic approach for the synthesis of norepinephrine from low-cost substrates, paving the way for industrial applications of enzymatic norepinephrine production.

Regulation of CuFeZn catalysts by K3PO4 and its effect on CO2 hydrogenation to C2+ alcohols

CO2 hydrogenation to C2+OH is an effective way to diminish CO2 emissions. Although challenges still exist in large-scale applications, CuFeZn catalysts attract extensive attention due to their low-cost. Herein, CuFeZn catalysts are modified by different amounts of K3PO4, (KP)0.1CuFeZn exhibits an excellent catalytic performance (total alcohols selectivity of 15.76 % at CO2 conversion of 38.10 %, C2+OH/ROH fraction of 94.23 %, and C2+ alcohols space–time-yield (STY) of 53.81 mg·mL−1·h−1). Combined with a series of characterization results, it is found that the effect of K3PO4 is complex, and the proportion of Fe2+, Cu0 and medium base shows perfect linear relation to STY of C2+OH. The significance level of the above three factors is in the following sequence: Cu0＞Fe2+＞medium base. The introduction of K3PO4 decreases the proportion of Fe2+ (active site for RWGS, the competitive reaction for C–C coupling) and increases the proportion of Cu+/(Cu++Cu0) (Cu+ is the active site for C–C coupling) due to the synergistic effect of Cu0 and Cu+, thereby improving the synthesis of C2+OH. Moreover, conversion of Fe0 to Fe3C or Fe3O4 plays negative roles in the stability of the catalysts.

The enhancing effect of Co2+ on propane non-oxidative dehydrogenation over supported Co/ZrO2 catalysts

Due to the increased production of shale gas containing propane, the share of non-oxidative propane dehydrogenation (PDH) in the large-scale production of propene is expected to continue to grow. There are, however, some ecofriendly and cost shortcomings associated with the currently applied Cr- or Pt-containing catalysts. Against this background, we present here Co/ZrO2 alternatives and reveal the fundamentals affecting their activity, which can be used for purposeful catalyst design. Co2+ species homogeneously distributed within the lattice of ZrO2 significantly increase the activity of coordinatively unsaturated Zr4+ for the PDH reaction. The increase is caused by accelerating both the cleavage of CH bonds in propane and the recombination of surface H species, with the latter reaction being the rate-limiting step. The best-performing catalyst outperformed an analogue of commercial K-CrOx/Al2O3 in terms of the rate of propene formation and demonstrated durable performance over a series of 10 PDH/regeneration cycles under industrially relevant conditions. It also outperformed most previously developed Co-containing catalysts in terms of propene productivity. The space–time yield of propene formation achieved at 57 % equilibrium propane conversion at 550 °C was 0.71 kg·h−1·kgcat-1.

Highly productive V/Zn-SiO2 catalysts for the selective oxidation of methane

The production of formaldehyde on industrial scale requires huge amounts of energy due to the involvement of reforming processes in combination with the demand in the megaton scale. Hence, a direct route for the transformation of (bio)methane to formaldehyde would decrease costs and puts less pressure on the environment. Herein, we report on the use of zinc modified silicas as possible support materials for vanadium catalysts and the resulting consequences for the performance in the selective oxidation of methane to formaldehyde. After optimization of the Zn content and reaction conditions, a remarkably high space-time yield of 12.4 kgCH2O·kgcat−1·h−1 was achieved. As a result of the extensive characterization by means of UV–vis, Raman, XANES and NMR spectroscopy it was found that vanadium is in the vicinity of highly dispersed zinc atoms which promote the formation of active vanadium species as supposed by theoretical calculations. This work presents a further step of catalyst development towards direct industrial methane conversion which may help to overcome current limitations in the future.

High performance Pt/Nb2W3O14 catalyst for glycerol valorization to 1,3-propanediol

Glycerol hydrogenolysis to 1,3-propanediol (1,3-PDO) is of significance in promoting the biomass valorization. To achieve the efficient conversion, the selective activation of the secondary C–O bonds in the glycerol is vital. In this work, we comparatively investigated the catalytic performances of Pt/Nb2W3O14 catalyst for glycerol hydrogenolysis controlled at the reacting conditions of 140 °C and 40 bar. Compared to Pt/WO3 and Pt/NbOx, the space–time yield (STY) of 1,3-PDO over Pt/Nb2W3O14 catalyst can be improved by a factor of 13, reaching 596.4 mg gcat−1 h−1. The cation ordering of Nb and W on atomic-scale were fully synergized their unique advantages, showing preferential adsorption of the secondary C–O bond under in-situ DRIFTS tracking. The prepared Nb2W3O14 is a tetragonal tungsten bronze (TTB) type complex oxides which can effectively promote the dispersion and reduction of Pt nanoparticles. Such strong interaction between Nb2W3O14 and Pt can coordinate the precise adsorption and activation of the secondary C–O bond, simultaneously triggering subsequent hydrogenation. Pt/Nb2W3O14 affords an ultrahigh activity in glycerol hydrogenolysis to produce 1,3-PDO, tripling the record productivity that was previously reported of these Pt-W based catalysts. This study reported the development of highly synergistic catalyst based on efficient and selective activation of the secondary C–O bond, which can be extended to catalyst design for other biomass valorization.

Efficient production of isomaltulose using engineered Yarrowia lipolytica strain facilitated by non-yeast signal peptide-mediated cell surface display.

Isomaltulose is a 'generally recognized as safe' ingredient and is widely used in the food, pharmaceutical and chemical industries. The exploration and development of efficient technologies is essential for enhancing isomaltulose yield. In the present study, a simple and efficient surface display platform mediated by a non-yeast signal peptide was developed in Yarrowia lipolytica and utilized to efficiently produce isomaltulose from sucrose. We discovered that the signal peptide SP1 of sucrose isomerase from Pantoea dispersa UQ68J (PdSI) could guide SIs anchoring to the cell surface of Y. lipolytica, demonstrating a novel and simple cell surface display strategy. Furthermore, the PdSI expression level was significantly increased through optimizing the promoters and multi-site integrating genes into chromosome. The final strain gained 451.7 g L-1 isomaltulose with a conversion rate of 90.3% and a space-time yield of 50.2 g L-1 h-1. The present study provides an efficient way for manufacturing isomaltulose with a high space-time yield. This heterogenous signal peptide-mediated cell surface display strategy featured with small fusion tag (approximately 2.2 kDa of SP1), absence of enzyme leakage in fermentation broth and ample room for optimization, providing a convenient way to construct whole-cell biocatalysts to synthesize other products and broadening the array of molecular toolboxes accessible for engineering Y. lipolytica. © 2024 Society of Chemical Industry.

A Ce-CuZn catalyst with abundant Cu/Zn-OV-Ce active sites for CO2 hydrogenation to methanol

CO2 hydrogenation to chemicals and fuels is a significant approach for achieving carbon neutrality. It is essential to rationally design the chemical structure and catalytic active sites towards the development of efficient catalysts. Here we show a Ce-CuZn catalyst with enriched Cu/Zn-OV-Ce active sites fabricated through the atomic-level substitution of Cu and Zn into Ce-MOF precursor. The Ce-CuZn catalyst exhibits a high methanol selectivity of 71.1% and a space-time yield of methanol up to 400.3 g·kgcat−1·h−1 with excellent stability for 170 h at 260 °C, comparable to that of the state-of-the-art CuZnAl catalysts. Controlled experiments and DFT calculations confirm that the incorporation of Cu and Zn into CeO2 with abundant oxygen vacancies can facilitate H2 dissociation energetically and thus improve CO2 hydrogenation over the Ce-CuZn catalyst via formate intermediates. This work offers an atomic-level design strategy for constructing efficient multi-metal catalysts for methanol synthesis through precise control of active sites.

Photocatalytic efficacy of air purifiers equipped with self-cleaning titanium dioxide xerogel coatings against gaseous formaldehyde: A study using DRIFTS and DFT analysis

In this research, the practical efficacy of a portable air purifier (AP) loaded with a self-cleaning titanium dioxide xerogel (TX) has been investigated for the photocatalytic degradation of formaldehyde (FA) from the air. The photocatalytic performance of the AP system is optimized through control on the synthesis variables (e.g., annealing temperatures (150–750°C), colloidal volume of photocatalysts in filter fabrication (1–10 mL), and process variables (e.g., air-circulation speeds (100-160 L/min), type of light sources (UVA vs. UVC), and FA concentrations (0.5–5 ppm)). The self-cleaning potential of the AP-TX system is validated with FA removal efficiencies of ≥96 % across diverse settings and over 10 repeated cycles. The optimum kinetic rate constant for FA (e.g., 0.0195 s−1) is attained by a TX-coated honeycomb filter annealed at 450°C based on a Langmuir–Hinshelwood first-order kinetic model. The high photocatalytic efficacy of the AP-TX system is supported further in terms of a clean air–delivery rate (CADR) of 19.57 L/min, a quantum yield (QY) of 1.93×10−3 molecules/photon, and a space–time yield (STY) of 2.57×10−2 molecules/photon/g. The formation of dioxymethylene and formate as intermediates of FA degradation is confirmed by diffuse reflectance infrared Fourier transform spectroscopy analysis (DRIFTS). The results derived from density functional theory (DFT) simulations also suggest that the photocatalytic degradation of FA should proceed endothermically. The overall findings of this research are expected to help establish advanced strategies for the fabrication of self-cleaning photocatalysts for air purification applications.

Mg enhanced the performance of Cu/ZnO/ZrO2 for CO2 hydrogenation to methanol and the mechanism investigation

Optimizing the microstructure of copper-based catalysts for CO2 hydrogenation to methanol is an attractive and widely reported strategy, but there are still certain barriers to improving both carbon dioxide conversion rate and methanol product selectivity. Herein, Cu/ZnO/ZrO2/MgO (CZZ1-xMx) catalysts were synthesized by co-precipitation method for CO2 hydrogenation to methanol. Furthermore, the structural features and reaction processes were systematically characterized by XRD, TEM, nitrogen adsorption/desorption, H2-TPR, CO2-TPD and in-situ DRIFT. The results showed that Mg species optimized the microstructure of the catalyst, increased the dispersion of active species and constructed appropriate basic sites. This further enhanced the capture of reactive species and improved the CO2 hydrotreating to methanol reaction performance, which was accompanied by a simultaneous increase in CO2 conversion and methanol yield. It could be convinced that the highest space time yield (STY) of methanol (305.3 gMeOH kgcat−1 h−1) was obtained at 220 °C, WHSV = 18,000 mL gcat−1 h−1 and 3 MPa (XCO2 = 7.28%, SMeOH = 71.8%) for the optimized CZZ0.8M0.2 catalyst, which exhibited twice the CO2 conversion than Cu/ZnO/ZrO2. This work elaborated a scheme for the preparation of efficient methanol catalysts. providing reference for the research of CO2 hydrogenation to methanol process.

Continuous Cu/keto-ABNO catalyzed aerobic oxidation of ethyl lactate to ethyl pyruvate in a micro-packed bed reactor: Process optimization and reaction kinetics

Pyruvic acid and its esters are increasingly utilized as precursors for synthesizing antioxidations or dietary supplement in the pharmaceutical industry. The selectivity of oxidation step holds paramount importance in the synthesis route. In this study, a continuous micro-packed bed reactor platform is developed to determine the kinetic parameters of Cu/keto-ABNO catalyzed aerobic ethyl lactate (EL) oxidation. Initially, various operating parameters including types of nitroxyl radical, phase ratio, pressure and temperature were systematically studied to reveal their effect on the oxidation performance. The Cu/keto-ABNO catalyzed aerobic oxidation method can efficiently transform EL to ethyl pyruvate (EP) without hydrolysis. Comparing the aerobic oxidation performances in batch reactors, the reaction time was shortened to 1/15 and the space time yield was increased by 6 times in micro-packed bed reactors, which is due to the enhanced gas–liquid mass transfer. Finally, the kinetic parameters of this reaction were promptly determined and the supplementary validation experiments were conducted to confirm the applicability and accuracy of the kinetic model.

DoE-based medium optimization for improved biosurfactant production with Aureobasidium pullulans.

Polyol lipids (a.k.a. liamocins) produced by the polyextremotolerant, yeast-like fungus Aureobasidium pullulans are amphiphilic molecules with high potential to serve as biosurfactants. So far, cultivations of A. pullulans have been performed in media with complex components, which complicates further process optimization due to their undefined composition. In this study, we developed and optimized a minimal medium, focusing on biosurfactant production. Firstly, we replaced yeast extract and peptone in the best-performing polyol lipid production medium to date with a vitamin solution, a trace-element solution, and a nitrogen source. We employed a design of experiments approach with a factor screening using a two-level-factorial design, followed by a central composite design. The polyol lipid titer was increased by 56% to 48gL-1, and the space-time yield from 0.13 to 0.20gL-1h-1 in microtiter plate cultivations. This was followed by a successful transfer to a 1L bioreactor, reaching a polyol lipid concentration of 41gL-1. The final minimal medium allows the investigation of alternative carbon sources and the metabolic pathways involved, to pinpoint targets for genetic modifications. The results are discussed in the context of the industrial applicability of this robust and versatile fungus.

Single-step propane transformation on vanadium-supported catalyst revealed by operando DRS UV–vis study

The present study investigated the influence of silica support texture on the catalytic performance of VOx/silica catalysts in the selective oxidation of propane. Two- and three-dimensional mesoporous materials, SBA-15 and MCF, were synthesized using hydrothermal methods to create different pore structures. Vanadium (approximately 5 wt%) was incorporated into the silica matrices (MCF, SBA-15) and SiO2 (used as a reference system) through impregnation. The surface composition, valence state, and reducibility of the VOx species accommodated in VOx/silica catalysts were characterized using X-ray diffraction (XRD), diffuse reflectance ultraviolet–visible spectroscopy (UV–vis DRS), temperature-programmed reduction with hydrogen (H2-TPR), X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared spectroscopy (FT-IR) techniques. The catalytic properties of the catalysts were evaluated in the propane selective oxidation conducted at 470 °C, utilizing a mixture of oxidants (N2O and O2). Propane oxidation resulted in propane conversion of 34 %, propene selectivity of 49 %, and propene oxide selectivity of 20 %, corresponding to space–time yield of propene reaching 37 gC3H6 kgcat−1·h−1and propene oxide equal to 20 gPO kgcat−1h−1. The textural properties of the support materials noticeably influenced the stability of the catalysts. The vanadium catalysts supported on three-dimensional mesocellular silica foams (MCF) demonstrated superior activity, achieving turnover frequency (TOF) values of 9.0 × 10−4 s−1 for propene and 6.67 × 10−4 s−1 for propene oxide (PO). The unique three-dimensional ultra-large pores of the MCF material facilitated the generation of significant amounts of propene oxide, along with propene, while minimizing the formation of CO, CO2, and other oxygen-bearing by-products. Operando UV–vis studies supported by two-dimensional correlation analysis (2D COS) were employed to explain the diversity in the catalytic performance of VOx/silica catalysts. It has been found that the oligomeric vanadium species are the active sites in propane oxidative dehydrogenation, whereas the monomeric forms participate in propene oxide formation. Moreover, the reduction of V5+ to V4+ and even V3+ was identified as a crucial step in the reaction.A reaction scheme has been proposed based on catalytic experiments and spectroscopic insights.

Local In-O-Pd Lewis acid-base pair boosting CO2 selective hydrogenation to methanol

CO2 hydrogenation into valuable chemicals is industrially essential but very challenging since CO2 is chemically inert and the selectivity is difficult to control. Here, we design and construct In2O3 supported Pd single atoms (Pd1/In2O3 SAC) to boost the methanol yield (254.8 gmethanol·gPd−1·h−1) and selectivity (99.4 %) via the Lewis acid-base pair, which activates the CO2 and forms the intermediate species of formate (HCOO*). The comprehensive experimental and theoretical results confirm that the local Lewis acid-base pair is composed of the isolated Pd atom coupling with the adjacent O and In atoms. The space–time yield (STY) of methanol over Pd1/In2O3 SAC is around 1.7 times higher than the best reported catalysts under comparable conditions. The strategy of constructing local Lewis acid-base pairs with single-atom site and metal oxides reported in this work opens new avenues to develop highly selective catalysts for CO2 utilization.

In2O3 crystal phase variation on In2O3/Co3O4 to boost CO2 hydrogenation to methanol

In2O3/Co3O4 catalysts with various crystal structure of In2O3 were successfully prepared by means of regulating the amount of citric acid, and were applied for CO2 hydrogenation to methanol to understand the structure-activity relationship. With the increase of citric acid content in the impregnation process, hexagonal In2O3 (h-In2O3) is gradually transformed into cubic In2O3 (c-In2O3). The interaction and electron transfer between c-In2O3 and Co3O4 are stronger than those between h-In2O3 and Co3O4. In the In2O3/Co3O4 catalysts prepared with citric acid, phase transformations were observed under reaction conditions of 4 MPa and 300 °C. Initially, h-In2O3 transitions into c-In2O3. Concurrently, there is a transformation of In2O3 and Co3O4 into metallic cobalt (Co0) and the compound Co3InC0.75. Except for h-In2O3/Co3O4 containing mixed h-In2O3 and c-In2O3, In2O3 in all other catalysts exists in the form of c-In2O3. Owing to stronger interaction between c-In2O3 and Co0, dissociated hydrogen atoms diffuse more easily from the metallic Co0 to c-In2O3 to produce more oxygen vacancies, accompanied with the formation of more inactive Co3InC0.75 (70 wt% for c-In2O3/Co3O4 vs 58 wt% for h-In2O3/Co3O4). However, h-In2O3/Co3O4 has stronger adsorption ability of CO to improve methanol selectivity. Thus, it can be observed that the CO2 conversion and methanol selectivity of the catalyst are directly related to the In2O3 crystal phase for In2O3/Co3O4 catalysts. To be specific, h-In2O3/Co3O4 has the higher selectivity of methanol, while c-In2O3/Co3O4 exhibits the higher conversion of CO2 and methanol space-time yield.