Diffuse Reflectance Infrared Fourier Transform Research Articles

Preparation of Single-Helical Curdlan Hydrogel and Its Activation with Coagulation Factor G.

β-1,3-glucans are a kind of natural polysaccharide with immunomodulatory, antitumor, and anti-inflammatory properties. Curdlan, as the simplest linear β-1,3-glucan, possesses a variety of biological activities and thermogelation properties. However, due to the complexity and variability of the conformations of curdlan, the exact structure-activity relationship remains unclear. We prepare a chemically crosslinked curdlan hydrogel with the unique single-helical skeleton (named S gel) in 0.4 wt% NaOH at 40 °C, confirmed by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). X-ray diffractometry (XRD) data show that S gel maintains the single-helical crystal structure, and the degree of crystallinity of the S gel is ~24%, which is slightly lower than that of the raw powder (~31%). Scanning electron microscopy (SEM) reveals that S gel has a continuous network structure, with large pores measuring 50-200 μm, which is consistent with its high swelling property. Using the 13C high-resolution magic angle spinning nuclear magnetic resonance (HRMAS NMR) method, we determine that most of the single-helical skeleton carbon signals in the swollen S gel are visible, suggesting that the single-helical skeleton of S gel exhibits fascinating mobility at room temperature. Finally, we reveal that the binding of S gel to coagulation Factor G from tachypleus amebocyte lysate increases and saturates at 20 μL tachypleus amebocyte lysate per mg of S gel. Our prepared S gel can avoid the transformation of curdlan conformations and retain the bioactivity of binding to coagulation Factor G, making it a valuable material for use in the food industry and the pharmaceutical field. This work deepens the understanding of the relationship between the single-helical structure and the activity of curdlan, promoting the development and application of β-1,3-glucans.

Unveiling the Mechanism of Plasma-Catalyzed Oxidation of Methane to C2+ Oxygenates over Cu/UiO-66-NH2.

Nonthermal plasma (NTP) offers the potential for converting CH4 with CO2 into liquid products under mild conditions, but controlling liquid selectivity and manipulating intermediate species remain significant challenges. Here, we demonstrate the effectiveness of the Cu/UiO-66-NH2 catalyst in promising the conversion of CH4 and CO2 into oxygenates within a dielectric barrier discharge NTP reactor under ambient conditions. The 10% Cu/UiO-66-NH2 catalyst achieved an impressive 53.4% overall liquid selectivity, with C2+ oxygenates accounting for ∼60.8% of the total liquid products. In situ plasma-coupled Fourier-transform infrared spectroscopy (FTIR) suggests that Cu facilitates the cleavage of surface adsorbed COOH species (*COOH), generating *CO and enabling its migration to the surface of Cu particles. This surface-bound *CO then undergoes C-C coupling and hydrogenation, leading to ethanol production. Further analysis using CO diffuse reflection FTIR and 1H nuclear magnetic resonance spectroscopy indicates that in situ generated surface *CO is more effective than gas-phase CO (g) in promoting C-C coupling and C2+ liquid formation. This work provides valuable mechanistic insights into C-C coupling and C2+ liquid production during plasma-catalytic CO2 oxidation of CH4 under ambient conditions. These findings hold broader implications for the rational design of more efficient catalysts for this reaction, paving the way for advancements in sustainable fuel and chemical production.

Effect of sulfation on the catalytic performance of Mn-Co composite oxide catalyst for the selective catalytic reduction of NOx by NH3

The effect of sulfation on the catalytic performance of Mn-Co composite oxide catalyst for the selective catalytic reduction of NOx by NH3 (NH3-SCR) has been investigated. Different concentrations of SO2 have been used to sulfate Mn-Co composite oxide catalyst. The catalyst sulfated with 30 ppm SO2 showed the widest activity temperature window, over which 80% NOx conversion was obtained in the temperature range of 80–350 °C. The sulfation leads to the appropriate redox property of Mn-Co composite oxide, thus improving the N2 selectivity. Meanwhile, the sulfation contributes to the generation of more Brønsted acid sites, which is crucial for the enhanced activity. In situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS) demonstrated that the adsorbed NH3 species on both Lewis acid and Brønsted acid sites, monodentate nitrite, bidentate nitrate and cis-nitrite species are the reactive intermediates in the NH3-SCR reaction. This study provides an idea for the regulating the activity temperature window of NH3-SCR catalyst to adapt to its practical application.

Evaluating the properties of deinking paper sludge from the Mediterranean area for recycling in local areas as a soil amendment and to enhance growth substrates

AbstractRecycling of paper generates large quantities of paper sludge that is rich in organic matter and can be exploited to counteract organic matter loss in agricultural soils, especially in some geographical areas, such as the Mediterranean. In order for deinking paper sludge (DPS) to be recycled, chemical and physical characterizations are required along with an analysis of possible contaminants. DPS from Italy and Tunisia, resulting from various deinking processes, were analyzed and compared in terms of their chemical properties (pH, OM, total N, C/N ratio, mineral nutrients, and trace metals), surface chemistry [diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy and Fourier-transform infrared (FTIR) spectroscopy], and thermal stability [thermogravimetric analysis (TGA)]. The aim was to improve their use as amendments in soils or growth substrates. Elemental analysis revealed higher carbon concentrations in the Tunisian DPS and similar nitrogen contents, high mineral nutrient levels, and potentially toxic trace element levels below the limits allowed for soil amendment. No evidence was found for the presence of organic pollutants, pathogens, or toxic heavy metals. Surface chemical analysis revealed comparable materials rich in aromatic, phenolic, aliphatic, and polysaccharide structures along with clay minerals and carbonates. The thermal analysis revealed similar decomposition temperatures for the organic matter. Practical implications of the results are discussed, highlighting the similar properties of sludge following ink removal by different processes and the need to integrate the N content in order to be able to employ sludge as an amendment in soil and growing media. Given the similarity of the compositions of the materials, appropriate DPS management is key to improving soil fertility, reducing paper waste disposal, and implementing a circular economy in the Mediterranean, where climate change is having a significant impact.

Revealing the roles of Zr on enhanced H2-SCR performances on Pt/TiO2 catalyst

The development of Hydrogen Internal Combustion Engine (H2-ICEs) to replace conventional fuel engines is expected to be an effective way to reduce CO2 emissions, but some NOx emitted from the H2-ICEs still should be eliminated by the selective catalytic reduction of NOx with H2 (H2-SCR). Large amount of platinum oxide existed on Pt/TiO2 leads to its low H2-SCR activity. In contrast, the Zr-modified Pt/TiO2 catalysts exhibit a higher NOx conversion and N2 selectivity in a wider temperature window (100–180 °C) than those of Pt/TiO2. The appropriately weakened strong interaction between Pt and TiO2 by Zr induces more Pt0 species, which are active sites for the activation of NOx and H2 in H2-SCR reaction. More oxygen vacancies caused by the formation of Zr-Ov-Ti3+ bands involve in the activation of NOx and the adsorption of nitrates (NOx−) species. Furthermore, in situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTs) demonstrates that Pt/ZrxTi1-x catalysts possess more adsorbed NOx− species and a faster reduction rate for them. Monodentate and bridged nitrates are considered to be more reactive with H2 than bidentate nitrates at relatively low temperatures. This work provides directions for the development of high-performance H2-SCR catalysts and the modulation of the conversion temperature.

The construction of iron-based catalysts encapsulated by graphite for CO2 hydrogenation to light olefins

Developing efficient catalytic materials and unveiling the active factors are significant for selective hydrogenation of CO2 to light olefins (C2–4=). Herein, Fe3O4-FeCx nanoparticles coated by graphite without other doped elements were synthesized successfully. The optimal catalyst exhibited CO2 conversion of 48.0%, C2–4= space–time yield of 29.0 mmol·g−1·h−1, and a stability of 100 h (3.0 MPa, 320 °C, and GHSV = 12000 mL·g−1·h−1). The core–shell structure derived from the strong interaction between the phenolic hydroxyl group of resin and iron ions, as well as the encapsulation of the copolymer P123. The characterization results revealed that the size of core–shell particles and thickness of graphite layers could be regulated by P123, which affected the conversion of CO2 and products distribution significantly. Moreover, the combined results of quasi in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTs) and Raman spectra suggested small particle size and thin graphite shell strengthen the adsorption and conversion of CO2, playing an important role in the formation of light olefins. This work proposes a simple and feasible synthesis strategy to construct Fe3O4-FeCx particles encapsulated by graphite shell, which provides insights into catalysts design and the reaction mechanism of CO2 conversion to light olefins.

Mechanism of Interfacial Molecular Interactions Reveals the Intrinsic Factors for the Highly Enhanced Sensing Performance of Ag-Loaded Co3O4.

The noble metal-loaded strategy can effectively improve the gas-sensing performances of metal oxide sensors. However, the gas-solid interfacial interactions between noble metal-loaded sensing materials and gaseous species remain unclear, posing a significant challenge in correlating the physical and chemical processes during gas sensing. In this study, in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and in situ Raman spectroscopy were conducted to collaboratively investigate the interfacial interactions involved in the ethanol gas-sensing processes over Co3O4 and Ag-loaded Co3O4 sensors. In situ DRIFTS revealed differences in the compositions and quantities of sensing reaction products, as well as in the adsorption-desorption interactions of surface species, among Co3O4 and Ag-loaded Co3O4 materials. In parallel, in situ Raman spectroscopy demonstrated that the ethanol atmosphere can modulate the electron scattering of Ag-loaded Co3O4 materials but not of raw Co3O4. In situ experimental results revealed the intrinsic reason for the highly enhanced sensing performances of the Ag-loaded Co3O4 sensors toward ethanol gas, including a decreased optimal working temperature (from 250 to 150 °C), an improved gas response level (from 24 to 257), and accelerated gas recovery dynamics. This work provides an effective platform to investigate the interfacial interactions of sensing processes at the molecular level and further advances the development of high-performance gas sensors.

Furfural adsorption on V2O5 surface: A combined experimental-theoretical study

The adsorption of furfural on the V2O5 surface was investigated using experimental and theoretical methods. In situ Diffuse Reflectance Infrared Fourier-Transform Spectroscopy results show the presence of physi- and chemi-sorption phenomena, where trans-furfural is mostly chemisorbed at the beginning of the adsorption process. These results are in agreement with theoretical DFT results, as the most thermodynamically favored configurations corresponds to the chemisorbed trans-furfural (T1) and cis-furfural (C1) with binding energies of −1.83 and −2.05 eV.

Ce-based three-dimensional mesoporous microspheres with Mn homogeneous incorporation for toluene oxidation

Ce-based three-dimensional (3D) mesoporous microspheres with Mn homogeneous incorporation were synthesized. The CeMn-0.4, characterized by a Ce/Mn molar ratio of 6:4, demonstrated exceptional catalytic activity and stability. The formation of CeMn solid solution strengthened the Ce-Mn interaction, yielding higher concentrations of Ce3+ and Mn4+. Mn4+ initiated toluene preliminary activation owing to its robust oxidative properties, while Ce3+ contributed to oxygen vacancy generation, enhancing the activation of gaseous oxygen and lattice oxygen mobility. Integrating experiments and Density Functional Theory (DFT) calculations elucidated the oxygen reaction mechanisms. A portion of oxygen was converted into surface reactive oxygen species (Oads) that directly oxidized toluene. Additionally, the presence of oxygen vacancies promoted the participation of oxygen in toluene oxidation by converting it into lattice oxygen, which was crucial for the deep oxidation of toluene. Diffuse Reflectance Fourier Transform Infrared Spectroscopy (DRIFTS) indicated the accumulation of benzene-ring intermediates on the catalyst surface hindered continuous toluene oxidation. Thus, the abundant oxygen vacancies in CeMn-0.4 played a pivotal role in sustaining the oxidation process by bolstering the activation of gaseous oxygen and the mobility of lattice oxygen.

Construction of an Electron Capture and Transfer Center for Highly Efficient and Selective Solar-Light-Driven CO2 Conversion.

Exploring high-efficiency photocatalysts for selective CO2 reduction is still challenging because of the limited charge separation and surface reactions. In this study, a noble-metal-free metallic VSe2 nanosheet was incorporated on g-C3N4 to serve as an electron capture and transfer center, activating surface active sites for highly efficient and selective CO2 photoreduction. Quasi in situ X-ray photoelectron spectroscopy (XPS), soft X-ray absorption spectroscopy (sXAS), and femtosecond transient absorption spectroscopy (fs-TAS) unveiled that VSe2 could capture electrons, which are further transferred to the surface for activating active sites. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and density functional theory (DFT) calculations revealed a kinetically feasible process for the formation of a key intermediate and confirmed the favorable production of CO on the VSe2/PCN (protonated C3N4) photocatalyst. As an outcome, the optimized VSe2/PCN composite achieved 97% selectivity for solar-light-driven CO2 conversion to CO with a high rate of 16.3 μmol·g-1·h-1, without any sacrificial reagent or photosensitizer. This work offers new insights into the photocatalyst design toward highly efficient and selective CO2 conversion.

SO2- and H2O-tolerant catalytic reduction of NOx at low temperatures through shielding ceria-based catalyst from poisoning: An efficient protection mechanism

Improving SO2/H2O resistance at low temperatures is a key challenge for industrial applications of NH3-SCR catalysts. Herein, a novel catalyst with remarkable low-temperature NH3-SCR activity and strong SO2/H2O resistance was designed by loading MoOx protective layer over porous kit-CeO2. The in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) coupled with basic characterization techniques were utilized to further elucidate the underlying mechanisms, and a dynamic balance between the deposition and decomposition of ammonia bisulfate was captured over porous kit-CeO2. Highly dispersed MoOx species pre-adsorbed with NH3 significantly curtailed the adsorption of NOx molecules, and the catalytic reaction over MoOx/kit-CeO2 primarily followed by the Eley-Rideal mechanism. At 250 °C, in the presence of SO2 and H2O, the Ce-O-Mo pairing site was almost unaffected and the super SO2- and H2O-tolerant property originated from the facilitated decomposition of ammonium bisulfate (ABS) and the shielding effect of Mo protective layer on SO2/H2O. This study provided an important guidance to the application of ceria-based catalysts for environmental control within low-temperature operations in non-power industries such as glass, steel, cement manufacturing, etc.

Enhanced performance of attapulgite-supported g-C3N4 for photocatalytic CO2 reduction

As a new type of non-metallic semiconductor photocatalyst, g-C3N4 has great potential in photocatalytic CO2 reduction. However, due to the low catalytic activity, it is still far from industrial reality for such applications. Herein, this work introduces attapulgite (ATP) into the photocatalyst system of g-C3N4. Additionally, ATP/Au-CN was obtained through the photodeposition method. The photocatalytic reduction ability of the photocatalyst for CO2 is enhanced. The photoelectric tests show that loading of ATP can promote the separation and migration of photocarriers. Through BET testing, it was found that the alkaline pore structure on the surface of ATP not only captures CO2, but also increases the specific surface area of the composite. According to the experimental results, the possible photocatalytic mechanism was verified by in-situ diffuse reflection infrared Fourier transform (DRIFT) spectral analysis and DFT calculation. This work provides new guidance for the construction of high efficient photocatalyst systems using abundant ATP as a support.

Efficient Lead Removal by Assembly of Bio-Derived Ellagate Framework, Which Enables Electrocatalytic Reduction of CO2 to Formate.

Lead (Pb) poisoning and CO2-induced global warming represent two exemplary environmental and energy issues threatening humanity. Various biomass-derived materials are reported to take up Pb and convert CO2 electrochemically into low-valent carbon species, but these works address the problems separately rather than settle the issues simultaneously. In this work, cheap, natural ellagic acid (EA) extracted from common plants is adopted to assemble a stable metal-organic framework (MOF), EA-Pb, by effective capture of Pb2+ ions in an aqueous medium (removal rate close to 99%). EA-Pb represents the first structurally well-defined Pb-based MOF showing selective electrocatalytic CO2-to-HCOO- conversion with Faradaic efficiency (FE) of 95.37% at -1.08V versus RHE. The catalytic mechanism is studied by 13CO2 labeling, in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and theoretical calculation. The use of EA-Pb as an electrocatalyst for CO2 reduction represents a 2-in-1 solution of converting detrimental wastes (Pb2+) as well as natural resources (EA) into wealth (electrocatalytic EA-Pb) for addressing the global warming issue.

Enhanced mineralization capacity for photocatalytic toluene degradation over Ag3PO4/TiO2: the critical role of oxygen vacancy

Mesoporous disk-like Ag3PO4/TiO2 heterojunctions with rich oxygen vacancies using MIL-125(Ti)-derived TiO2 as support were prepared for photocatalytic degradation toward toluene. The low amount of Ag3PO4 into Ag3PO4/TiO2-10 (1.7 wt% Ag3PO4) greatly improved the toluene mineralization capacity up to 95 %, which was much higher than that of the TiO2 alone (41.3 %). In-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) directly verified that the benzene ring was opened rapidly by the Ag3PO4/TiO2-10, while intermediate (like benzaldehyde and benzoic acid) accumulation occurred using pristine TiO2 as photocatalyst. It was demonstrated that Z-scheme heterojunction was formed between Ag3PO4 and TiO2, in which the photo-induced electrons were transferred from conduction band (CB) of the Ag3PO4 to valence band (VB) of the TiO2 under photoexcitation, boosting the generation of reactive oxygen species and inhibiting the photocorrosion of Ag3PO4. Interestingly, quantitative structure-activity relationship suggested that oxygen vacancies as crucial active sites both activated molecular oxygen and captured the photo-induced electrons to form •O2− that dominated in toluene mineralization. This work proved that the construction of Z-scheme heterojunction between MIL-125(Ti)-derived TiO2 and Ag3PO4 solved the inactivation of TiO2 and photocorrosion of Ag3PO4 in photocatalysis, highlighting the role of oxygen vacancy in determining the active species and mineralization degree for photocatalytic toluene elimination.

The impact of indium and manganese modifiers on the catalytic properties of zinc-alumina propane dehydrogenation catalysts

Supported zinc-containing catalysts are considered as a viable alternative to the currently-deployed Cr-based (toxic) and Pt-based (costly) catalysts of alkane dehydrogenation, as reflected also in the increased number of reports related to the Zn-based catalysts in recent years. Here, we present a study of alumina-supported Zn-In and Zn-Mn propane dehydrogenation (PDH) catalysts prepared by the tailored methods. Specifically, the introduction of zinc relied on the chemical vapor deposition (CVD, using Zn vapor) onto alumina or alumina-supported indium or manganese materials, the latter two prepared by the impregnation of alumina with aqueous solutions of the respective metal nitrates followed by the calcination and hydrogen treatment. Alternatively, both zinc and indium were introduced by the co-impregnation of alumina with aqueous zinc and indium nitrates. The PDH tests revealed that the “dilution” of the active Zn2+ surface sites with In+ cations lead to a significant improvement in the catalytic performance, i.e., the introduction of In+ increased propene selectivity and attenuated the undesirable cracking and hydrogenolysis side reactions as well as decreased coke formation. In contrast, Mn2+ cations improved the catalytic properties of Zn2+ surface sites to a lesser extent than In+ cations. All prepared catalysts were characterized by DRIFT (diffuse reflectance infrared Fourier transform) spectroscopy of the adsorbed CO and H2 probe molecules. It was found that surface In+ and Mn2+ cations affect Zn2+ sites (electronic and geometric effect), which can be assessed from the position of the IR bands of zinc hydridespecies, formed due to the heterolytic hydrogen dissociation on the Zn2+ active sites. The effect of In and Mn dopants also was confirmed by the molecular DFT simulation.

Engineering of Thickness Tunable 2D Graphdiyne Film to ZnO Nanowalls via Nanospace‐Confined Synthesis Promotes NO2 Gas Sensing Performance

Achieving rapid response and recovery rates at low operating temperatures for NO2 is desirable for the application of sensors in industrial safety. In this study, we integrate a thickness tunable 2D graphdiyne (GDY) film into ZnO nanowalls (GDY/ZnO) via thermal evaporation of GDY, where ZnO nanowalls are used as the template to confine the growth space of the GDY film. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) is used to reveal the transformation process of NO2. Ultraviolet photoemission spectroscopy (UPS) is utilized to analyze changes about the energy band of the materials. Density functional theory (DFT) calculations explain the reason for the selectivity of the samples to NO2. The scanning electron microscopy (SEM) results demonstrate that the thickness of the GDY film with a specific mesoporous structure (25‐53 nm) increases as the thermal evaporation temperature rises from 400 to 800°C.The representative ZG-600, synthesized with a thickness of 46 nm via thermal evaporation at 600°C, exhibits superior NO2 sensing performance. This is evidenced by its ultrahigh response (13.86, at 100 ppm and 150°C) and rapid response/recovery speeds (150 s/198 s), outperforming the ZnO sensor (198 s and 326 s). Moreover, it offers remarkable stability.

Exploiting the continuity equation for mechanistic understanding through spatially resolved SSITKA-DRIFTS: The role of carbonyls in RWGS over Pt/CeO2

Insight into mechanisms of heterogeneously catalyzed reactions holds importance in the development and optimization of new catalytic materials. Yet, the approaches often used in such investigations heavily rely on assumptions concerning the reactor and kinetics. Herein we report a new kind of kinetic investigation taking CO2 hydrogenation reaction, specifically the reverse water–gas shift (RWGS) reaction over 3 wt% Pt/CeO2, as an exemplifying case. The reported approach is based on spatially resolved steady-state isotopic transient kinetic analysis (SSITKA) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) identifying gaseous/surface species and their spatial variations along the reactor. This approach allows accurate evaluation of reaction mechanism by identifying correlations among the concentrations of gaseous/surface species and by quantitative description of their spatial variations by a kinetic model. Spatially resolved SSITKA-DRIFTS experiments show carbonate decomposition via a Pt-bound carbonyl to be the main route towards the production of carbon monoxide. Further kinetic modeling of the spatially resolved data confirms this mechanism proposal, and points to the production of water as the rate-limiting step.

DIFFUSE REFLECTANCE INFRARED FOURIER TRANSFORM SPECTROSCOPIC METHOD FOR ESTIMATION OF NERATINIB IN PHARMACEUTICALS: APPLICATION TO ANALYTICAL QUALITY BY DESIGN AND GREENNESS ASSESSMENT

In this research paper, we report an eco-friendly diffuse reflectance infrared fourier transform spectroscopic (DRIFTS) method for quantifying neratinib. The systematic method development was performed as per the recent analytical quality by design concept. The critical method variables such as resolution (cm-1) and the total number of scans were investigated using a central composite design to determine their influence on the measurements at 2204.64 cm-1. The method was valid over a linear (R2 > 0.99) range of 5-30 µg mg-1 of neratinib, with adequate accuracy (recovery > 100 %) and precision (RSD < 1%). Afterwards, the method greenness assessment was performed using the Analytical Greenness Metric and White Analytical Chemistry approach to establish the overall green sustainability of the current method. In a nutshell, the different functional groups of the drug were identified, and neratinib was quantified from the pharmaceutical tablets with optimum method robustness.

Heterogeneous reaction of NO2 with hematite: The effects of UV irradiation, O2 and relative humidity

Heterogeneous reactions on mineral dust surfaces are increasingly considered important in the removal of gaseous pollutants and the formation of secondary aerosols. Although the heterogeneous reaction of NO2 on the hematite surface has been investigated in many previous studies, little is known about the reaction of NO2 with hematite under ambient conditions. In this work, heterogeneous reactions of NO2 with hematite at 298 K were investigated via a coated-wall flow tube reactor and in situ diffuse reflectance Fourier transformed infrared spectroscopy (DRIFTS). The influence of UV illumination, relative humidity (RH) and O2 on the uptake coefficients and adsorption amount of NO2, as well as the nitrate formation on the hematite surface, has been analyzed comprehensively. UV irradiation shows a significant effect on the true uptake coefficient (γBET), which increases from 2.00 × 10−6 to 4.76 × 10−6 in the N2 stream and 1.32 × 10−6 to 4.07 × 10−6 in the air stream under dry conditions (∼0.3 % RH). RH (in the range of 0–67 %) exhibits an inhibitory effect on the adsorption of NO2 on the hematite surface because of the competition between NO2 and water molecules, that is, γBET and adsorption amount of NO2 decrease with an increase in RH under both the dark and light reaction conditions. Meanwhile, both the γBET and adsorption amount of NO2 on hematite decrease in the air stream compared to those in N2 conditions. In addition, the results from the DRIFTS experiments indicate that the presence of UV irradiation promotes the conversion of NO2 to nitrate and both the RH and O2 suppress the nitrate formation. From this research, the heterogeneous reactions between NO2 with mineral dust under ambient conditions will be better understood.

Morphologically tuned CuO-ZnO-CeO2 catalyst for CO2 hydrogenation to methanol.

Morphologically modified composite CuO-ZnO-CeO2 catalysts were synthesized using a single-step hydrothermal technique. The study highlights the influence of solvent on the structural and physico-chemical properties of the catalysts. Various techniques, such as XRD, FE-SEM, BET, XPS, and H2-TPR, were used to analyze the catalyst properties. Among the synthesized materials, the catalyst, prepared with a N,N-dimethyl formamide (DMF)-to-metal nitrates ratio of 20 (named as CZC-1), showed enhanced active sites in the form of surface features such as nanowire-like morphology, large surface area, low crystallite size, increased oxygen vacancies, and high CuO dispersion. A bench-scale fixed-bed flow reactor was used to examine the catalytic performance of the catalysts. At 225 °C reactor temperature, 30 bar reactor pressure, and with a space velocity of 6000 cm3 gcat-1 h-1, the CZC-1 catalyst showed 13.6% CO2 conversion and 74.1% methanol selectivity. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) analysis confirmed the carbonate-formate-methoxy reaction pathway for methanol formation using the CZC-1 catalyst.