Diffuse Reflectance Research Articles

Visible light sensitive BiVO4–TiO2 nanocomposites for photocatalytic dye degradation

Abstract The hydrothermal approach was used to prepare visible light active BiVO4–TiO2 nanosheet composites in varying molar ratios. The photoluminescence (PL) spectrum, X-ray photoelectron spectroscopy (XPS), UV-Visible Diffuse Reflectance Spectroscopy (DRS), Transmission electroscopy (TEM), Brunauer-Emmett-Teller (BET) and field emission scanning electron microscopy (FESEM), were used to analyze the photocatalysts and composites. Photocatalytic activity of BiVO4–TiO2 composites was investigated by decolorizing methylene blue. Out of four different molar ratio BiVO4–TiO2 composites with a molar ratio of 3:1 BiVO4 TiO2 composite showed enhanced photocatalytic activity which is further proved by photoluminescence investigation of coumarin and Scavenger test. The DRS of BiVO4 TiO2 composite showed red shift in optical absorption. The enhanced photocatalytic activity is due to minimizing electron hole recombination by making composite with TiO2.

Synthesis, Structure, and Properties of Dion–Jacobson Double‐Layered Perovskites A′SmNb2O7 (A′=Rb, K, Na, Li, H)

AbstractDion‐Jacobson‐type layered perovskite compounds A′SmNb2O7 (A′=Rb, K, Na, Li, H) were synthesized using solid‐state and ion‐exchange methods. While the parent solid‐state product RbSmNb2O7, has previously been studied, the ion‐exchanged compounds were obtained and studied for the first time. The phase and chemical purity of the compounds were confirmed by X‐ray diffraction (XRD) and energy‐dispersive X‐ray spectroscopy (EDX). The crystal structures of RbSmNb2O7 (I2 cm, a=0.54356(1) nm, b=0.53935(1) nm, c=2.1891(5) nm), KSmNb2O7 (I2 cm, a=0.53660(7) nm, b=0.54481(6) nm, c=2.1527(1) nm) and LiSmNb2O7 (B2 cm, a=0.54546(4) nm, b=0.53567(4) nm, c=2.04582(5) nm) were refined using the Rietveld method. Polyhedral distortions in these structures have been studied in detail. The thermal behavior of the compounds has been determined using differential thermal analysis (DTA), revealing that A′=Na, Li and H compounds are metastable hydrates, while A′=Rb and K compounds are stable. The optical band gap, valence band edge, and conduction band edge potentials of the compounds obtained were calculated using diffuse reflection spectroscopy data. A photocatalytic experiment was performed on the degradation of methylene blue under ultraviolet light. All of the samples obtained showed some asctivity in the reaction of dye photooxidation.

Humic Substances from Waste-Based Fertilizers for Improved Soil Fertility

This research explores how different organic waste transformation methods influence the production of humic substances (HSs) and their impact on soil quality. Using olive and orange wastes as substrates, the study compares vermicomposting, composting, and anaerobic digestion processes to determine which method produces the most humic-substance-rich products. The characterization of HSs in each product included analyses of total organic carbon (TOC), humic and fulvic acid content, humification rate, humification degree, and E4/E6 ratio, with HSs extracted using potassium hydroxide (KOH) and analyzed via Diffuse Reflectance Infrared Fourier-Transform (DRIFT) spectroscopy to assess structural complexity. The results revealed that the chemical composition of the input materials significantly influenced the transformation dynamics, with orange by-products exhibiting a higher humification rate and degree. Vermicomposting emerged as the most efficient process, producing fertilizers with superior humic content, greater microbial biodiversity, and enhanced cation exchange capacity, thus markedly improving soil quality. Composting also contributed to the stabilization of organic matter, albeit less effectively than vermicomposting. Anaerobic digestion, by contrast, resulted in products with lower levels of HSs and reduced nutrient content. Aerobic processes, particularly vermicomposting, demonstrated the most rapid and effective transformation, producing structurally complex, stable humus-like substances with pronounced benefits for soil health. These findings underscore vermicomposting as the most sustainable and efficacious approach for generating HS-rich organic fertilizers, presenting a powerful alternative to synthetic fertilizers. Furthermore, this study highlights the potential of organic waste valorization to mitigate environmental pollution and foster circular economy practices in sustainable agriculture.

Gallium Methylene Ga8(CH2)12 on Mesoporous Silica

Gallium methylene Ga8(CH2)12 was grafted onto large‐pore mesoporous silica SBA‐15500 and mesoporous silica MCM‐41500 with smaller mesopores, each thermally pretreated at 500 °C. For comparability reasons, trimethylgallium was employed as a grafting reagent. The hybrid materials Ga8(CH2)12@SBA‐15500, GaMe3@SBA‐15500, Ga8(CH2)12@MCM‐41500 and GaMe3@MCM‐41500 were characterized by ICP‐OES, N2 physisorption, elemental analysis, solid‐state 1H/13C/29Si NMR spectroscopy and diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy. To gain further insight into potential surface species, the molecular compound Ga8(CH2)12 was treated with excess (eight equivalents) of HOSi(OtBu)3, which gave the dimeric species [GaMe2{OSi(OtBu)3}]2, being isolable also from the reaction of GaMe3 with one equivalent of silanol. The hybrid materials revealed high metal contents and surface species with intact Ga–CH2–Ga linkages as proposed by NMR spectroscopy and their reactivity toward benzophenone.

Tunable Optical Properties and Relaxor Behavior in Ni/Ba Co-Doped NaNbO3 Ceramics: Pathways Toward Multifunctional Applications

In this study, Ni/Ba co-doped NaNbO3 ceramics (NBNNOx) were synthesized using a solid-state method to explore the effects of Ni2+ and Ba2+ ion substitution on the structural, optical, and dielectric properties of NaNbO3. X-ray diffraction (XRD) confirmed that the ceramics retained an orthorhombic structure, with crystallinity improving as the doping content (x) increased. Significant lattice distortions induced by the Ni/Ba co-doping were observed, which were essential for preserving the perovskite structure. Raman spectroscopy revealed local structural distortions, influencing optical properties and promoting relaxor behavior. Diffuse reflectance measurements revealed a significant decrease in band gap energy from 3.34 eV for undoped NaNbO3 to 1.08 eV at x = 0.15, highlighting the impact of co-doping on band gap tunability. Dielectric measurements indicated relaxor-like behavior at room temperature for x = 0.15, characterized by frequency-dependent anomalies in permittivity and dielectric loss, likely due to ionic disorder and structural distortions. These findings demonstrate the potential of Ni/Ba co-doped NaNbO3 ceramics for lead-free perovskite solar cells and other functional devices, where tunable optical and dielectric properties are highly desirable.

Incorporation of a Binuclear Cobalt Complex into MOFs for Photocatalytic CO2 Reduction with H2O as an Electron Donor.

The development of molecular composite photocatalysts for cost-effective, sacrificial-reagent-free CO2 reduction is desirable but challenging. Herein, we employed an in situ encapsulation strategy to encapsulate the binuclear cobalt complex (Co2L) within NH2-MIL-125 and synthesized a range of MOF-based composites with varying cobalt content for photocatalytic CO2 reduction. The photocatalytic results showed that the catalytic performance increased with the increase in Co2L content, reaching a rapid CO generation rate of 27.95 μmol·g-1·h-1, over 5 times that of bare NH2-MIL-125, with water as the electron donor instead of any organic sacrificial agent. This composite catalyst effectively harnesses the advantages of both molecular catalysts and MOFs, leveraging the superior catalytic activity of molecular catalysts while also capitalizing on the light absorption and water oxidation capabilities of MOFs, resulting in a remarkable ability for photocatalytic CO2 reduction. The photocatalytic mechanism involving electron transfer and CO2 activation has been revealed by photoluminescence spectroscopy, in situ X-ray photoelectron spectroscopy, in situ diffuse reflectance infrared Fourier transform spectroscopy, and other control experiments.

La-supported SnO2–CaO composite catalysts for efficient malachite green degradation under UV–vis light

This study presents the development and optimization of La@SnO2–CaO composite catalysts for efficient photocatalytic degradation of malachite green dye in aqueous solutions under UV–vis light irradiation. The catalysts were prepared via conventional incipient-wetness impregnation and thoroughly characterized using advanced analytical techniques, including X-ray diffraction, Fourier transform infrared spectroscopy, UV–vis diffuse reflectance spectroscopy, N2 adsorption–desorption analysis, and scanning electron microscopy. To optimize photodegradation efficiency, the effects of three independent factors were systematically investigated using response surface methodology: Temperature, pH, and Sn/Ca molar ratio. Our results reveal optimal conditions for maximum dye degradation: pH 7, Sn/Ca molar ratio of 0.33, and a process time of 35 min, resulting in a maximum photodegradation efficiency of 98.80% for malachite green dye. Notably, visible light exhibited a more pronounced effect on dye degradation compared to UV light over time, with visible light achieving 25% greater dye removal after 60 min of illumination. Furthermore, the catalyst showed excellent recyclability, retaining 85% of its initial activity after five consecutive cycles. These findings contribute significantly to the development of sustainable methods for dye removal from wastewater and highlight the potential of La@SnO2–CaO composite catalysts in environmental remediation processes, particularly in treating textile industry effluents.

Controllability of optical, electrical, and magnetic properties of synthesized Cd-doped MgFe2O4 nanostructure

This study explores the synthesis of cadmium-magnesium co-doped magnesium ferrite (Mg1+xCdxFe2–2xO4, 0.00 ≤ x ≤ 0.30, Δx = 0.05) via a citric acid-assisted sol-gel auto-combustion method. X-ray diffraction (XRD) analysis revealed crystal structure changes due to Cd and Mg co-doping, with the 0.25 Cd sample showing the smallest crystallite size and highest lattice strain. High-resolution transmission electron microscopy (HRTEM) confirmed the nanostructure and largest surface area for this sample. Diffuse reflectance spectra, analyzed using the Kubelka-Munk relation, indicated that the 0.25 Cd sample had the lowest energy gap (2.08 eV), supported by band position calculations. Electrical conductivity and charge transport mechanisms were examined at various temperatures. Magnetization studies showed reduced saturation magnetization at x = 0.25, ascribed to cation distribution changes and spin canting, with coercivity and anisotropy decreasing with higher Cd content. Overall, the 0.25 Cd sample exhibited optimized optical, electrical, and magnetic properties due to its distinct microstructure.

The global well-posedness of the relativistic Boltzmann equation with hard potentials and diffuse reflection boundary condition in bounded domains

The global well-posedness of the relativistic Boltzmann equation with hard potentials and diffuse reflection boundary condition in bounded domains

Theoretical and experimental investigation of BaY2(MoO4)4:xSm3+ phosphors

In this paper, the novel BaY2(MoO4)4:xSm3+ phosphors with strong red emission and high thermal stabilization were prepared by a conventional method of high temperature solid state reaction in air atmosphere. Morphology, phase purity, element distribution, UV–Vis–NIR diffuse reflectance spectroscopy (DRS), and luminescence properties were investigated in detail. The crystal structure of the BaY2(MoO4)4 host was refined with the aid of the Rietveld refinement method by the GSAS program. The electronic band structure and phonon dispersion were performed using plane-wave density functional theory (DFT). The prepared BaY2(MoO4)4:Sm3+ phosphor exhibits excellent red emission under near-ultraviolet excitation. Strong red emission intensity and high thermal stability suggest potential application in backlighting or phosphor-covered white light-emitting diodes (pc-LEDs).

Construction of Chiral Covalent Organic Frameworks Through a Linker Decomposition Chiral Induction Strategy for Circularly Polarized Light Detection

AbstractExploring new strategies for construction of chiral covalent organic frameworks (COFs) is of paramount importance yet remains a challenge. Herein, we report the rational design and construction of chiral COFs through a linker decomposition chiral induction (LDCI) strategy. Three pairs of azine‐linked chiral COFs are successfully synthesized by the condensation reactions of C3‐symmetric 4,4′,4′′‐(1,3,5‐triazine‐2,4,6‐triyl)tribenzaldehyde (Tz) with flexible chiral dihydrazide linkers derived from malic acid, aspartic acid and tartaric acid, respectively. Remarkably, upon complete or partial decomposition from flexible chiral dihydrazides to hydrazine during COF synthesis, the homochirality of these COFs, originating from the single‐handedness conformation of propeller‐like Tz cores, is well preserved. Such a stereoselective chiral memory realized via the LDCI strategy is confirmed by time‐dependent powder X‐ray diffraction (PXRD), Fourier transform infrared (FT‐IR) and diffuse reflectance circular dichroism (DRCD). Moreover, the resultant azine‐linked chiral COFs are used as the active materials to fabricate photodetectors to directly distinguish circularly polarized light (CPL), showing impressive recognition performances on the identification of left‐handed circularly (LHC) and right‐handed circularly (RHC) polarized lights. Notably, the residual undecomposed flexible chiral linkers within the COFs are found to be conducive to improving the polarization discrimination ratio. This work highlights LDCI as a new and effective strategy for constructing homochiral COFs with promising future in chiral optical application.

Phytomediated synthesis of WO3 nanoparticles using Solanum lycopersicum fruit extract for enhanced photocatalytic activity of 2,4-dichlorophenol

ABSTRACT In the present study, bio-citric acid/tungsten oxide (WO3) (BCAWO) nanoparticles (NPs) were prepared by using Solanum lycopersicum fruit extract as a reducing as well as a capping agent. The photocatalysts were characterized by UV–vis diffuse reflection spectroscopy, powder X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectrometry (EDS), high-resolution transmission electron microscopy, and photoluminescence spectroscopy techniques. Diffraction peaks in the XRD spectrum were identified as the crystal planes of crystalline tungsten oxide. The BCAWO had an average size of 23.14 nm. For W–O bonds, the Fourier transform infrared spectrum displays the vibrational peak at 671.23 cm−1. A prominent absorption band was observed at 268 nm, indicating the 1.2 eV bandgap. Under xenon (Xe) lamp irradiation, the synthesized BCAWO nanoparticles showed notable photocatalytic degradation of 2,4-dichlorophenol (2,4-DCP), with a degradation rate of 96%. With BCAWO concentrations of 2.5 g/L, pH of 4, reaction period of 180 min, and 2,4 DCP concentration of 10 mg/L, the degradation of 2,4-DCP had the highest efficacy, 96%. The degradation of phenols in wastewater may be facilitated by using the green WO3 nanoparticles as a photocatalyst, according to the results.

Construction of Chiral Covalent Organic Frameworks Through a Linker Decomposition Chiral Induction Strategy for Circularly Polarized Light Detection

AbstractExploring new strategies for construction of chiral covalent organic frameworks (COFs) is of paramount importance yet remains a challenge. Herein, we report the rational design and construction of chiral COFs through a linker decomposition chiral induction (LDCI) strategy. Three pairs of azine‐linked chiral COFs are successfully synthesized by the condensation reactions of C3‐symmetric 4,4′,4′′‐(1,3,5‐triazine‐2,4,6‐triyl)tribenzaldehyde (Tz) with flexible chiral dihydrazide linkers derived from malic acid, aspartic acid and tartaric acid, respectively. Remarkably, upon complete or partial decomposition from flexible chiral dihydrazides to hydrazine during COF synthesis, the homochirality of these COFs, originating from the single‐handedness conformation of propeller‐like Tz cores, is well preserved. Such a stereoselective chiral memory realized via the LDCI strategy is confirmed by time‐dependent powder X‐ray diffraction (PXRD), Fourier transform infrared (FT‐IR) and diffuse reflectance circular dichroism (DRCD). Moreover, the resultant azine‐linked chiral COFs are used as the active materials to fabricate photodetectors to directly distinguish circularly polarized light (CPL), showing impressive recognition performances on the identification of left‐handed circularly (LHC) and right‐handed circularly (RHC) polarized lights. Notably, the residual undecomposed flexible chiral linkers within the COFs are found to be conducive to improving the polarization discrimination ratio. This work highlights LDCI as a new and effective strategy for constructing homochiral COFs with promising future in chiral optical application.

Isothermal conversion of methane to methanol over Cu-CHA using different oxidants

Methane oxidation to methanol in cyclic processes using CuO-zeolites has traditionally employed O2 and N2O as oxidants. This study explores the use of Cu-CHA zeolite, demonstrating that CO2 can substitute O2 in an isothermal reaction at 400 °C, analogous to previous findings using Cu-MAZ. The use of in situ UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS) and density functional theory (DFT) theoretical calculations identified the formation of a binuclear copper hydroxide complex, Z-[CuOH-HOCu]2+-Z, on the Cu-CHA. Initial treatment using CO2 led to marginally superior catalytic activity, compared to the use of O2 alone, indicating the stability of the Z-[CuOH-HOCu]2+-Z complex against self-reduction at 400 °C. In subsequent cycles, activation with O2 facilitated the oxidation of adsorbed methanol, yielding water and reconstituting the active sites. Conversely, activation with CO2 led to the partial desorption of methanol, precluding water production and subsequent catalyst regeneration. The findings suggested that both O2 and CO2 activations necessitated a post-reaction water extraction step, followed by thermal treatment to replenish the active sites. Importantly, the results indicated that CO2 could be used as a viable alternative oxidant to O2 in this catalytic process, potentially enhancing the sustainability of industrial methanol production.

Enhancing the Light‐Driven Photocatalytic Degradation Activity of ZnO Nanoparticles With the Synergistic Incorporation of Er and Tb Elements

ABSTRACTThe existence of organic pollutants in aqueous media has become a vital issue and a critical threat to human health, where organic toxic dyes represent the major contaminants in wastewater. Over the past few years, photocatalytic techniques have garnered a lot of interest in dye removal from wastewater. In this study, a series of ErxTbxZn1 − 2xO nanophotocatalysts (where x = 0.00, 0.01, 0.03, and 0.05) were synthesized and coded as ZET0, ZET1, ZET2, and ZET3 NPs (nanoparticles). The chemical and physical characteristics of the NPs were investigated using Fourier‐transform infrared spectroscopy (FT‐IR), X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), energy‐dispersive X‐ray (EDX) spectroscopy, and ultraviolet–visible diffuse reflectance spectroscopy (UV–vis DRS) techniques. Further examination by performing photocatalytic experiments, ZET1 NPs demonstrated effective Rhodamine B (RhB) dye degradation within 60 min. It was found that the kinetic rate constant values were 0.008, 0.097, 0.050, and 0.040 min−1 for ZET0, ZET1, ZET2, and ZET3 NPs, respectively. Aside from their remarkable photocatalytic degradation efficiency, these ZET1 photocatalysts are highly stable even after five consecutive cycles. In addition, the active species test revealed that the primary oxidation species involved in the photocatalytic process are holes (h+) and hydroxyl radicals (•OH), and a possible photocatalytic mechanism for degrading RhB by ZET1 photocatalysts was tentatively proposed. The enhancement of the photocatalytic degradation efficiency is due to the low recombination rate of photogenerated charge carriers, as well as a strong synergistic impact of Tb, Er, and ZnO components. Thus, the current study could offer a versatile strategy for the design of new and effective nano photocatalysts for wastewater purification in the future.

Regional differences in soil stable isotopes and vibrational features at depth in three California grasslands

AbstractThere are major gaps in our understanding of how Mediterranean ecosystems will respond to anticipated changes in precipitation. In particular, limited data exists on the response of deep soil carbon dynamics to changes in climate. In this study we wanted to examine carbon and nitrogen dynamics between topsoils and subsoils along a precipitation gradient of California grasslands. We focused on organic matter composition across three California grassland sites, from a dry and hot regime (~ 300 mm precipitation; MAT: 14.6 $$\boldsymbol{^\circ{\text{C}} }$$ ∘ C ) to a wet, cool regime (~ 2160 mm precipitation/year; MAT: 11.7 $$\boldsymbol{^\circ{\text{C}} }$$ ∘ C ). We determined changes in total elemental concentrations of soil carbon and nitrogen, stable isotope composition (δ13C, δ15N), and composition of soil organic matter (SOM) as measured through Diffuse Reflectance Infrared Fourier Transformed Spectroscopy (DRIFTS) to 1 m soil depth. We measured carbon persistence in soil organic matter (SOM) based on beta ($${\varvec{\beta}}$$ β ), a parameter based on the slope of carbon isotope composition across depth and proxy for turnover. Further, we examined the relationship between δ15N and C:N values to infer SOM’s degree of microbial processing. As expected, we measured the greatest carbon stock at the surface of our wettest site, but carbon stocks in subsoils converged at Angelo and Sedgwick, the wettest and driest sites, respectively. Soils at depth (> 30 cm) at the wettest site, Angelo, had the lowest C:N and highest δ15N values with the greatest proportion of simple plant-derived organic matter according to DRIFTS. These results suggest differing stabilization mechanisms of organic matter at depth across our study sites. We infer that the greatest stability was conferred by associations with reactive minerals at depth in our wettest site. In contrast, organic matter at our driest site, Sedgwick, was subject to the most microbial processing. Results from this study demonstrate that precipitation patterns have important implications for deep soil carbon storage, composition, and stability.

Optical and surface properties of Schiff base ligands and Cu(II) and Co(II) complexes

Objectives. To study the transition of electrons in 1,2-phenyl(4’-carboxy)benzylidene Schiff base ligand and transition metal ions, optical properties, as well as the surface chemistry of supported transition metals using diffuse reflectance spectroscopy (DRS); to study the roughness and morphology of the Schiff base ligand and its complexes using atomic force microscopy (AFM).Methods. DRS, AFM, and Fourier-transform infrared spectroscopy instruments were used to identify electron transitions, optical properties, and surface morphology in Schiff base ligands and their complexes.Results. The DRS revealed the d–d transitions and charge transfer shifts of all compounds, and helped identify the structure of the ligand. One of the optical properties studied was the energy gap calculation of the ligand and its complexes. The copper complex exhibited more semiconducting behavior with surface morphology properties such as surface roughness parameters lower than those of the ligand and the cobalt complex. This can be attributed to the smaller size of the copper atom, as well as lower electron transitions compared to the cobalt complex and the square planar bonding shape.Conclusions. In Schiff base ligands, the reflectance spectrum bands reveal three electron transitions: n→π*, π→π*, and σ→σ* transitions. In cobalt complexes, four transitions are indicated: 4A2(F)→4T1(F), 4A2(F)→4T1(P), charge transfer bands, and tetrahedral geometry. Copper complexes exhibit three transitions: 2B1g→2A1g, 2B1g→2Eg, and charge transfer bands, with a square planar geometry for their structure. The energy gap calculations were 2.42, 2.29, and 2.30 eV, respectively. In the case of the SH ligands, copper complexes, and cobalt complexes, all compounds exhibited semiconductor properties. However, the complexes displayed increased conductivity due to the influence of the metal and coordination structure.

Near-Infrared Spectroscopy for Growth Estimation of Spirulina platensis Cultures

The present study proposes the use of Near-Infrared (NIR) spectroscopy as a rapid method for estimating the growth of Spirulina platensis cultures, avoiding any sample manipulation or pretreatment. NIR spectroscopy in diffuse reflectance mode was used on culture volumes as received, with Principal Component Analysis (PCA) and Partial Least Squares (PLS) linear regression, for developing the calibration model in the wavelength range of 1000–2500 nm, in order to choose the appropriate wavelength to estimate the growth of the microalga. The local reflectance maximum at 1062.6 nm, connected with reduced water absorption and scattering effects by the microalga, was identified from PCA as the positive peak in the first loading plot, correlating diffuse reflectance with dilution levels. The calibration curve of diffuse reflectance at 1062.6 nm in response to dilution presented strong linearity, supported by a coefficient of determination (R2) of 0.995. Cross-validation of NIR spectra with a S. platensis culture confirmed the method’s reliability, showing that the growth follows an exponential pattern. The study shows that diffuse reflectance NIR spectroscopy can be used for the rapid monitoring of Spirulina platensis growth.

Rational design of ZnO/SrTiO3 S-scheme heterojunction for photo-enhanced piezocatalytic hydrogen production

Photopiezocatalysis have been frequently investigated for hydrogen evolution reactions in recent years. Herein, ZnO, SrTiO3 and ZnO/SrTiO3 S-scheme heterojunction were investigated for photo/piezocatalytic hydrogen production. Piezocatalytic hydrogen production under ultrasonic vibration by using ZnO, SrTiO3 and ZnO/SrTiO3 was obtained as 270 µmol g-1h−1, 200 µmol g-1h−1 and 1265 µmol g-1h−1, respectively. In addition, ZnO/SrTiO3 S-scheme heterojunction showed 2200 µmol g-1h−1 photopiezocatalytic hydrogen production under simultaneous exposure to white LED light and ultrasonic sound. ZnO/SrTiO3 heterojunction displayed significantly higher hydrogen production rate due to the decreased charge recombination, increased charge transfer with strong piezoelectric polarization and internal electrical field. The piezoelectric effect of ZnO/SrTiO3 heterojunction is also confirmed by piezoresponse force microscope technique with butterfly and phase hysteresis loops. Also, piezoelectric coefficient of ZnO/SrTiO3 found about 2-folds higher than those of their pristine forms. Electron transfer and reaction mechanism of ZnO/SrTiO3 and activity differences are confirmed by advanced optical and electrochemical techniques such as diffuse reflectance spectroscopy, electronic impedance spectroscopy, Mott-Schottky calculation and chronoamperometry. The whole electrochemical measurements have been performed with or without mechanical stress and light irradiation, which signify their band bending properties, electron transfer mechanism and catalytic activities.

B-containing ionic liquid modified SBA-15 for CO2-epoxide coupling reaction metal-free catalysis

A novel external-skeleton B-containing ionic liquid modified SBA-15 catalyst BBN-Imi-SBA-15-I (BBN denotes borabicyclo[3.3.1]nonane, Imi represents imidazolium ionic liquid) was successfully constructed by a post-modification method for efficiently catalyzing CO2-epoxide coupling reaction under both metal- and solvent-free conditions. 5BBN-Imi-SBA-15-I (5 refers to the molar ratio of Si to B), thanks to its synergistic effects of Lewis acid, weak base sites from tertiary amine and quaternary ammonium, hydrogen bond group and nucleophilic group, displayed good catalytic activity with 97 % product yield and 99 % selectivity at 100 °C, 2 MPa in the absence of cocatalyst. The obtained catalyst demonstrated good recyclability during six consecutive catalytic runs, also presented generality for various mono-substitute epoxides. Through in-situ NH3 diffuse reflectance infrared Fourier transform spectroscopy (NH3-DRIFTS) characterization, the Lewis acidity of organo-boron was verified. Besides, kinetics research also proved the positive effect of multiple active components on efficient catalysis under milder conditions over SiO2-based metal-free catalysts.