Rate Constants For Reduction Research Articles

Green preparation of nitrogen vacancies enriched g-C3N4 for efficient photocatalytic reduction of CO2 and Cr(VI)

Introducing vacancies has emerged as one of the valid strategies to modulate the photocatalytic performance of graphitic carbon nitride (g-C3N4). Introduction of nitrogen vacancies into g-C3N4 can create defect energy levels and trap electrons, consequently accelerating the separation of e−/h+ pairs and effectively boosting photocatalytic activity. Nitrogen vacancies can also serve as adsorption active sites, enhancing the adsorption capacity of the catalyst towards the target molecule (CO2). In this study, a series of g-C3N4 with abundant nitrogen vacancies were prepared using a green and facile strategy using sodium bisulfite treatment. Successful introduction of nitrogen vacancies endows with the photocatalyst more active sites, optimizes the band structure, significantly boosts the separation of photoexcited carriers, thereby remarkably enhancing photocatalytic CO2 and Cr(VI) reduction. On the 11CN photocatalyst (0.5 g g-C3N4 was treated by 11 g sodium bisulfite), the generation rate of CO and CH4 is 5.74 μmol·g−1·h−1 and 1.30 μmol·g−1·h−1, respectively, which is 3.19 times and 8.29 times higher than those on the reference g-C3N4 (CO: 1.37 μmol·g−1·h−1, CH4: 0.14 μmol·g−1·h−1). Under irradiation by three distinct monochromatic lights, the apparent quantum yield (AQY) of 11CN is also superior to that of the reference g-C3N4. Moreover, photocatalytic Cr(VI) reduction experiments were performed on the catalysts to demonstrate the universality of the catalysts The results show that the photocatalytic reduction rate constant of Cr(VI) by 11CN is 1.79 times higher than that over the reference g-C3N4. Stability of the catalyst was verified through cycling experiments, and the samples exhibit promising practical application prospect. The mechanism of photocatalytic CO2 reduction and the transformation pathway of intermediate products were elucidated using in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). This study introduces a new strategy of introducing nitrogen vacancies into g-C3N4-based photocatalytic materials, providing an effective approach to enhance the photocatalytic activity of g-C3N4 in photocatalytic CO2 and Cr(VI) reduction.

Polarized Bimetallic Site Synergy in Ionic Structures of Cu(II), Fe(III), and Mn(III) Porphyrins: Electrochemistry and Catalytic Hydrogenation of Nitroaromatics.

Binuclear catalytic sites attained in a controlled way with complementary and cooperative metal ion centers are highly relevant in the development of new or enhanced catalytic processes. Herein, binuclear sites carrying Fe(III), Cu(II), or Mn(III) metal ions with a polarized structure have been prepared using the ionic self-assembly of oppositely charged metalloporphyrins. Binary porphyrin structures (BIPOS) have been prepared based on metalloporphyrin cations carrying pyridinium or methylpyridinium groups in conjugation with metalloporphyrin anions carrying sulfonatophenyl groups. BIPOS carrying [cation/anion] tecton pairs of [Cu/Fe], [Fe/Cu], [Cu/Cu], [Fe/Fe], [Mn/Fe], [Fe/Mn], and [Mn/Mn] have been compared. Electrochemical interaction and enhanced catalytic behavior are noticeable for BIPOS [Fe/Cu], [Fe/Fe], and [Mn/Fe] carrying a Fe center and [less electronegative/more electronegative] metal ion centers in the [cation/anion] porphyrin ionic pairs. For high-performance BIPOS, cyclic voltammograms showed a greater separation of the cathodic and anodic peaks, within ΔEp = 0.095-0.125 V, and the rate constants for the catalytic reduction of 4-nitrophenol were within k = 0.380-0.535 min-1/mg of catalyst, significantly superior to the related individual metalloporphyrins. Inverse heterobimetallic [Cu/Fe] and [Fe/Mn] and the homometallic BIPOS [Cu/Cu] and [Mn/Mn] were significantly less active or inefficient. A [Fe/Cu] material could be reused in at least 5 catalytic cycles, maintaining catalytic activity; the best catalysts were also active in the reduction of nitrobenzene to aniline in mild conditions (visible light, 30 °C, 0.5 mol % catalyst), and an [Fe/Fe] catalyst showed 100% aniline yield after 2 h.

Efficient photocatalytic CO2 and Cr(VI) reduction on carbon spheres/g-C3N4 composites with enriched nitrogen vacancies

In this study, carbon spheres (CS)/g-C3N4 composite materials were fabricated by a hydrothermal method, and the characterizations have confirmed the successful anchoring of CS onto the surface of g-C3N4, constructing enriched nitrogen vacancies during the synthesis process. The photocatalytic CO2 reduction activity of g-C3N4 is enhanced by all of these advantageous factors. The significant enhancement can be attributed to the tight interfacial interaction between CS and g-C3N4, which endows with the photocatalyst a larger specific surface area, higher light utilization efficiency and stronger capability for photoinduced charges separation. Furthermore, the presence of nitrogen vacancies further accelerates the separation and migration efficiency of photogenerated charges, provides additional active sites to promote the adsorption and activation of CO2 molecules, thereby effectively boosting the photocatalytic activity for CO2 reduction. The CO2 conversion rate on CS/g-C3N4 composite materials is higher than that on the reference g-C3N4. The apparent quantum yield (AQY) is also superior to that of the reference g-C3N4 under three different monochromatic light irradiations. The stability of the catalyst was verified through cycling experiments, indicating promising potential practical industrial application. The CO2 reduction mechanism and transformation pathways were elucidated using in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The photocatalytic reduction rate constant of Cr(VI) by 50CS/CN is 2.9 times higher than that by CN. This study introduces a facile approach for synthesizing g-C3N4-based photocatalytic materials, providing an interesting strategy to boost photocatalytic activity of g-C3N4 for photocatalytic CO2 and Cr(VI) reduction.

The screening of iron oxides for long-term transformation into vivianite to recover phosphorus from sewage

The reducibility of iron oxides, depending on their properties, influences the kinetics of dissimilatory iron reduction (DIR) during vivianite recovery in sewage. This study elucidated the correlation between properties of iron oxides and kinetics of DIR during the long-term transformation into vivianite, mediated by Geobacter sulfurreducens PCA and sewage. The positive correlation between surface reactivity of iron oxides and reduction rate constant (k) influenced the terminal vivianite recovery efficiency. Akaganeite with the highest adhesion work and surface energy required the lowest reduction energy (Ea), obtained the highest k of 1.36 × 10–2 day-1 and vivianite recovery efficiency of 43 %. The vivianite yield with akaganeite as iron source was 76–164 % higher than goethite, hematite, feroxyhyte, and ferrihydrite in sewage. The distribution of P with akaganeite during DIR in sewage further suggested a more efficient pathway of direct vivianite formation via bio-reduced Fe(II) rather than indirect reduction of ferric phosphate precipitates. Thus, akaganeite was screened out as superior iron source among various iron oxides for vivianite recovery, which provided insights into the fate of iron sources and the cycle of P in sewage.

Predicting Abiotic TCE Transformation Rate Constants—A Bayesian Hierarchical Approach

AbstractFe(II) minerals can mediate the abiotic reduction of trichloroethylene (TCE), a widespread groundwater contaminant. If reaction rates are sufficiently fast for natural attenuation, the process holds potential for mitigating TCE pollution in groundwater. To assess the variability of abiotic TCE reduction rate constants, we collected pseudo‐first‐order rate constants for natural sediments and rocks from the literature, as well as intrinsic (surface‐area‐normalized) rate constants of individual minerals. Using a Bayesian hierarchical modeling approach, we were able to differentiate the contributions of natural variability and experimental error to the total variance. Applying the model, we also predicted rate constants at new sites, revealing a considerable uncertainty of several orders of magnitude. We investigated whether incorporating additional information about sediment composition could reduce this uncertainty. We tested two sets of predictors: reactive mineral content (measured by X‐ray diffraction) combined with surface areas and intrinsic rate constants, or the extractable Fe(II) content. Knowledge of the mineral composition only marginally reduced the uncertainty of predicted rate constants. We attribute the low information gain to the inability to measure the (reactive) surface areas of individual minerals in sediments or rocks, which are subject to environmental factors like aqueous geochemistry and redox potential. In contrast, knowing the Fe(II) content reduced the uncertainty about the first‐order rate constant by nearly two orders of magnitude, because the relationship between Fe(II) content and rate constants is approximately log–log‐linear. We demonstrate how our approach provides estimates for the range of cleanup times for a simple example of diffusion‐controlled transport in a contaminated aquitard.

CO Oxidation Mechanism of Silver-Substituted Mo/Cu CO-Dehydrogenase - Analogies and Differences to the Native Enzyme.

The aerobic oxidation of carbon monoxide to carbon dioxide is catalysed by the Mo/Cu-containing CO-dehydrogenase enzyme in the soil bacterium Oligotropha carboxidovorans, enabling the organism to grow on the small gas molecule as carbon and energy source. It was shown experimentally that silver can be substituted for copper in the active site of Mo/Cu CODH to yield a functional enzyme. In this study, we employed QM/MM calculations to investigate whether the reaction mechanism of the silver-substituted enzyme is similar to that of the native enzyme. Our results suggest that the Ag-substituted enzyme can oxidize CO and release CO2 following the same reaction steps as the native enzyme, with a computed rate-limiting step of 10.4 kcal/mol, consistent with experimental findings. Surprisingly, lower activation energies for C-O bond formation have been found in the presence of silver. Furthermore, comparison of rate constants for reduction of copper- and silver-containing enzymes suggests a discrepancy in the transition state stabilization upon silver substitution. We also evaluated the effects that differences in the water-active site interaction may exert on the overall energy profile of catalysis. Finally, the formation of a thiocarbonate intermediate along the catalytic pathway was found to be energetically unfavorable for the Ag-substituted enzyme. This finding aligns with the hypothesis proposed for the wild-type form, suggesting that the creation of such species may not be necessary for the enzymatic catalysis of CO oxidation.

Assessment of abiotic reduction rates of organic compounds by interpretable structural factors and experimental conditions in anoxic water environments

For organic contaminants in lake sediments, aquifers, and anaerobic bioreactors, their reduction is one of the primary transformation paths in these anoxic water environments. A simple model is introduced to predict pseudo-first order rate constants (kobs) for the abiotic reduction of organic compounds featuring diverse reducible functional groups. It utilizes the largest experimental dataset of –log kobs, encompassing 59 organic compounds (278 data points). Unlike available complex quantitative structure–activity relationship (QSAR) methods, the novel approach requires both experimental conditions and structural parameters. In comparison to one of the available general QSAR methods, the new model demonstrates favorable performance. The average absolute deviation (AAD), absolute maximum deviation (ADmax), average absolute relative deviation (AARD%), and R-squared (R2) values of the estimated outputs for 54/5 training/test data sets of the new model are 0.641/1.761, 1.761/1.417, 20.52/83.87, and 0.797/0.949, respectively. On the other hand, the available general comparative QSAR method shows the AAD: 1.311/2.301, ADmax: 3.795/3.732, AARD%: 641.0/821.2, and R2: 0.003/0.447. For the test set, AAD, AARD%, ADmax, and R2 values for the new/comparative models are 0.649/2.403, 62.20/190.5, 1.215/3.732 and 0.974/0.789, respectively. In summary, the new model offers a straightforward approach for the manual calculation of –log kobs, demonstrating excellent goodness-of-fit, reliability, precision, and accuracy.

Spatial separation of photocarriers and selective adsorption on flower-like core-shell heterojunction of Cr(VI) imprinted polymer@BiOI for boosted photocatalytic Cr(VI) reduction

BackgroundConstructing heterojunction photocatalyst is a well-established strategy for enhancing photocatalytic Cr(VI) reduction due to the heightened separation and transfer of photocarriers. Whereas, aimless and random transfer of photocarriers and low photocarrier utilization rate deriving from the weak interface interaction between heterojunction and Cr(VI) are still limited the photocatalytic reduction performance of Cr(VI). MethodsHerein, a flower-like core-shell heterojunction photocatalyst was designed by wrapping a pyridine-based Cr(VI) imprinted polymer (PCIP) onto flower-like BiOI to achieve spatial separation of photocarriers and selective adsorption of Cr(VI), resulting in an outstanding photocatalytic reduction performance of Cr(VI). Significant findingsIn the core-shell heterojunction, photocarriers could be spatially separated, and then brought about high-efficient photocatalytic Cr(VI) reduction close to the selective adsorption sites of Cr(VI). After measurement, the optimal PCIP@BiOI core-shell heterojunction, polymerized for ≈30 min, exhibited a robust photocatalytic reduction performance of Cr(VI), without adding any free radical sacrifice agents. Within 1 h, the aqueous solution containing 100 mg/L of Cr(VI) could be completely removed, and the photocatalytic reduction rate constant of Cr(VI) was ≈20 times superior to BiOI. This study presents a methodology for designing core-shell heterojunction photocatalysts on the basis of inorganic/organic conjunction for environmental remediation of high concentrations of Cr(VI).

Interfacial engineering of 0D/2D CoMn2O4 nanoparticles/CdS nanosheets p-n heterostructures for boosted photocatalytic H2 production and U(VI) reduction

Developing effective heterojunction photocatalysts that efficiently separate charge carriers and improve light-harvesting capabilities is crucial in addressing energy and environmental issues. Herein, a unique nanocomposite photocatalyst is constructed by attaching CoMn2O4 nanoparticles onto 2D CdS nanosheets for H2 production and U(VI) reduction. The optimized 2% CoMn2O4/CdS nanocomposite showcases the highest photocatalytic H2 production efficiency, 5.8 times higher than CdS nanosheets. Additionally, the U(VI) reduction rate constant of 2% CoMn2O4/CdS is 0.0192 min−1, approximately 1.9 folds over the pristine CdS (0.0101 min−1). The exceptional photocatalytic performance toward photocatalytic H2 evolution and U(VI) reduction reactions directly result from the electronic integration between CoMn2O4/CdS p-n heterojunction, facilitated by the efficient photoexcited charge separation. Feasible photocatalytic mechanisms are proposed through experimental analyses and theoretical calculations. This study provides a straightforward method for designing effective CdS-based heterostructured photocatalysts, contributing to the advancement of solar-to-H2 conversion and environmental abetment.

Selenate reduction mediated by underpotentially deposited Cu on the low index faces of Au in aqueous perchloric acid

Underpotential deposited Cu on the low index faces of single crystal Au electrodes has been found to promote the reduction of selenate, SeO42−(aq),in 0.1 M HClO4 solutions, a behavior analogous to that reported earlier in our laboratory for polycrystalline Au (Strobl et al. J. Electrochem. Soc.2016,163 (13), H1066). Sequential potential step-linear scan voltammetry data collected for Au(111) film electrodes in solutions containing Cu2+(aq) in the μM range afforded evidence that the onset for the electrocatalytic activity occurs for Cu(UPD) coverages, θCu ≈ 0.18, the same value at which complementary microgravimetric data displayed a clear increase in mass. On this basis, a reaction mechanism has been proposed involving the initial reversible formation of an adsorbed adduct, we denote as Cu|SeO42−(ads), followed by a first order irreversible reduction to yield a yet to be identified species, which we denote as Cu|Se(ads), as the rate determining step. Support for this reaction scheme was obtained from numerical solutions of the coupled differential equations that govern the time evolution of Cu|SeO4−(ads) and Cu|Se(ads), yielding best agreement with the experimental data for values of the equilibrium constant for adduct formation and the adduct reduction rate constant of 2.5 × 106 cm3 mol−1, and 9.1 × 10−3 s−1, respectively. This unique electrocatalytic effect has been attributed to a shift in the potential of zero charge of the bare Au substrates induced by Cu(UPD), which promotes the adsorption of HSeO4−(aq) at potentials more negative than those found for the bare substrates, allowing access to overpotentials high enough for its activation and further reduction to ensue.

Reduction of Methylene Blue Using Silica Nanoparticles Obtained from Waste ZrC

AbstractThe study conducted an extraction of pure amorphous nano‐silica (SiO2 NP) from waste product at the ZrC factory. Various techniques such as TEM, SEM‐EDX, ICP, XRD, FTIR, BET, and DLS were utilized to synthesize and characterize the silica nanoparticle. The results showed successful production of pure amorphous silica, with no discernible difference in purity percentage between samples prepared with or without acidic pre‐treatment. It was found that the leaching temperature, process time, and reactant ratio all played a role in the production of nano‐silica. The ideal leaching temperature was determined to be 368 K, with an optimal process time of 2 h. The weight ratio of WPZF/NaOH that yielded the highest percentage of silica extraction was 9 : 10. Additionally, at pH 7, the nano‐silica exhibited the best specific surface area (BET) of 472.51 m2/g. The average size of the spherical nano‐silica, as determined by DLS, was approximately 38 nm. Furthermore, the produced nano‐silica was found to be an effective catalyst for the treatment of methylene blue (MB). MB could be degraded by more than 99 % of the initial concertation (10 mg/L) in the presence of NaBH4 within 16 min and rate constant of the catalytic reduction achieved as 0.134 min−1. These findings demonstrate the potential of amorphous nano‐silica as a valuable resource in various applications.

Comparative Study of Catalytic Activity of Recyclable Au/Fe3O4 Microparticles for Reduction Of 2,4-Dinitrophenol and Anionic, Cationic Azo Dyes.

We synthesized Au/Fe3O4 microparticles. Initially, citrate-capped Fe3O4 micro-sized particles were synthesized by the co-precipitation method with an excess amount of trisodium citrate. Gold ions were reduced on the surface of citrate-capped Fe3O4 and grew as gold sub-microparticles with an average diameter of 210 nm on the surface. The characteristic SPR peak of gold nanoparticles on the surface of Fe3O4 was detected at 584 nm, whereas the absorption in the near-infrared region was increased. SEM images has proved that the synthesized Au/Fe3O4 composite microparticles has an average diameter of 1.7 micrometers. The results of XRD patterns proved the existence of both crystal phases of Fe3O4 and Au particles. To investigate the catalytic activity, the reaction rate constant of reduction of 2,4-dinitrophenol (2,4-DNP) and degradation of Congo red (CR), and methylene blue (MB) with NaBH4 in the presence of Au/Fe3O4 catalyst was monitored by UV-Vis spectroscopy. The initial reaction rate constant calculated from the change in characteristic peak absorptions of 2,4-dinitrophenol was 3.97×10-3 s-1, while the reaction rate constants for the degradation of CR and MB were 9.72×10-3 s-1 and 14.25×10-3 s-1 respectively. After 5 cycles, Au/Fe3O4 microparticles preserved 99 % of the reaction rate constant, exhibiting considerable recycling efficiency in the reduction of nitro groups.

Enhanced Fe(OH)2-driven reductive Dechlorination via shortened Fe-O bonds and colloidal medium

Fe2+ is usually adsorbed to the surface of iron-bearing clay, and iron (hydr)oxide in groundwater. However, the reductive activity of Fe(OH)2, a prevalent intermediate during the transformation of Fe2+, remains unclear. In this study, high-purity Fe(OH)2 was synthesized and tested for its activity in the degradation of carbon tetrachloride (CT). XRD data confirm that the synthesized material is a pure Fe(OH)2 crystal, exhibiting sharp peaks of (001) and (100) facets. Zeta potential analysis confirms that the off-white Fe(OH)2 is a colloidal suspension with a positive charge of ∼+35-50 mV. FTIR spectra reveal the formation of a coordination compound Fe2+ with OH−/OD−, derived from NaOH/OD. SEM and HRTEM results demonstrate that the Fe(OH)2 crystal has a regular octahedral structure with a size of ∼30-70 nm and average lattice spacings of 2.58 Å. Mössbauer spectrum verifies that the Fe2+ in Fe(OH)2/Fe(OD)2 is hexacoordinated with six Fe-O bonds. XAFS data demonstrate that the Fe-O bonds become shorter as the OH−:Fe(II) ratios increase. DFT results indicate that the (100) crystal face of Fe(OH)2 more readily transfers electrons to CT. In addition to being adsorbed to iron compounds, structural Fe2+ compounds such as Fe(OH)2 could also accelerate the electron transfer from Fe2+ to CT through shortened Fe-O bonds. The rate constant of CT reduction by Fe(OH)2 is as high as 0.794 min−1 when the OH−:Fe(II) ratio is 2.5 in water. This study aims to enhance our understanding of the structure-reactivity relationship of Fe2+ compounds in groundwater, particularly in relation to electron transfer mechanisms.

Understanding the Interplay of the Brønsted Acidity of Catalyst Ancillary Groups and the Solution Components in Iron-porphyrin-Mediated Carbon Dioxide Reduction.

The rapid and efficient conversion of carbon dioxide (CO2) to carbon monoxide (CO) is an ongoing challenge. Catalysts based on iron-porphyrin cores have emerged as excellent electrochemical mediators of the two proton + two electron reduction of CO2 to CO, and many of the design features that promote function are known. Of those design features, the incorporation of Brønsted acids in the second coordination sphere of the iron ion has a significant impact on catalyst turnover kinetics. The Brønsted acids are often in the form of hydroxyphenyl groups. Herein, we explore how the acidity of an ancillary 2-hydroxyphenyl group affects the performance of CO2 reduction electrocatalysts. A series of meso-5,10,15,20-tetraaryl porphyrins were prepared where only the functional group at the 5-meso position has an ionizable proton. A series of cyclic voltammetry (CV) experiments reveal that the complex with -OMe positioned para to the ionizable -OH shows the largest CO2 reduction rate constants in acetonitrile solvent. This is the least acidic -OH of the compounds surveyed. The turnover frequency of the -OMe derivative can be further improved with the addition of 4-trifluoromethylphenol to the solution. In contrast, the iron-porphyrin complex with -CF3 positioned opposite the ionizable -OH shows the smallest CO2 reduction rate constants, and its turnover frequency is less enhanced with the addition of phenols to the reaction solutions. The origin of this effect is rationalized based on kinetic isotope effect experiments and density functional calculations. We conclude that catalysts with weaker internal acids coupled with stronger external acid additives provide superior CO2 reduction kinetics.

Study of the Mechanism of 7‐exo‐trig Cyclizations of Aryl, Vinyl, and Alkyl Radicals on Oxime Ethers

AbstractIn this work, we conducted a study of 7‐exo‐trig cyclizations mechanism involving aryl, vinyl, and alkyl radicals on oxime ethers. Initially, the reaction of brominated oxime ether 9 a with (TMS)3SiH and AIBN gave rise to aryl radicals that underwent a 7‐exo‐trig cyclization on the oxime ether, yielding dibenzoxepine 10 a, and the ipso reaction and reduction products were obtained as well. Approximate rate constants at 80 °C for the 7‐exo‐trig (1.0×108 s−1) and the ipso cyclization (4.3×107 s−1) were determined by competition experiments. DFT calculations showed good agreement with the experimental results. The reduction rate constant of the N‐alkoxyaminyl radical with (TMS)3SiH was calculated to be 4.1×10−1 M−1 s−1; while the rate constants for the 7‐exo‐trig cyclizations of vinyl and alkyl radicals on the oxime ether were estimated in the ranges of 106 s−1–108 s−1 and 103 s−1–108 s−1, respectively. The 7‐exo‐trig cyclization reactions involving aryl, vinyl, and alkyl radicals with oxime ethers were found to be an exothermic and irreversible process, with the oximic carbon showing a preference for nucleophilic alkyl radicals. This kinetic study contributes to the deeper understanding of radical‐mediated cyclizations, enabling the efficient design of complex synthetic routes.

Enhanced photocatalytic detoxification performance of OVs-enriched Co3O4/BiVO4 benefited from S-scheme interfacial charge pairs separation mechanism

Photocatalysts possess great application prospects in the environmental and energy field, and heterojunction photocatalysts can optimize the separation and transfer of photoinduced carriers to achieve high performance photocatalysis. Herein, Co3O4/BiVO4 (CoBVO) heterojunction photocatalysts were prepared in-situ using a one-step hydrothermal method. The impact of heterojunction structure and oxygen vacancies (OVs) on the light absorption range, band structure, and photogenerated carriers separation behavior of BiVO4 were studied by characterizing the photoelectric properties of the material. The results indicate that the concentration of OVs on BiVO4 samples changes due to formation of heterojunctions. Under simulated solar light irradiation, photocatalytic performance of the synthesized catalysts was investigated using Cr(VI) and moxifloxacin as simulated contaminants, photocatalytic reduction rate constant of Cr(VI) on 2CoBVO (molar ratio of Co/Bi is 2%) is 4.4 times of that on the single BiVO4, and the photocatalytic degradation rate constant of moxifloxacin on 2CoBVO is 1.6 times of that on the reference BiVO4. S-scheme interfacial charges separation and enhanced photocatalytic performance mechanism of OVs-enriched Co3O4/BiVO4 heterojunctions were elucidated based on the experimental observations. This work provides ideas for one-step synthesis of bismuth-based composite photocatalysts, which can be applied to the photocatalytic treatment of heavy metals and antibiotics.

Simultaneous Detection and Decontamination of Dichromate Ions: The Fluorescence Response and Photocatalysis of Thiadiazole-Modified Zr-Metal-Organic Frameworks.

The simultaneous analysis and removal of highly toxic hexavalent chromium (Cr (VI)) in contaminated water via an easy method remain a serious task. Based on the guidance of bibliometric analysis, a thiadiazole ligand-modified zirconium metal-organic framework (Zr-MOF) heralds a new and simple approach to Cr (VI) treatment. The concentration can be determined by fluorescence quenching with a low detection limit of 1.4 μM and a high quenching constant of 6.88 × 103 M-1. For the sensing mechanism, the fluorescence intensity of the Zr-MOF decreased rapidly due to the competition of Cr (VI) with the Zr-MOF for absorption excitation energy and the induction of Zr-MOF aggregation. The analysis system also displayed satisfactory stability and applicability. Apart from sensing application, Zr-MOF can convert Cr (VI) to Cr (III), and the reduction rate constant was 0.004 min-1 under irradiation. Therefore, the bifunctional Zr-MOF provided a potential application method for controlling the pollution caused by Cr (VI) in wastewater.

Incorporation of N-doped biochar into zero-valent iron for efficient reductive degradation of neonicotinoids: mechanism and performance

The extensive use of neonicotinoids on food crops for pest management has resulted in substantial environmental contamination. It is imperative to develop an effective remediation material and technique as well as to determine the evolution pathways of products. Here, novel ball-milled nitrogen-doped biochar (NBC)-modified zero-valent iron (ZVI) composites (named MNBC-ZVI) were fabricated and applied to degrading neonicotinoids. Based on the characterization results, NBC incorporation introduced N-doped sites and new allying heterojunctions and achieved surface charge redistribution, rapid electron transfer, and higher hydrophobicity of ZVI particles. As a result, the interaction between ZVI particles and thiamethoxam (a typical neonicotinoid) was improved, and the adsorption–desorption and reductive degradation of thiamethoxam and ·H generation steps were optimized. MNBC-ZVI could rapidly degrade 100% of 10 mg·L−1 thiamethoxam within 360 min, its reduction rate constant was 12.1-fold greater than that of pristine ZVI, and the electron efficiency increased from 29.7% to 57.8%. This improved reactivity and selectivity resulted from increased electron transfer, enhanced hydrophobicity, and reduced accumulation of iron mud. Moreover, the degradation of neonicotinoids occurred mainly via nitrate reduction and dichlorination, and toxicity tests with degradation intermediates revealed that neonicotinoids undergo rapid detoxification. Remarkably, MNBC-ZVI also presented favorable tolerance to various anions, humic acid, wastewater and contaminated soil, as well as high reusability. This work offers an efficient and economic biochar-ZVI remediation technology for the rapid degradation and detoxification of neonicotinoids, significantly contributes to knowledge on the relevant removal mechanism and further advances the synthesis of highly reactive and environmentally friendly materials.Graphical

Cellulose nanofibril/titanate nanofiber modified with CdS quantum dots hydrogel with 3D porous structure: A stable photocatalytic adsorbent for Cr(VI) removal

A novel cellulose nanofibril/titanate nanofiber modified with CdS quantum dots hydrogel (CTH) was synthesized as an effective, stable, and recyclable photocatalytic adsorbent using cellulose nanofibril (CN), titanate nanofiber (TN), and CdS quantum dots. Within the CTH structure, CN formed an essential framework, creating a three-dimensional (3D) porous structure that enhanced the specific surface area and provided abundant adsorption sites for Cr(VI). Simultaneously, TN modified with CdS quantum dots (TN-CdS) served as a nanoscale Z-type photocatalyst, facilitating the efficient separation of photoinduced electrons and holes, further increasing the photocatalytic efficiency. The morphological, chemical, and optical properties of CTH were thoroughly characterized. The CTH demonstrated the maximum theoretical adsorption capacity of 373.3 ± 14.2 mg/g, which was 3.4 times higher than that of CN hydrogel. Furthermore, the photocatalytic reduction rate constant of the CTH was 0.0586 ± 0.0038 min−1, which was 6.4 times higher than that of TN-CdS. Notably, CTH displayed outstanding stability, maintaining 84.9 % of its initial removal efficiency even after undergoing five consecutive adsorption–desorption cycles. The remarkable performance of CTH in Cr(VI) removal was attributed to its 3D porous structure, comprising CN and TN-CdS. These findings provide novel insights into developing a stable photocatalytic adsorbent for Cr(VI) removal.

Systematic Study on the Precursor Reduction Kinetics and Growth Pattern for Size-Tunable Palladium Nanocubes.

Unveiling the underlying chemistry during the growth of well-defined nanocrystals is a fundamental but challenging task in materials chemistry. Herein, Pd NCs with tunable sizes ranging from 4.5 to 23.5 nm have been synthesized in the presence of potassium acetate (KOAc). The Pd precursor variation trends of these preparation systems along with reaction time have been determined using a UV-vis spectrometer, and corresponding reduction kinetic parameters, including the apparent reduction rate constant (k) and activation energy (Ea), are calculated by regarding the reduction processes as quasi-first-order reactions. It is confirmed that the introduction of KOAc does not affect the value of the Ea of different reaction systems. The interrelationship of k, product size (d), and reaction temperature (T) is discussed in depth. Results indicate that the three parameters are closely related, and for given reaction systems, they are specified. With the careful investigation of six specific systems (reaction systems with 10 mM, 20 mM KOAc at 55 °C, with 5 mM, 10 mM KOAc at 65 °C, without KOAc at 75 °C, and with 5 mM KOAc at 85 °C), the growth pattern of Pd NCs is described with an empirical expression and is further confirmed as a synergistic result of k and T.