Enhanced Co-Adsorption of Alcohols and Amines for Visible Light Driven Oxidative Condensation Using Iron-Based MOF.

Imines are essential intermediates in organic transformations, and is generally produced by dehydrogenative condensation of alcohols and amines with the assist of specialized catalysts and additives. Heterogeneous photocatalysis provides a sustainable platform for such process without the using of toxic oxidants, yet a functionalized photocatalyst with optimized co-adsorption of reactants needs to be developed to promote the stoichiometric oxidative condensation under ambient conditions. Here, we show that benzyl alcohol and aniline adsorb non-interferingly on the Fe node and the linker sites of the MIL-53(Fe) metal organic frameworks (MOFs), respectively. The co-adsorption of both reactants barely influences the reduction of molecular oxygen to generate oxygen radicals, resulting in efficient formation of benzaldehyde under visible light. Additionally, the weak adsorption of water together with surface acidity of the MIL-53(Fe) promote a rapid condensation of benzaldehyde with aniline and the depletion of generated water, achieving an efficient C-N bond creation for a wide range of substrates.

A comprehensive review on the boosted effects of anion vacancy in the heterogeneous photocatalytic degradation, part I: Focus on sulfur, nitrogen, carbon, and halogen vacancies.

The greenest environmental remediation way is the photocatalytic degradation of organic pollutants. However, limited photocatalytic applications are due to poor sunlight absorption and photogenerated charge carriers' recombination. These limitations can be overcome by introducing anion vacancy (AV) (O, S, N, C, and Halogen) defects in semiconductors that enhance light harvesting, facilitate charge separation, modulate electronic structure, and produce reactive radicals. In continuing part A of this review, in this part, we summarized the recent AVs' research, including S, N, C, and halogen vacancies on the boosted photocatalytic features of semiconductor materials, like metal oxides/sulfides, oxyhalides, and nitrides in detail. Also, we outline the recently developed AV designs for the photocatalytic degradation of organic pollutants. The AV creating and analysis methods and the recent photocatalytic applications and mechanisms of AV-mediated photocatalysts are reviewed. AV engineering photocatalysts' challenges and development prospects are illustrated to get a promising research direction.

Robust Photocatalytic MICROSCAFS® with Interconnected Macropores for Sustainable Solar-Driven Water Purification.

Advanced oxidation processes, including photocatalysis, have been proven effective at organic dye degradation. Tailored porous materials with regulated pore size, shape, and morphology offer a sustainable solution to the water pollution problem by acting as support materials to grafted photocatalytic nanoparticles (NPs). This research investigated the influence of pore and particle sizes of photocatalytic MICROSCAFS® on the degradation of methyl orange (MO) in aqueous solution (10 mg/L). Photocatalytic MICROSCAFS® are made of binder-less supported P25 TiO2 NPs within MICROSCAFS®, which are silica-titania microspheres with a controlled size and interconnected macroporosity, synthesized by an adapted sol-gel method that involves a polymerization-induced phase separation process. Photocatalytic experiments were performed both in batch and flow reactors, with this latter one targeting a proof of concept for continuous transformation processes and real-life conditions. Photocatalytic degradation of 87% in 2 h (batch) was achieved, using a calibrated solar light simulator (1 sun) and a photocatalyst/pollutant mass ratio of 23. This study introduces a novel flow kinetic model which provides the modeling and simulation of the photocatalytic MICROSCAFS® performance. A scavenger study was performed, enabling an in-depth mechanistic understanding. Finally, the transformation products resulting from the MO photocatalytic degradation were elucidated by high-resolution mass spectrometry experiments and subjected to an in silico toxicity assessment.

Novel TiO2-Supported Gold Nanoflowers for Efficient Photocatalytic NOx Abatement.

In this study, we pioneered the synthesis of nanoflower-shaped TiO2-supported Au photocatalysts and investigated their properties. Au nanoflowers (Au NFs) were prepared by a Na-citrate and hydroquinone-based preparation method, followed by wet impregnation of the derived Au NFs on the surface of TiO2 nanorods (TNR). A uniform and homogeneous distribution of Au NFs was observed in the TNR + NF(0.7) sample (lower Na-citrate concentration), while their distribution was heterogeneous in the TNR + NF(1.4) sample (higher Na-citrate concentration). The UV-Vis DR spectra revealed the size- and shape-dependent optical properties of the Au NFs, with the LSPR effect observed in the visible region. The solid-state EPR spectra showed the presence of Ti3+, oxygen vacancies and electron interactions with organic compounds on the catalyst surface. In the case of the TNR + NF(0.7) sample, high photocatalytic activity was observed in the H2-assisted reduction of NO2 to N2 at room temperature under visible-light illumination. In contrast, the TNR + NF(1.4) catalyst as well as the heat-treated samples showed no ability to reduce NO2 under visible light, indicating the presence of deformed Au NFs limiting the LSPR effect. These results emphasized the importance of the choice of synthesis method, as this could strongly influence the photocatalytic activity of the Au NFs.

Sol-gel and Pechini niobium modified: synthesis, characterization and application in the 2,4-D herbicide degradation.

In this work, a comparison was made between the synthesis of niobium-based materials (Nb2O5), both in terms of material characterization and catalytic performance. The methods used were chemical mixtures: modified sol-gel and Pechini. The materials were calcined at different temperatures (753, 873 and 993K) and characterized by the following techniques: photoacousticspectroscopy (PAS), zero charge point (pHPZC), scanning electron microscopy (SEM/EDS), thermogravimetric analysis (TGA/DTG) and X-ray diffraction (XRD). The photocatalytic process was carried out to evaluate the degradation of 2,4-dichlorophenoxyacetic acid (2,4-D) under UV radiation (250 W mercury vapor lamp) and different experimental conditions. In addition, to better understand the influence of parameters such as pH, catalyst concentration (0.2, 0.5 and 0.8 g L-1) and calcination temperature, a Design of Experiments (DoE) was used. The results indicated that despite having similar structures and phases in the XRD analysis, the morphology presents two distinct surfaces, due to the preparation method. Differences in the synthesis method affected the catalytic activity in the parameters studied. Although the zero charge point values are close (6.18-6.36), we observed differences in the band gap depending on the calcination temperature. In the optimal condition studied, the catalyst prepared by the sol-gel method obtained the best results.

Unveiling the Role of Water in Heterogeneous Photocatalysis of Methanol Conversion for Efficient Hydrogen Production.

Water molecules, which act as both solvent and reactant, play critical roles in photocatalytic reactions for methanol conversion. However, the influence of water on the adsorption of methanol and desorption of liquid products, which are two essential steps that control the performance in photocatalysis, has been well under-explored. Herein, we reveal the role of water in heterogeneous photocatalytic processes of methanol conversion on the platinized carbon nitride (Pt/C3N4) model photocatalyst. In situ spectroscopy techniques, isotope effects, and computational calculations demonstrate that water shows adverse effects on the adsorption of methanol molecules and desorption processes of methanol oxidation products on the surface of Pt/C3N4, significantly altering the reaction pathways in photocatalytic methanol conversion process. Guided by these discoveries, a photothermal-assisted photocatalytic system is designed to achieve a high solar-to-hydrogen (STH) conversion efficiency of 2.3 %, which is among the highest values reported. This work highlights the important roles of solvents in controlling the adsorption/desorption behaviours of liquid-phase heterogeneous catalysis.

Heterogeneous Photocatalytic Hydrogenative Reactions Using Liquid Hydrogen Donors: Mechanisms, Catalysts Design, and Applications.

Heterogeneous photocatalysis is a promising approach for a wide range of hydrogenative reactions owing to the mild reaction conditions and the possibility of employing liquid hydrogen donors. Currently, the major interest is focused on the development of high performance photocatalyst materials and the expansion of reaction scope. An overview from a perspective of hydrogen donor and thus the related mechanistic understanding of the light-induced hydrogenative reactions is rare. Here, we have categorized the photocatalytic hydrogenative reactions by the type of employed liquid hydrogen donors (hydrocarbons and water), discussed the basic criteria of hydrogen abstraction from these donors, and elaborated the design strategy of the photocatalyst materials.

Heterogeneous vs homogenous photocatalysis: what dominates in the degradation of methyl orange and methylene blue mixtures?

Photocatalysis has been oft proposed as a green solution for pollution remediation, however, majority of the existing literature only studies the degradation of solitary analytes. The degradation of mixtures of organic contaminants is inherently more complicated due to a variety of photochemical processes that occur in parallel. Here, we describe a model system comprised of methylene blue and methyl orange dyes whose degradation carried out by two common photocatalysts, P25 TiO2 and g-C3N4. With P25 TiO2 as the catalyst, the degradation rate of methyl orange slowed by 50% when degraded in a mixture compared to when alone. Control experiments with radical scavengers showed this to occur due to competition between the dyes for oxidative photogenerated species. In the presence of g-C3N4, methyl orange's degradation rate in the mixture increased by 2300% due to two homogeneous photocatalysis processes sensitized by methylene blue. Homogenous photocatalysis was found to be fast relative to heterogeneous photocatalysis by g-C3N4 but slow relative to photocatalysis by P25 TiO2 and explains the change observed between the two catalysts. Changes in dye adsorption to the catalyst when in a mixture were also explored but not found to coincide with changes in degradation rate.

Enhanced photodegradation of organic contaminants using V-ZnSQDs@TiO2 photocatalyst in an aqueous medium.

Vanadium-doped zinc sulfide quantum dots complexed with TiO2 have been designed using the sol-gel technique and characterized using analytical techniques, such as X-ray diffraction analysis (XRD), UV-Vis diffuse reflectance spectra (DRS), Fourier transforms Infra Red (FTIR), Brunauer-Emmett-Teller analysis (BET), X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM), and transmission electron microscopy (TEM). The X-ray diffraction analysis of the composite material showed sharp peaks corresponding to both TiO2 and ZnSQDs. The FTIR analysis exhibits a strong and broad absorption at 807 cm-1 indicating the assimilation of vanadium metal in the ZnSQDs lattice. The DRS spectra showed a bathochromic shift of 25 nm in the synthesized V-ZnSQDs@TiO2 composite compared with the pure sample. The photocatalytic performance of the synthesized composite was tested by studying the degradation of two different chromophoric organic dyes, rhodamine B (RhB), methylene blue (MB) and a drug derivative paracetamol (PCM) in aqueous suspension under UV-light illumination. Among the synthesized materials, the composite (V-ZnSQDs@TiO2) was established to be more active than the pure ZnSQDs, TiO2, and V-ZnSQDs for the degradation of compounds under investigation. The activity of the synthesized catalyst was also tested for the mineralization of all compounds by measuring the depletion in total organic carbon (TOC) at different irradiation times. The results showed that the catalyst degrades the compounds and mineralizes them efficiently. The primary reactive species involved in the photodegradation reaction were determined by quenching studies, terephthalic acid, and NBT probe methods. A probable mechanistic pathway for the decomposition of compounds has been proposed.

Statistical Analysis of Methotrexate Degradation by UV-C Photolysis and UV-C/TiO2 Photocatalysis.

Methotrexate (MTX) is a folic acid analog and has been used to treat a wide variety of malignant and non-malignant diseases. The wide use of these substances has led to the continuous discharge of the parent compound and its metabolites in wastewater. In conventional wastewater treatment plants, the removal or degradation of drugs is not complete. In order to study the MTX degradation by photolysis and photocatalysis processes, two reactors were used with TiO2 as a catalyst and UV-C lamps as a radiation source. H2O2 addition was also studied (absence and 3 mM/L), and different initial pHs (3.5, 7, and 9.5) were tested to define the best degradation parameters. Results were analyzed by means of ANOVA and the Tukey test. Results show that photolysis in acidic conditions with 3 mM of H2O2 added is the best condition for MTX degradation in these reactors, with a kinetic constant of 0.028 min-1. According to the ANOVA test, all considered factors (process, pH, H2O2 addition, and experimentation time) caused statistically significant differences in the MTX degradation results.

Low bandgap high entropy alloy for visible light-assisted photocatalytic degradation of pharmaceutically active compounds: Performance assessment and mechanistic insights.

The incessant accumulation of pharmaceutically active compounds (PhACs) in various environmental compartments represents a global menace. Herein, an equimolar high entropy alloy (HEA), i.e., FeCoNiCuZn, is synthesized via a facile and scalable method, and its effectiveness in eliminating four different PhACs from aqueous matrices is rigorously examined. Attributing to its relatively low bandgap and multielement active sites, the as-synthesized quinary HEA demonstrates more pronounced photocatalytic decomposition efficiency, towards tetracycline (86%), sulfamethoxazole (94%), ibuprofen (80%), and diclofenac (99%), than conventional semiconductor-based photocatalysts, under visible light irradiation. Additionally, radical trapping assays are conducted, and the dissociation intermediates are identified, to probe the plausible photocatalytic degradation pathways. Further, the end-products of FeCoNiCuZn-mediated photocatalysis are apparently non-toxic, and the HEA can be successfully recycled repeatedly, with no obvious leaching of heavy metal ions. Overall, the findings of this study testify the applicability of FeCoNiCuZn as a visible light-active photocatalyst, for treating wastewaters contaminated with PhACs.

Comparison of Ten Metal-Doped LaFeO3 Samples on Photocatalytic Degradation of Antibiotics in Water under Visible Light: Role of Surface Area and Aqueous Phosphate Ions.

Doping semiconducting oxides, such as LaFeO3 (LF), with metallic elements is a good strategy to improve the performance of photocatalysts. In this study, LF and ten different nanopowders metal-doped at the La or Fe site of LaFeO3 were evaluated in the photocatalytic degradation of ciprofloxacin (CP) and oxytetracycline (OTC). The following metals were used in the doping (mol%) process of LF: Pd 3% and 5%; Cu 10%; Mg 5%, 10%, and 20%; Ga 10%; Y 10% and 20%; and Sr 20%. The doped samples were synthetized using a citrate auto-combustion technique. From the X-ray diffraction (XRD) data, only a single crystalline phase, namely an orthorhombic perovskite structure, was observed except for trace amounts of PdO in the sample with Pd 5%. The specific surface area (SSA) ranged from 9 m2 g-1 (Ga 10%) to 20 m2 g-1 (Mg 20%). SEM images show that all samples were constituted from agglomerates of particles whose sizes ranged from ca. 20 nm (Mg 20%) to ca. 100 nm (Pd 5%). Dilute aqueous solutions (5 × 10-6 M) prepared for both CP and OTC were irradiated for 240 min under visible-light and in the presence of H2O2 (10-2 M). The results indicate a 78% removal of OTC with Cu 10% doped LF in a phosphate buffer (pH = 5.0). The degradation of CP is affected by pH and phosphate ions, with 78% (in unbuffered solution) and 54% (in phosphate buffer, pH = 5.0) removal achieved with Mg 10% doped LF. The reactions follow a pseudo-first order kinetic. Overall, this study is expected to deepen the assessment of photocatalytic activity by using substrates with different absorption capacities on photocatalysts.

Heterogeneous Photocatalysis as a Potent Tool for Organic Synthesis: Cross-Dehydrogenative C-C Coupling of N-Heterocycles with Ethers Employing TiO2/N-Hydroxyphthalimide System under Visible Light.

Despite the obvious advantages of heterogeneous photocatalysts (availability, stability, recyclability, the ease of separation from products and safety) their application in organic synthesis faces serious challenges: generally low efficiency and selectivity compared to homogeneous photocatalytic systems. The development of strategies for improving the catalytic properties of semiconductor materials is the key to their introduction into organic synthesis. In the present work, a hybrid photocatalytic system involving both heterogeneous catalyst (TiO2) and homogeneous organocatalyst (N-hydroxyphthalimide, NHPI) was proposed for the cross-dehydrogenative C-C coupling of electron-deficient N-heterocycles with ethers employing t-BuOOH as the terminal oxidant. It should be noted that each of the catalysts is completely ineffective when used separately under visible light in this transformation. The occurrence of visible light absorption upon the interaction of NHPI with the TiO2 surface and the generation of reactive phthalimide-N-oxyl (PINO) radicals upon irradiation with visible light are considered to be the main factors determining the high catalytic efficiency. The proposed method is suitable for the coupling of π-deficient pyridine, quinoline, pyrazine, and quinoxaline heteroarenes with various non-activated ethers.

Photocatalytic degradation of bisphenol-A (BPA) over titanium dioxide, and determination of its by-products by HF-LPME/GC-MS.

In this work, analytical strategies were developed based on the technique of hollow fiber liquid-phase microextraction and chromatographic methods (LC-UV and GC/MS). These methods allowed the identification of the main Bisphenol-A by-products applying heterogeneous photocatalysis in water samples. BPA degradation in this study was in the order of 90%, and the conditions used in the HF-LPME were optimized through 23 factorial design (6 cm fiber length, stirring speed of 750 rpm, and an extraction time of 30 min). Using a HF-LPME/GC-MS analytical strategy, it was possible to identify six by-products of BPA photodegradation, two of which have not been reported in the literature so far. This knowledge was quite important since the degradation can lead to the formation of more toxic and persistent by-products than the BPA. With the Toxtree software, three degradation products were found to be persistent to the environment, in addition to BPA; however, in 360 minutes of reaction, chromatographic peaks of the precursors were not identified, suggesting that there may have been a total degradation of these compounds. The results showed a great application potential of a miniaturized extraction technique to extract and pre-concentrate the degradation products of emerging contaminants.

Effective Activation of Strong C-Cl Bonds for Highly Selective Photosynthesis of Bibenzyl via Homo-Coupling.

Carbon-carbon (C-C) coupling of organic halides has been successfully achieved in homogeneous catalysis, while the limitation, e.g., the dependence on rare noble metals, complexity of the metal-ligand catalylst and the poor catalyst stability and recyclability, needs to be tackled for a green process. The past few years have witnessed heterogeneous photocatalysis as a green and novel method for organic synthesis processes. However, the study on C-C coupling of chloride substrates is rare due to the extremely high bond energy of C-Cl bond (327 kJ mol-1 ). Here, we report a robust heterogeneous photocatalyst (Cu/ZnO) to drive the homo-coupling of benzyl chloride with high efficiency, which achieves an unprecedented high selectivity of bibenzyl (93 %) and yield rate of 92 % at room temperature. Moreover, this photocatalytic process has been validated for C-C coupling of 10 benzylic chlorides all with high yields. In addition, the excellent stability has been observed for 8 cycles of reactions. With detailed characterization and DFT calculation, the high selectivity is attributed to the enhanced adsorption of reactants, stabilization of intermediates (benzyl radicals) for the selective coupling by the Cu loading and the moderate oxidation ability of the ZnO support, besides the promoted charge separation and transfer by Cu species.

A Modular Tubular Flow System with Replaceable Photocatalyst Membranes for Scalable Coupling and Hydrogenation.

Heterogeneous photocatalysis is effective for the selective synthesis of value-added chemicals at lab-scale, yet falls short of requirements for mass production (low cost and user friendliness). Here we report the design and fabrication of a modular tubular flow system embedded with replaceable photocatalyst membranes for scalable photocatalytic C-C, C-N homocoupling and hydrogenation reactions, which can be operated in either circular and continuous flow mode with high performance. The photocatalyst membranes almost fully occupy the volume of the reactor, thus enabling optimal absorption of the incident light. Additionally, the porous structured photocatalyst membranes facilitate the mass transfer of the reactants to efficiently use the active sites, resulting in 0th -order reaction kinetics and a high space-time yield compared to the batch reaction system at practical application levels and prolonged reaction times.

Heterogeneous Photocatalytic Recycling of FeX2 /FeX3 for Efficient Halogenation of C-H Bonds Using NaX.

Environmental-friendly halogenation of C-H bonds using abundant, non-toxic halogen salts is in high demand in various chemical industries, yet the efficiency and selectivity of laboratory available protocols are far behind the conventional photolytic halogenation process which uses hazardous halogen sources. Here we report an FeX2 (X=Br, Cl) coupled semiconductor system for efficient, selective, and continuous photocatalytic halogenation using NaX as halogen source under mild conditions. Herein, FeX2 catalyzes the reduction of molecular oxygen and the consumption of generated oxygen radicals, thus boosting the generation of halogen radicals and elemental halogen for direct halogenation and indirect halogenation via the formation of FeX3 . Recycling of FeX2 and FeX3 during the photocatalytic process enables the halogenation of a wide range of hydrocarbons in a continuous flow, rendering it a promising method for applications.

Enhanced Energy Transfer in A π-Conjugated Covalent Organic Framework Facilitates Excited-State Nickel Catalysis.

Covalent organic frameworks (COFs) have received broad interest owing to their permanent porosity, high stability, and tunable functionalities. COFs with long-range π-conjugation and photosensitizing building blocks have been explored for sustainable photocatalysis. Herein, we report the first example of COF-based energy transfer Ni catalysis. A pyrene-based COF with sp2 carbon-conjugation was synthesized and used to coordinate NiII centers through bipyridine moieties. Under light irradiation, enhanced energy transfer in the COF facilitated the excitation of Ni centers to catalyze borylation and trifluoromethylation reactions of aryl halides. The COF showed two orders of magnitude higher efficiency in these reactions than its homogeneous control and could be recovered and reused without significant loss of catalytic activity.

Tin(II)-Based Metal-Organic Frameworks Enabling Efficient, Selective Reduction of CO2 to Formate under Visible Light.

Certain metal complexes are known as high-performance CO2 reduction photocatalysts driven by visible light. However, most of them rely on rare, precious metals as principal components, and integrating the functions of light absorption and catalysis into a single molecular unit based on abundant metals remains a challenge. Metal-organic frameworks (MOFs), which can be regarded as intermediate compounds between molecules and inorganic solids, are potential platforms for the construction of a simple photocatalytic system composed only of Earth-abundant nontoxic elements. In this work, we report that a tin-based MOF enables the conversion of CO2 into formic acid with a record high apparent quantum yield (9.8 % at 400 nm) and >99 % selectivity without the need for any additional photosensitizer or catalyst. This work highlights a new MOF with strong potential for photocatalytic CO2 reduction driven by solar energy.

Ambient Preparation of Benzoxazine-based Phenolic Resins Enables Long-term Sustainable Photosynthesis of Hydrogen Peroxide.

Rational design of polymer structures at the molecular level promotes the iteration of high-performance photocatalyst for sustainable photocatalytic hydrogen peroxide (H2 O2 ) production from oxygen and water, which also lays the basis for revealing the reaction mechanism. Here we report a benzoxazine-based m-aminophenol-formaldehyde resin (APFac) polymerized at ambient conditions, exhibiting superior H2 O2 yield and long-term stability to most polymeric photocatalysts. Benzoxazine structure was identified as the crucial photocatalytic active segment in APFac. Favorable adsorption of oxygen/intermediates on benzoxazine structure and commendable product selectivity accelerated the reaction kinetically in stepwise single-electron oxygen reduction reaction. The proposed benzoxazine-based phenolic resin provides the possibility of production in batches and industrial application, and sheds light on the de novo design and analysis of metal-free polymeric photocatalysts.