Pure Water Research Articles

Developing Catalysts for Membrane Electrode Assemblies in High Performance Polymer Electrolyte Membrane Water Electrolyzers.

Extensive research is underway to achieve carbon neutrality through the production of green hydrogen via water electrolysis, powered by renewable energy. Polymer membrane water electrolyzers, such as proton exchange membrane water electrolyzer (PEMWE) and anion exchange membrane water electrolyzer (AEMWE), are at the forefront of this research. Developing highly active and durable electrode catalysts is very important for commercializing these electrolyzers. However, most research is conducted in half-cell setups, which may not fully represent the catalysts' effectiveness in membrane-electrode-assembly (MEA) devices. This review explores the catalysts developed for high-performance PEMWE and AEMWE MEA systems. Only the catalysts reporting the MEA performance were discussed in this review. In PEMWE, strategies aim to minimize Ir use for oxygen evolution reaction (OER) by maximizing activity, employing metal oxide-based supports, integrating secondary elements into IrOx lattices, or exploring non-Ir materials. For AEMWE, the emphasis is on enhancing the performance of NiFe-based and Co-based catalysts by improving electrical conductivity and mass transport. Pt-based and Ni-based catalysts for hydrogen evolution reaction (HER) in AEMWE are also examined. Additionally, this review discusses the unique considerations for catalysts operating in pure water within AEMWE systems.

AttenGpKa: A Universal Predictor of Solvation Acidity Using Graph Neural Network and Molecular Topology.

Rapid and accurate calculation of acid dissociation constant (pKa) is crucial for designing chemical synthesis routes, optimizing catalysts, and predicting chemical behavior. Despite recent progress in machine learning, predicting solvation acidity, especially in nonaqueous solvents, remains challenging due to limited experimental data. This challenge arises from treating experimental values in different solvents as distinct data domains and modeling them separately. In this work, we treat both the solutes and solvents equally from a perspective of molecular topology and propose a highly universal framework called AttenGpKa for predicting solvation acidity. AttenGpKa is trained using 26,522 experimental pKa values from 60 pure and mixed solvents in the iBonD database. As a result, our model can simultaneously predict the pKa values of a compound in various solvents, including pure water, pure nonaqueous, and mixed solvents. AttenGpKa achieves universality by using graph neural networks and attention mechanisms to learn complex effects within solute and solvent molecules. Furthermore, encodings of both solute and solvent molecules are adaptively fused to simulate the influence of the solvent on acid dissociation. AttenGpKa demonstrates robust generalization in extensive validations. The interpretability studies further indicate that our model has effectively learnt electronic and solvent effects. A free-to-use software is provided to facilitate the use of AttenGpKa for pKa prediction.

Supercritical hydrothermal synthesis of ultra-fine Cu powders

ABSTRACT Ultra-fine Cu powders were synthesized using supercritical water as a reaction medium and formic acid as a reducing agent. The effects of reducing agent, reaction temperature, and complexing agent on the phase constituents, particle size distributions and morphology of the synthesized ultra-fine Cu powders were investigated. A complex mixture of Cu2O and Cu powders formed by pure supercritical water while high purity homogeneous ultra-fine Cu powders can be synthesized by supercritical water with formic acid as a reducing agent. Moreover, fine tuning of particle size and morphology can be realized by the addition of Ethylenediamine tetraacetic acid (EDTA). The modification mechanism of EDTA on the surfaces of ultra-fine Cu powders was investigated by X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. EDTA adsorbed on the surfaces of nanoparticles by the dehydration reaction of carboxyl groups in the molecule of EDTA and hydroxyl groups on surfaces of copper nanoparticles (CuOH).

Solar photocatalysts: non-metal (C, N, and S)-doped ZnO synthesized through an industrially sustainable in situ approach for environmental remediation applications.

One of the biggest issues the world is currently experiencing is the scarcity of pure water due to the contamination of pure water by human activities. Highly efficient, semiconducting photocatalytic materials have great potential as future catalytic materials for facilitating the clean-up process of contaminated water. Among the many semiconductor photocatalysts, non-metal-doped zinc oxide (ZnO) nanoparticles have attracted special attention in the scientific field for environmental remediation applications. The present paper reports an easy and viable synthesis of C-, N-, and S-based ZnO semiconductor photocatalysts through a simple heating method. The structural changes in the obtained samples were studied using XRD, TG/DTA, and FT-IR analyses, and morphological examinations were performed using TEM and SEM. The quantification of non-metal dopants was carried out using CNS and XPS analyses. The surface areas of the samples were analyzed using the BET method and the band energies of the samples were measured using UV-vis-diffuse reflectance Kubelka-Munk plots. Photoactivity studies were performed and revealed that the utilized in situ method resulted in the development of high-performance sulphur - (81.4%, k = 1.951 × 10-2 min-1), nitrogen - (78.5%, k = 2.271 × 10-2 min-1), and carbon - (67.2%, k = 1.392 × 10-2 min-1) doped ZnO photocatalysts. As revealed through XPS and UV analyses, a possible electron-transfer mechanism is suggested, wherein electronic transition occurred from different sub-bands when non-metal elements were introduced into the ZnO lattice. The study paves the way for the bulk-scale fabrication of doped nanoparticles through a simple heating method, whereby the unique combination of the present method with bandgap engineering will ultimately produce advanced non-metal-based ZnO photocatalysts that could find useful applications in sustainable industrial sectors.

Electrostatic Surface Charging by Water Dewetting.

Water dewetting generates static electricity. We reviewed historical experiments of this phenomenon, and we studied the charging of polymer slides and metal electrode supported polymer films withdrawn vertically from a pool of aqueous solutions. For pure water, charging was negative and surface charge densities increased with the speed of dewetting, which we explain by the thermally activated entrainment of nanometer-sized water droplets or clusters charged by unbalanced adsorbed electric double-layer ions. Surface charge densities increased for reduced polymer film thickness following a power law, which we explain by reduced discharge of the entrained water volumes. At low salinity c ≲ 10 μM, charging was proportional to electrokinetic interfacial charge densities: the negative charging was increased for alkaline solutions and for most salts at μM concentrations and the charge polarity was inversed to positive for a cationic surfactant, a salt with a highly positively charged cation, and for a strong acid at approximately pH 4. Charging was reduced again for c ≳ 100 μM, especially at high dewetting speeds and for chaotropic ions, which we explain by the entrainment of larger and more discharged droplets. We determined adsorption energies of the charged water clusters on the dewetted surface from thermally stimulated discharge of the charged polymer slides and we show that the surface charge distribution, imaged by charged toner powders and measured microscopically by Kelvin probe force microscopy, is a record of the dewetting process that provides spatial and kinetic information about the three-phase contact line motion.

Innovative two-dimensional porphyrin-integrated metal-organic frameworks for enhanced photocatalytic hydrogen peroxide generation in pure water

In the quest for eco-friendly and efficient synthesis of hydrogen peroxide (H2O2), a chemical with extensive applications, photocatalytic production emerges as a promising clean technique. Metal-organic frameworks (MOFs), known for their exceptional porosity and geometric customizability, stand at the forefront of potential photocatalytic materials. Yet, the conventional three-dimensional topologies of MOFs pose a challenge, impeding the swift transit of photogenerated electrons and thereby curbing performance enhancements. In this vein, we have engineered novel 2D porphyrin-based MOFs, specifically Ce-TCPP and La-TCPP, utilizing diverse metal sources while maintaining a consistent topological framework. This design strategy streamlines the electron and hole transport pathways, thus elevating the photocatalytic activity. Delving into the structural nuances of these MOFs, our research unveiled that the photocatalytic activity experienced a marked shift upon altering the metal cluster types. Notably, La-TCPP, as an efficacious catalyst, demonstrated an H2O2 yield of 79.75 μmol/g/h in pure water, sans any sacrificial agents. Rigorous testing confirmed the robust stability of both MOFs. This study marks the inaugural design and synthesis of a single crystal structure of La-TCPP. By strategically varying metal cluster compositions, we have fine-tuned the architecture of two-dimensional MOFs. This approach sheds light on the intricate structure-activity relationship governing the photocatalytic synthesis of H2O2, paving the way for future advancements in the field.

Electrochemical polymer synthesis using thiophene and pyrrole/carbazole: Their electrochemical behaviours and capacitor performance

In this study, carbazole-derived monomers were synthesized on ITO-coated PET via electrochemical reactions and conductivity measurements of the resulting polymeric films were performed by UV, FT-IR, NMR, TG-DTG, SEM and AFM analyses. Their spectroelectrochemical properties were investigated. The carbazole (C) based thiophene (Th) polymer abbreviated as pThC and its copolymer with pyrrole (Py), named as pThC-Py were obtained by electrochemical polymerization method. The surface stability of the resulting polymer films was good depending on time. The contact angle (CA) between the water and theco- polymer surface was determined by dropping 6.09 μL of pure water and CA average was calculated as 68.19° < 90°. According to the thermal analysis data of the polymers, the thermal stability of the pThC-Py was better than pThC as it had higher thermal decomposition temperature. Comparisons of electrical conductivity measurements of the polymer films were made depending on the temperature (25, 50 and 90 °C). Due to increasing temperature, the electrical conductivity of pThC-Py film was read as 29.3 S/cm at 90 °C, and also the electrical conductivity values of the pThC-Py were determined as 1.92 × 10−2 S/cm at 25 °C and 14.2 S/cm at 50 °C. Because of the high electrical conductivity of the pThC-Py, its capacitor performance was tried to be determined from cyclic voltammetric measurements. According to the voltammetric results, the power density (P) and the energy density (E) values of the synthesized substance were calculated as 290.532 W/g and 9.684 Wh/g, respectively. This indicates that the amount of energy the material storable is relatively high. Moreover, it is possible to say that it can be included in the classical capacitor class and in the supercapacitor category by improving its features. Moreover, since the electrical conductivity of pThC-Py is quite good, it is thought that it may be suitable for use in electronic devices.

Ultra-selective pyrene-based fluorescent sensor for detection of Fe+3 in neat aqueous medium

Transition metals, particularly Fe+3, play vital roles in biological and environmental systems, yet their chronic elevation can lead to severe diseases. Early detection of Fe+3 is crucial for diagnosing associated ailments. While traditional detection methods have drawbacks, fluorescent sensors offer promising alternatives due to their ease of use, cost-effectiveness, and real-time monitoring capability. Pyrene-based sensors have demonstrated notable sensitivity and selectivity for Fe+3, but challenges remain in achieving applicability in neat aqueous systems. We present two novel turn-off pyrene-based sensors, APTS (sodium 8-aminopyrene-1,3,6-trisulfonate) and APSS (sodium (E)-4-hydroxy-3-((pyren-1-ylimino)methyl)benzenesulfonate), incorporating sulfonate groups to enable their use in pure water samples and achieve nanomolar-level detection limits. Through meticulous experimental and characterization efforts, we elucidate the significance of the imine linkage in enhancing selectivity towards Fe+3 ions. Our sensors exhibit exceptional selectivity and sensitivity, with LODs of 45.6 nM and 45.9 nM for APTS and APSS, respectively, surpassing environmental protection guidelines. Additionally, binding stoichiometry studies reveal insights into the interaction mechanisms, supported by fluorescence lifetime analysis and DFT studies. APSS particularly stands out for its lack of interference from other metal ions, notably Cu2+ as well as Fe2+, offering promising potential for real-time applications and development of paper strip tests. The practical applicability of our sensors is demonstrated through successful Fe+3 detection in various water samples with recoveries ranging from 94 % to 104 %. Overall, our study highlights the effectiveness of APTS and APSS as robust fluorescent probes, with implications for environmental monitoring and biomedical diagnostics.

Magnetic properties of Ferromagnetic nanoparticles of FexGeTe2(x = 3, 5) directly exfoliated and dispersed in pure water.

FexGeTe2 (x = 3, 5) are two-dimensional ferromagnetic materials that have gained significant attention from researchers due to their relatively high curie temperature and tunability. However, the methods for preparing ferromagnetic nanoparticles and large-area FexGeTe2 films are still in the early stages. Here, we studied the magnetic properties of FexGeTe2 ferromagnetic nanoparticles exfoliated via wet exfoliation in pure water. The coercive field of Fe3GeTe2 ferromagnetic nanoparticles increases significantly, up to 60 times, while that of Fe5GeTe2 only slightly increases from that of bulk crystals. Further investigation related to the dimension of nanoparticles and the Henkel plot analysis reveals that the variation in their coercive field stems from the material's thickness-dependent coercive field and the type of term that governs the interaction between single-domain nanoparticles. Our work demonstrates a facile method for preparing ferromagnetic nanoparticles using van der Waals ferromagnetic materials and tuning their magnetic properties.&#xD.

Bioavailability of Bilastine Oral Self-nanoemulsion: Comparative Study with Commercial Formula in Rats

Background: Bilastine (BL) is a novel non-sedating second-generation antihistamine, and its bioavailability is about 60%. Objective: To compare the bioavailability of prepared oral self-nanoemulsions of BL (BL-SNE) with that of pure BL and marketed tablets. Methods: Four groups of Wistar rats were used in this study, each with six rats weighing between 200 and 250 g. They were treated orally using a a gavage tube. The groups were fed either with conventional tablets ("Alerbix®") after being ground and dispersed with deionized water (DIW), treated with BL-SNE or fed with pure BL powder suspension. The fourth group did not receive any medication. The concentration of BL in the rat’s plasma was measured using HPLC. We used Trandolapril as an an internal standard. Results: The bioavailability results for the the prepared formula, tablet, and pure BL were 24289.91 ng/ml, 0.75 h, 12.81, 97844.7 ng.h/ml, and 98732.9 ng/ml, respectively, for the BL-SNE formula, and 15840.37, 1.0, 13.014, 66140.4, and 67088.3 for the tablets. Meanwhile, the BL suspension demonstrates 10830.12, 1.0 h, 12.96, 59397.12 ng/ml, and 60534.64 ng/ml, respectively. Conclusions: The relative bioavailability of BL-SNE was 1.47 and 1.6 times higher than that of marketed tablets and pure BL, respectively. This indicates an improvement in BL's bioavailability.

Tandem Proton Transfer in Carboxylated Supramolecular Polymer for Highly Efficient Overall Photosynthesis of Hydrogen Peroxide

Proton supply is as critical as O2 activation for artificial photosynthesis of H2O2 via two‐electron oxygen reduction reaction (2e‐ ORR). However, proton release via water dissociation is frequently hindered because of the sluggish water oxidation reaction (WOR), extremely limiting the efficiency of photocatalytic H2O2 production. To tackle this challenge, carboxyl‐enriched supramolecular polymer (perylene tetracarboxylic acid ‐ PTCA) is elaborately prepared by molecular self‐assembly for overall photosynthesis of H2O2. Interestingly, the interconversion between carboxyl as Brønsted acid and its conjugated base realizes rapid proton circulation. Through this efficient tandem proton transfer process, the spatial effect of photocatalytic reduction and oxidation reaction is greatly enhanced with reduced reaction barrier. This significantly facilitates 2e‐ photocatalytic ORR to synthesize H2O2 and in the meanwhile promotes 4e‐ photocatalytic WOR to evolve O2. Consequently, the as‐developed PTCA exhibits a remarkable H2O2 yield of 185.6 μM h‐1 in pure water and air atmosphere under visible light illumination. More impressively, an appreciable H2O2 yield of 78.6 μM h‐1 can be well maintained in an anaerobic system owing to in‐situ O2 generation by 4e‐ photocatalytic WOR. Our study presents a novel concept for artificial photosynthesis of H2O2 via constructing efficient proton transfer pathway to enable rapid proton circulation.

Experimental investigation of a 10 kW-class flat-type loop heat pipe for waste heat recovery

A flat-type 10 kW-class loop heat pipe (LHP) with a box-type wick was designed and developed to handle the higher heat loads in waste heat recovery applications, such as industrial processing and internal combustion engines. Additionally, a numerical model was developed to predict the overall thermal performance of the LHP. The LHP used a stainless steel wick with a pore diameter of 2.0 µm and pure water as the working fluid. The LHP was tested using two types of cooling for the condenser (forced and natural convection), two types of evaporator orientations (horizontal and vertical), and with and without gravity assist (0.3 m and 0 m). For all the tests, the maximum heat load ranged from 5 kW to 10 kW, with the test with a gravity assist of 0.3 m, vertical evaporator orientation, and natural convection performing the best. This test sustained a 10 kW heat load at a steady-state temperature of 182 °C for the evaporator. During the same test, a maximum evaporative heat transfer coefficient of 92,000 W/m2/K at 4.5 kW and a thermal resistance between the evaporator and condenser value of less than 0.007 K/W was achieved. A numerical model was developed to compare the experimental results with the numerical temperature results for the heater block, evaporator, vapor line, condenser, liquid line, and compensation chamber. Overall, the average temperature difference for all components ranged from 7.1 °C to 10.6 °C, with the horizontal orientation without gravity assist and natural convection test predicting the best. The findings demonstrate that LHPs can handle the higher heat loads that are found in waste heat recovery applications for industrial processing and internal combustion engines.

Enhanced filtration membranes with graphene oxide and tannic acid for textile industry wastewater dye removal

ABSTRACT A novel modification technique employing a layer-by-layer (LbL) self-assembly method, integrated with a pressure-assisted filtration system, was developed for enhancing a commercial polyethersulfone (PES) microfiltration (MF) membrane. This modification involved the incorporation of tannic acid (TA) in conjunction with graphene oxide (GO) nanosheets. The effectiveness of the LbL method was confirmed through comprehensive characterization analyses, including ATR-FTIR, SEM, water contact angle (WCA), and mean pore size measurements, comparing the modified membrane with the original commercial one. Sixteen variations of PES MF membranes were superficially modified using a three-factorial design, with the deposited amount of TA and GO as key factors. The influence of these factors on the morphology and performance of the membranes was systematically investigated, focusing on parameters such as pure water permeability (PWP), blue corazol (BC) dye removal efficiency, and flux recovery rate (FRR). The membranes produced with the maximum amount of GO (0.1 mg, 0.55 wt%) and TA as the inner and outer layers demonstrated remarkable FRR and significant BC removal, exceeding 80%. Notably, there was no significant difference observed when using either 0.2 (1.11 wt%) or 0.4 mg (2.22 wt%) in the first layer, as indicated by the Tukey mean test. Furthermore, the modified membrane designated as MF/TA0.4GO0.1TA0.4 was evaluated in the filtration of a simulated dye bath wastewater, exhibiting a BC removal efficiency of 49.20% and a salt removal efficiency of 27.74%. In conclusion, the novel PES MF membrane modification proposed in this study effectively enhances the key properties of pressure-driven separation processes.

"Coir Raincoat"-Boosted Biomimetic Hydrogel for Efficient Solar Desalination and Wastewater Purification.

Solar-driven interfacial evaporation is an efficient method for purifying contaminated or saline water. Nonetheless, the suboptimal design of the structure and composition still necessitates a compromise between evaporation rate and service life. Therefore, achieving efficient production of clean water remains a key challenge. Here, a biomimetic dictyophora hydrogel based on loofah/carbonized sucrose@ZIF-8/polyvinyl alcohol is demonstrated, which can serve as an independent solar evaporator for clean water recovery. This special structural design achieves effective thermal positioning and minimal heat loss, while reducing the actual enthalpy of water evaporation. The evaporator achieves a pure water evaporation rate of 3.88kg m-2 h-1 and a solar-vapor conversion efficiency of 97.16% under 1 sun irradiation. In comparison, the wastewater evaporation rate of the evaporator with ZIF-8 remains at 3.85kg m-2 h-1 for 30 days, which is 16.3% higher than the light irradiation without ZIF-8. Equally important, the evaporator also showcases the capability to cleanse water from diverse sources of contaminants, including those with small molecules, oil, heavy metal ions, and bacteria, greatly improving the lifespan of the evaporator.

Effect of anti‐Agglomerants on carbon dioxide hydrate formation in oil–water systems

AbstractThe experiments in high‐pressure pipelines simulate the formation and fluid of hydrate under deep‐sea conditions, which has practical significance for the deep‐sea landfill of carbon dioxide (CO2) and the safe running of oil and gas pipelines. In this paper, pure water, white oil, CO2, and arquad 2C‐75 were used to study the formation and flow characteristics of CO2 hydrate in the oil–water system with the help of a loop device, and the growth morphology of hydrate was observed through the view‐window on the loop. The experimental results show that in the low water cut system without anti‐agglomerates, hydrate mainly forms on the surface of water droplets and the surface of the free water layer at the bottom of the loop. In the high water cut system, hydrate forms on the pipe wall in the form of hydrate film. Increasing water cuts can shorten the induction period of hydrate formation. Anti‐agglomerates in the oil–water system can inhibit the growth of hydrate film on the pipe wall effectively. Anti‐agglomerates can shorten the induction time of hydrate formation.

Convective heat transfer analysis in turbulent nanofluid flow through a rectangular channel with staggered obstacles: A numerical simulation

This study explores the hydraulic and thermal characteristics of a staggered rectangular baffled channel. The first baffle is inserted in the top channel surface, with subsequent baffles placed on the bottom. Numerical simulations were conducted across a Reynolds number range of 5000 to 50,000. In this study three different baffle inclination angles are examined: Case A involves staggered obstacles perpendicular to the channel wall, while Cases B and C feature obstacles inclined at ±10 ° to the channel surface. Three different types of nanoparticles (SiO2, Al2O3, and CuO) are added to the base fluid (pure water) at a volume fraction of 4 % to formulate the nanofluids utilized in this study. Computational Fluid Dynamics (CFD) simulations were performed using ANSYS Fluent software, to solve the governing equations. The numerical results were validated against experimental data, demonstrating good agreement. The findings reveal that the maximum thermal enhancement factor is 2 at a Reynolds number of 5000 for Case A. Additionally, the heat transfer coefficient experiences a 10.3 % increase for water-CuO nanofluid compared to pure water in Case A. The highest average Nusselt number is observed with pure water, reaching 812 for Case C at a Reynolds number of 50,000.

Enhancing efficiency in ethanol production from high solid corn stover: Insights into enzymatic hydrolysis parameters and cellulase recovery

BackgroundThe simultaneous saccharification and co-fermentation (SSCF) at high solid loading is an effective approach to improve the economic feasibility of bioethanol. MethodsIn this study, the high-solid SSCF of superfine grinding corn stover was treated with cheap and readily available deionized water (DW) instead of sodium citrate buffer solution (SCBS). Additionally, the evaluation of temperature, enzyme loading, solid loading, and cellulose recovery were carried out to determine their impact on ethanol production. Significant FindingsThe results of the analysis indicated that replacing SCBS with DW had negligible effects on the SSCF of ethanol and byproducts (acetic acid and glycerol). The ethanol yield increased by 18 % at 35 °C compared to the yield at 30 °C. As enzyme loading increased, more cellulose active sites in corn stover were bound by cellulase, which increased the ethanol yield by improving the efficiency of enzymatic hydrolysis. The SSCF process didn't incorporate any buffer, resulting in an even higher ethanol titer (55.42 g/L). Furthermore, the cellulase productivity increased by 71 % after recovery, compared to the non-recovery. The results indicated that the optimized SSCF process is a potential technique for producing bioethanol on a commercial level because it improves the production efficiency while keeping costs low.

Hydrothermal oxidation improves the corrosion resistance of titanium and initial cellular responses

Hydrothermal oxidation is the key reaction in the hydrothermal treatment for titanium-based biomedical materials. However, there is still a lack of detailed characterization and in-depth research on the bonding between the oxide film and the substrate, the protection for substrate and the early cellular responses. In this study, nanostructured oxide films were prepared on the titanium surface through hydrothermal oxidation in pure water. The interfacial structure was thoroughly analyzed, corrosion resistance was evaluated, and wetting properties, surface energy and protein adsorption capacity were measured; the interaction between cells and the oxide film was revealed through fluorescence staining and microscopic observations. The results showed that nanocrystalline anatase grew in situ on the titanium surface between 150–200 °C, forming a dense oxide film of approximately 40–50 nm. The oxide film significantly improved the corrosion resistance of the substrate, providing strong shielding protection even after immersion in a solution containing fluoride ions for 30 days. Furthermore, the oxide film endowed the titanium substrate with superhydrophilicity and high surface energy, enhancing protein adsorption, accelerating the polymerization of actin and the formation of stress fibers, and facilitating a tight bond between the cell matrix and the substrate surface; cell attachment and spreading were greatly improved.

Site engineering of linear conjugated polymers to regulate oxygen adsorption affinity for boosting photocatalytic production of hydrogen peroxide without sacrificial agent

Artificial photosynthesis of hydrogen peroxide (H2O2) is a hopeful alternative to the industrial anthraquinone process. However, rational fabrication of the photocatalysts for the production of H2O2 without any sacrificial agents is still a formidable challenge. Herein, two kinds of linear conjugated polymers (LCPs) including pyridinic N functionalized polymer (DEB-N2) and pyridinic N non-contained polymer (DEB-N0) were successfully synthesized. DEB-N2 displays enhanced light capturing ability and good dispersion in water, leading to a substantial initial H2O2 generation rate of 3492μmol g-1h−1 as well as remarkable photocatalytic stability in pure water. Furthermore, the temperature programmed desorption (TPD) and density functional theory (DFT) analysis reveal that highly electronegative pyridine-N atoms in DEB-N2 boost the adsorption affinity of oxygen molecules, which facilitates the occurrence of the oxygen reduction reaction, therefore enhancing the performance of photocatalytic H2O2 production. This study unveils that the presence of pyridinic N in DEB-N2 has a significant impact on photocatalytic H2O2 production, suggesting the precise manipulation of the chemical structure of polymer photocatalysts is essential to achieve efficient solar-to-chemical energy conversion.

Tandem Proton Transfer in Carboxylated Supramolecular Polymer for Highly Efficient Overall Photosynthesis of Hydrogen Peroxide.

Proton supply is as critical as O2 activation for artificial photosynthesis of H2O2via two-electron oxygen reduction reaction (2e- ORR). However, proton release via water dissociation is frequently hindered because of the sluggish water oxidation reaction (WOR), extremely limiting the efficiency of photocatalytic H2O2 production. To tackle this challenge, carboxyl-enriched supramolecular polymer (perylene tetracarboxylic acid - PTCA) is elaborately prepared by molecular self-assembly for overall photosynthesis of H2O2. Interestingly, the interconversion between carboxyl as Brønsted acid and its conjugated base realizes rapid proton circulation. Through this efficient tandem proton transfer process, the spatial effect of photocatalytic reduction and oxidation reaction is greatly enhanced with reduced reaction barrier. This significantly facilitates 2e- photocatalytic ORR to synthesize H2O2 and in the meanwhile promotes 4e- photocatalytic WOR to evolve O2. Consequently, the as-developed PTCA exhibits a remarkable H2O2 yield of 185.6 μM h-1 in pure water and air atmosphere under visible light illumination. More impressively, an appreciable H2O2 yield of 78.6 μM h-1 can be well maintained in an anaerobic system owing to in-situ O2 generation by 4e- photocatalytic WOR. Our study presents a novel concept for artificial photosynthesis of H2O2 via constructing efficient proton transfer pathway to enable rapid proton circulation.