Ternary heterojunction of cross-linked benzene Polymer/Bi2MoO6-Graphene oxide catalysts promote efficient adsorption and photocatalytic removal of oxytetracycline.

Antibiotics are refractory degradable organic pollutants that present a significant hazard to water environments. In this work, a ternary composite (KB/BMO-GO) comprising of graphene oxide (GO), Bi2MoO6 (BMO), and a cross-linked benzene polymer (KB) was synthesized and applied to promote the synergistic adsorption-photocatalytic degradation of the refractory pollutant, oxytetracycline (OTC). The inclusion of GO and KB in the composite enhanced the OTC adsorption performance of the catalysts, and the construction of Z-scheme heterojunction promoted the photogenerated charge separation efficiency and broadened the range of light absorption, thereby enhancing the photocatalytic performance. Moreover, we compared the performance of catalysts loaded with different mass ratios of KB (x% KB/BMO-GO). Among them, the 15 % KB/BMO-GO catalyst sample had the best OTC degradation performance. Specifically, 15 % KB/BMO-GO could adsorb 69.7 % of OTC in 30 min, reaching an OTC degradation rate of 93.3 % under visible light irradiation. h+ and 1O2 are the main active substances in the photocatalytic process. In addition, the catalysts are acid-alkali and salt-resistant, as well as good reusability. This study provides a valuable reference for the preparation of highly efficient photocatalysts for synergistic adsorption-photodegradation processes.

Triazine-based conjugated polymers with regulation of D-A configuration for enhanced photocatalytic activity.

Photocatalysis is a green and environmentally friendly method for degrading dangerous and nonbiodegradable pollutants. In this study, a sequence of metal-free triazine-based electronic donor-acceptor (D-A) conjugated polymers Tr-X (X = Th, BT, BTh) were prepared by D-A configuration regulation between triazine (Tr) and monomers containing N and S, such as thiophene (Th), bithiophene (BTh) and benzothiadiazole (BT) units, for the photocatalytic degradation of bisphenol A (BPA) and benzene contaminants in water under visible light. Among these, Tr-BTh exhibited complete photocatalytic degradation owing to its excellent D-A configuration. Moreover, the N and S atoms, which are rich in triazine and thiophene units, serve as highly dispersed reactive sites. The separation and transfer of photogenerated carriers can be further improved by expanding the light-absorption range of polymers. In addition, the polymers showed good adsorption for BPA and other aromatic organic pollutants through π-π interaction and surface hydrogen bonding, which provides a facile strategy for efficient polymer-based photocatalysts for water purification.

Optimizing Intermediate Adsorption over PdM (M=Fe, Co, Ni, Cu) Bimetallene for Boosted Nitrate Electroreduction to Ammonia.

Electrochemical reduction of nitrate to ammonia (NO3RR) is a promising and eco-friendly strategy for ammonia production. However, the sluggish kinetics of the eight-electron transfer process and poor mechanistic understanding strongly impedes its application. To unveil the internal laws, herein, a library of Pd-based bimetallene with various transition metal dopants (PdM (M=Fe, Co, Ni, Cu)) are screened to learn their structure-activity relationship towards NO3RR. The ultra-thin structure of metallene greatly facilitates the exposure of active sites, and the transition metals dopants break the electronic balance and upshift its d-band center, thus optimizing intermediates adsorption. The anisotropic electronic characteristics of these transition metals make the NO3RR activity in the order of PdCu>PdCo≈PdFe>PdNi>Pd, and a record-high NH3 yield rate of 295 mg h-1 mgcat -1 along with Faradaic efficiency of 90.9 % is achieved in neutral electrolyte on PdCu bimetallene. Detailed studies further reveal that the moderate N-species (*NO3 and *NO2) adsorption ability, enhanced *NO activation, and reduced HER activity facilitate the NH3 production. We believe our results will give a systematic guidance to the future design of NO3RR catalysts.

Interfacial Self-Assembly-Induced Lattice Distortion in Ti3C2 for Enhanced Piezocatalytic Activity.

Herein, self-assembled monolayers (SAMs) are constructed on the surface of Ti3C2 MXene to improve its environmental stability and piezocatalytic activity. Ti3C2/SAMs-X (X = H, Cl, and NH2) was prepared to enhance the piezocatalytic degradation of bisphenol A (BPA) and hydrogen production. Surface-treated Ti3C2 exhibits different lattice parameters and symmetry, thus leading to an increased polarization. The presence of polar functional groups in SAMs remarkably increases the surface potential of Ti3C2, thereby promoting the migration of piezoelectric electrons. Ti3C2/SAMs-NH2 exhibits the highest piezocatalytic performance, thus improving BPA removal and H2 generation by 7 and 1.8 times, respectively. In addition, Ti3C2/SAMs-NH2 remained stable under 100% relative humidity for 15 days. Therefore, it provides a facile strategy for modulating piezocatalytic properties through interfacial self-assembly-induced lattice distortion.

Eliminating Concentration Polarization with Cationic Covalent Organic Polymer to Promote Effective Overpotential of Nitrogen Fixation.

Electrocatalytic nitrogen reduction reaction offers a sustainable alternative to the conventional Haber-Bosch process. However, it is currently restricted by low effective overpotential due to the concentration polarization, which arises from accumulated products, ammonium, at the reaction interface. Here, a novel covalent organic polymer with ordered periodic cationic sites is proposed to tackle this challenge. The whole network exhibits strong positive charge and effectively repels the positively charged ammonium, enabling an ultra-low interfacial product concentration, and successfully driving the reaction equilibrium to the forward direction. With the given potential unchanged, the suppressed overpotential can be much liberated, ultimately leading to a continuous high-level reaction rate. As expected, when this tailored microenvironment is coupled with a transition metal-based catalyst, a 24-fold improvement is generated in the Faradaic efficiency (73.74 %) as compared with the bare one. The proposed strategy underscores the importance of optimizing dynamic processes as a means of improving overall performance in electrochemical syntheses.

Vibration-driven Reduction of CO2 to Acetate with 100 % Selectivity by SnS Nanobelt Piezocatalysts.

Converting CO2 into high-value C2 chemicals such as acetate with high selectivity and efficiency is a critical issue in renewable energy storage. Herein, for the first time we present a vibration-driven piezocatalysis with tin(II) monosulfide (SnS) nanobelts for conversion of CO2 to acetate with 100 % selectivity, and the highest production rate (2.21 mM h-1 ) compared with reported catalysts. Mechanism analysis reveal that the polarized charges triggered by periodic mechanical vibration promote the adsorption and activation of CO2 . The electron transfer can be facilitated due to built-in electric field, decreased band gap and work function of SnS under stress. Remarkably, reduced distance between active sites leads to charge enrichment on Sn sites, promoting the C-C coupling, reducing the energy barriers of the rate determining step. It puts forward a bran-new strategy for converting CO2 into high-value C2 products with efficient, low-cost and environment-friendly piezocatalysis utilizing mechanical energy.

Built-in electric field and oxygen absorption synergistically optimized an organic/inorganic heterojunction for high-efficiency photocatalytic hydrogen peroxide production.

The production of hydrogen peroxide (H2O2) from oxygen and water is an attractive route for converting solar energy into chemical energy. In order to achieve high solar-to-H2O2 conversion efficiency, floral inorganic/organic (CdS/TpBpy) composite with strong oxygen absorption and S-scheme heterojunction was synthesized by simple solvothermal-hydrothermal methods. The unique flower-like structure increased the active sites and oxygen absorption. The existence of S-scheme heterojuntion facilitated the charge transfer across the built-in electric field. Without sacrificial reagents or stabilizers, the optimal CdS/TpBpy had a higher H2O2 production (3600 µmol g-1 h-1), which was 2.4 and 25.6 times than those of TpBpy and CdS, respectively. Meanwhile, CdS/TpBpy inhibited the H2O2 decomposition, thus increasing the overall output. Furthermore, a series of experiments and calculations were carried out to verify the photocatalytic mechanism. This work demonstrates a modification method to improve the photocatalytic activity of hybrid composites, and shows potential applications in energy conversion.

PVDF/PLA electrospun fiber membrane impregnated with metal nanoparticles for emulsion separation, surface antimicrobial, and antifouling activities.

Although many superwetting materials have been designed for the treatment of oil-containing wastewater, separation strategies for oil-in-water systems containing bacteria have rarely been reported. Herein, poly(vinylidene difluoride)- and poly(lactic acid)-blended fibrous membranes loaded with silver and copper oxide nanoparticles were successfully prepared by a two-step method of electrostatic spinning and liquid-phase synthesis. The product membrane showed excellent super-oleophilic properties in air and hydrophobicity under oil. It could separate water-in-oil emulsion systems containing surfactants with an efficiency above 90%. More importantly, the nanoparticle-loaded fibers were characterized by material degradability and slowly released ions. The fibers exhibited excellent antibacterial activities against both gram-positive and -negative bacteria. This work provides a feasible strategy for water-in-oil emulsion separation and bacterial treatment of wastewater.

Solvent-in-Gas System for Promoted Photocatalytic Ammonia Synthesis on Porous Framework Materials.

Photocatalytic nitrogen reduction reaction (PNRR) is emerging as a sustainable ammonia synthesis approach to meet global carbon neutrality. Porous framework materials with well-designed structures have great opportunities in PNRR; however, they suffer from unsatisfactory activity in the conventional gas-in-solvent system (GIS), owing to the hindrance of nitrogen utilization and strong competing hydrogen evolution caused by overwhelming solvent. In this study, porous framework materials are combined with a novel "solvent-in-gas" system, which can bring their superiority into full play. This system enables photocatalysts to directly operate in a gas-dominated environment with a limited proton source uniformly suspended in it, achieving the accumulation of high-concentrated nitrogen within porous framework while efficiently restricting the solvent-photocatalyst contact. An over eightfold increase in ammonia production rate (1820.7 µmol g-1 h-1 ) compared with the conventional GIS and an apparent quantum efficiency as high as ≈0.5% at 400 nm are achieved. This system-level strategy further finds applicability in photocatalytic CO2 reduction, featuring it as a staple for photosynthetic methodology.

Efficient photocatalytic hydrogen peroxide production induced by the strong internal electric field of all-organic S-scheme heterojunction.

Light-driven reaction of oxygen and water to hydrogen peroxide (H2O2) is an environmental protection method, which can convert solar energy into green products. In this work, perylene-3, 4, 9, 10-tetracarboxylic diimide (PDINH) could be recrystallized in situ on the surface of porous carbon nitride (PCN), to obtain an all-organic S-scheme heterojunction (PDINH/PCN). The design of the hierarchical porous photocatalyst improved the mass transfer, enhanced the light absorption and increased specific surface area. Moreover, the construction of the S-scheme heterojunction at the interface of PDINH and PCN exhibited suitable band, which facilitated the separation and transfer of carriers. The H2O2 production rate was up to 922.4 µmol g-1h-1, which was 2.6 and 53.3 times higher than that of PCN and PDINH. Therefore, the all-organic S-scheme heterojunction provides an insight for improving the photocatalytic H2O2 production.

Low quantity of Pt loaded onto CeCoOx nanoboxes: Surface-rich reactive oxygen species for catalytic oxidation of toluene.

An optimized oxygen activity of catalysts can facilitate oxidation of volatile organic compounds. This work shows the first construction of Ce-Co oxide thin-walled nanoboxes. Bulk-phase lattice oxygen is activated by metal-metal interactions. The subsequent uniform dispersion of low loaded Pt nanoparticles further enhances the surface-adsorbed oxygen content, and creates an oxygen-rich reaction interface. Competitive adsorption of water vapor was also inhibited, and complete catalytic oxidation of toluene was achieved at low temperature (T90 =140 °C). A diffuse reflectance infrared Fourier-transform spectroscopy probe was used to investigate the adsorption-catalytic process and the possible synergistic catalytic mechanism (Langmuir-Hinshelwood and Mars-van Krevelen). This work provides a strategy for improving the catalyt Crystal structure ic oxidation performance of nanocatalysts for volatile organic compounds by increasing the catalytic oxygen activity.

Sulfonate-modified calixarene-based porous organic polymers for electrostatic enhancement and efficient rapid removal of cationic dyes in water.

Developing of fast and efficient adsorbents for removal of low concentration refractory organics in water is significant. Herein, a novel calix[4]arene-based porous organic polymer CaPy is constructed through Sonogashira-Hagihara cross-coupling polycondensation. The strong polar sulfonate is further anchored onto the polymer skeleton of CaPy and three sulfonate-modified anionic polymers CaPy-S1, CaPy-S2, and CaPy-S3 were obtained and fully characterized. The adsorption isotherms showed that the maximum adsorption capacities of CaPy, CaPy-S1, CaPy-S2, and CaPy-S3 toward methylene blue (MB) were 270, 1454, 558 and 1381 mg g-1, whereas those for Rhodamine B (RhB) were 183, 2653, 1132, and 1796 mg g-1, respectively. The maximum adsorption capacity toward RhB was the highest reported vale among the currently used synthetic adsorbents. In addition, the pseudo-second-order rate constants of CaPy, CaPy-S1, CaPy-S2, and CaPy-S3 toward MB were 0.00572, 0.488, 2.24, and 0.192 g mg-1 min-1, respectively, and those toward RhB were 0.000234, 0.138, 0.0819, and 0.203 g mg-1 min-1, respectively. The pseudo-second-order rate constant of CaPy-S2 toward MB was 2.24 g mg-1 min-1 indicating one of the highest adsorption speeds. The activation energy of CaPy-S1 for RhB and MB were 121 and 109 kJ mol-1, respectively, demonstrating that the adsorption of both dyes on CaPy-S1 was chemisorption process. Further, the obtained values of Gibbs free energy were negative, revealing that the adsorption process was spontaneous. This work provides an effective approach for improving adsorption performance via post-modification.

Construction of Perylene-based Amphiphilic Micelle and Its Efficient Adsorption and In Situ Photodegradation of Bisphenol A in Aqueous Solution.

Low mass-transfer efficiency and reaction-driving force make it difficult to realize thorough purification in traditional low-concentration pollutant treatments. Herein, we propose an "adsorption/catalysis in situ" perylene based bifunctional micelle for efficient, accurate and rapid adsorption and catalytic degradation of low-concentration bisphenol A (BPA). They show super-fast (within 10 s), high capacity (448 mg g-1 ) and selectivity for BPA adsorption, due to π-π, hydrophobic interactions and hydrogen bonding. The BPA degradation efficiency improves by up to 8 times after forming micelles compared with simple perylene nanorods, which is primarily due to the superior mass-transfer from adsorption. Moreover, self-assembly can optimize the stacking of the perylene moieties and facilitate charge transfer in micelle, and the regular π-π stacking of inside perylene units enhances the response to visible light, resulting in high catalytic capacity and good cycling stability.

NH2-MIL-125(Ti) modified graphitic carbon nitride with carbon vacancy for efficient photocatalytic NO removal.

This paper reports the application of NH2-MIL-125(Ti) modified carbon nitride Cv-C3N4 with carbon vacancies in the removal of NO. We performed a series of characterizations of the complex and compared various ratios with the individual components. The results of UV spectrum analysis show that the composite's range of light absorption expanded due to the modification of Ti metal-organic framework. Furthermore, the results of photocurrent and electrical impedance indicate the compound has a better ability to generate and transfer electrons. The increase in the compound's NO removal efficiency (up to 63%) indicates that MOF has a positive effect on Cv-C3N4 modification-a good method for photocatalysis. Moreover, the compound can promote photocatalysis in a favorable direction.

Metal-organic frameworks-derived manganese trioxide with uniformly loaded ultrasmall platinum nanoparticles boosting benzene combustion.

Four morphologies of metal-organic frameworks derived Mn2O3 were prepared by calcination of metal-organic frameworks self-assembled from metal ions and organic ligands and loaded with platinum. The catalyst showed excellent catalytic performance for benzene (T90% = 131 °C). ESR (electron spin resonance) test showed that due to the strong electron metal support interaction between Pt and Mn2O3, there were a large number of oxygen vacancies on the surface of the catalyst as active sites to promote the oxidation of benzene. The presence of a large number of Lewis acid sites on the catalyst surface was confirmed by Py-IP (Pyridine adsorption infrared spectroscopy) test. The intermediates of benzene catalytic oxidation are ethyl acetate, carboxylic acids and aldehydes, which can be verified by in-situ DRIFTS. In summary, the catalysts synthesized in this work provide a novel perspective for combining metal-organic frameworks-derived oxides and precious metals for the catalytic oxidation of volatile organic compounds.

Ni-Co Bimetallic Hydroxide Nanosheet Arrays Anchored on Graphene for Adsorption-Induced Enhanced Photocatalytic CO2 Reduction.

Photocatalytic CO2 reduction can be implemented to use CO2 , a greenhouse gas, as a resource in an energy-saving and environmentally friendly way, in which suitable catalytic materials are required to achieve high-efficiency catalysis. Insufficient accessible active sites on the catalyst surface and inhibited electron transfer severely limit the photocatalytic performance. Therefore, porous aerogels are constructed from composites comprising different ratios of Ni-Co bimetallic hydroxide (Nix Coy ) grown on reduced graphene oxide (GR) into a hierarchical nanosheet-array structure using a facile in situ growth method. Detailed characterization shows that this structure exposes numerous active sites for enhanced adsorption-induced photocatalytic CO2 reduction. Moreover, under the synergistic effect of Ni-Co bimetallic hydroxide, the CO2 adsorption capacity as well as charge-carrier separation and transfer are excellent. As a result, the Ni7 Co3 -GR catalyst exhibits highly improved catalytic performance when compared with recently reported values, with a high CO release rate of 941.5 µmol h-1  g-1 and a selectivity of 96.3% during the photocatalytic reduction of CO2 . This work demonstrates a new strategy for designing nanocomposites with abundant active sites structures.

Self-supported MoO2-MoO3/Ni2P hybrids as a bifunctional electrocatalyst for energy-saving hydrogen generation via urea-water electrolysis.

The electronic modulation and morphology control of electrocatalysts are effective strategies to improve their catalytic performance. Herein, MoO2-MoO3/Ni2P nanoflowers were fabricated on the skeleton of conductive nickel foam as an electrocatalyst with enhanced performance via a universal hydrothermal and phosphating method. The introduction of P and Mo into the nickel-based catalyst through the co-doping strategy effectively adjusted the electronic structure of the Ni active sites, thereby significantly improving the performance of the catalyst. Particularly, the introduction of Mo allowed adjusting the morphology of the material, thereby increasing the electrochemical active area and promoting the exposure of more active sites. This strategy for improving the electrocatalyst's performance in urea-assisted water splitting will provide a new concept for the simultaneous mitigation of the energy crisis and environmental contamination.

High-Performance and Stable Two-Dimensional MXene-Polyethyleneimine Composite Lamellar Membranes for Molecular Separation.

Two-dimensional (2D) materials are candidates for use in advanced molecular separation and water treatment. Among them, MXenes are cutting-edge two-dimensional (2D) materials with favorable properties such as high hydrophilicity, adjustable interlayer spacing, high mechanical strength, and structural stability. Therefore, they can be used to construct advanced lamellar membranes to ensure enhanced separation performance of modified membranes. Here, we prepared novel stable lamellar membranes through electrostatic attraction between polycation polyethyleneimine (PEI) and a negatively charged MXene, with hydrogen bond formation between their functional groups. By changing the pH of the suspension, the interlayer d-spacing of the prepared membrane could be altered to achieve precise molecular separation and ultrahigh organic solvent penetration. Furthermore, inserting PEI into the interlayer d-spacing of the membrane did not hinder the passage of water molecules. The prepared pH = 2-MXene-PEI membrane for dyes larger than 1.5 nm exhibited a rejection rate of greater than 96%, and the pH = 10-MXene-PEI membrane had a rejection rate of greater than 96% for dyes larger than 1.6 nm. In addition, the optimized MXene-PEI membranes showed channel stability. In this work, high-performance, stable, 2D MXene-PEI membranes with tunable nanochannels were developed. These membranes have great potential for use in precise molecular separation applications.

Pt-Co nanoparticles supported on hollow multi-shelled CeO2 as a catalyst for highly efficient toluene oxidation: Morphology control and the role of bimetal synergism.

A series of hollow multi-shelled CeO2 (HoMS-CeO2) support materials with tunable shell numbers were fabricated and applied to the catalytic oxidation of toluene. HoMS-CeO2 possess much higher catalytic activity (T90 = 236 ℃) than hollow CeO2 with only a single shell (h-CeO2) (T90 = 275℃). The porous multiple-shelled structure has a higher SBET, which strongly promotes gas distribution and provides more active sites. The superiority of this kind of structure was also verified by comparing h-Co3O4 and HoMS-Co3O4. Furthermore, Pt-Co bimetallic nanoparticles were loaded onto HoMS-CeO2. The synergistic effect between Pt and Co was verified by XPS and O2-TPD, which was observed to allow electron transfer between Pt and Co and thus regulate the electronic state of the Pt. Compared with Pt alone, Pt-Co bimetallic nanoparticles could stronglypromotethe activation of O2and oxygen mobility, as revealed by a much higher Oads content and a lower oxygen desorption temperature. Of the catalysts prepared in this study, the 1 wt% PtCo3/CeO2 catalyst was found to be the most suitable for toluene oxidation owing to its excellent activity (T90 = 158 ℃), long-term stability, and water resistance. Finally, in situ DRIFTS was employed to investigate mechanism during toluene oxidation and the possible reaction pathway was proposed.

SuFEx modification of silk fibroin silicon aerogel and its adsorption behavior and antibacterial performance.

A silk fibroin silicon-based composite aerogel (SSA) has been modified via a SuFEx reaction for application in the adsorption of anionic pollutants and antimicrobials in water. The tyrosine fragment in the silk fibroin was modified by a high yielding SuFEx click reaction. A quaternary ammonium salt functionality was introduced into the silk fibroin protein and the modified silk fibroin protein was crosslinked with tetraethyl orthosilicate. The aerogel was then prepared by freeze-drying. The aerogel obtained has biocompatibility and biodegradability properties. Four types of dyes (Methyl orange, Rhodamine B, Methylene blue and Acid red) were applied as targets and the saturated adsorption amounts were calculated. The adsorption behavior of the dyes towards SSA was studied by fitting Langmuir and Freundlich adsorption models. A pseudo-first order kinetic model and a pseudo-second order kinetic model were used to study the kinetics of the adsorption process. After 6 cycles, the removal rate of methyl orange by SSA remained at 81.25%. The adsorption capacity and anti-interference ability of SSA on some other polluting anions such as PO43- and CrO42- were also measured and the efficiency adsorption reached up to 70.94% and 77.91%, respectively. The antibacterial effect of SSA was evaluated with Escherichia coli and Staphylococcus aureus as representative examples.