Visible-light-driven Oxygen Vacancy and Carbon Doping of C@TiO2-x Photocatalyst for Enhanced Pollutants Degradation Performance.

Oxygen Vacancy (OVs) and carbon doping of the photocatalyst body will significantly enhance the photocatalytic efficiency. However, synchronous regulation of these two aspects is challenging. In this paper, a novel C@TiO2-x photocatalyst was designed by coupling the surface defect and doping engineering of titania, which can effectively remove rhodamine B (RhB) and has a relatively high performance with wide pH range, high photocatalytic activity and good stability. Within 90 minutes, the photocatalytic degradation rate of RhB by C@TiO2-x (94.1 % at 20 mg/L) is 28 times higher than that of pure TiO2 . Free radical trapping experiments and electron spin resonance techniques reveal that superoxide radicals (⋅O2- ) and photogenerated holes (h+ ) play key roles in the photocatalytic degradation of RhB. This study demonstrates the possibility of regulating photocatalysts to degrade pollutants in wastewater based on an integrated strategy.

Critical size effect for the surface heat capacities of nano-CdS: theoretical and experimental studies.

The unique physical and chemical properties of nanomaterials are closely related to their surface thermodynamic functions, which mainly depend on their sizes. In this study, the thermodynamic properties of nano-cadmium sulphide (nano-CdS) were investigated by solubility technology. The nano-CdS powders with different particle sizes were prepared via a traditional solvothermal method, and the electrical conductivities of nano-CdS aqueous solutions at different temperatures were measured. The standard dissolution equilibrium constants of nano-CdS at different temperatures were calculated using the theory of dissolution thermodynamics. The standard molar dissolution thermodynamic functions, the molar surface thermodynamic functions and the specific surface thermodynamic functions of nano-CdS with different particle sizes were calculated by combining the thermodynamic functions of bulk-CdS, the principle of the thermodynamic cycle and the principle of electrochemical equilibrium. The experimental results show that the critical size values for the molar surface heat capacity and the specific surface heat capacity for approximately spherical nanoparticles are 9.3 nm and 8.7 nm, respectively. Within an acceptable range of error, the thermodynamic functions have linear and curved relationships with particle sizes and temperatures. Based on these results, it is disclosed that the critical size effect on surface heat capacities of nano-CdS is valuable to understand the energy storage processes of nanomaterials.

Correction: Critical size effect for the surface heat capacities of nano-CdS: theoretical and experimental studies.

Correction for 'Critical size effect for the surface heat capacities of nano-CdS: theoretical and experimental studies' by Shengjiang Zhang et al., Phys. Chem. Chem. Phys., 2022, 24, 6193-6207, https://doi.org/10.1039/D1CP04619E.

Highly Electrocatalytic Ethylene Production from CO2 on Nanodefective Cu Nanosheets.

The electrochemical synthesis of chemicals from carbon dioxide, which is an easily available and renewable carbon resource, is of great importance. However, to achieve high product selectivity for desirable C2 products like ethylene is a big challenge. Here we design Cu nanosheets with nanoscaled defects (2-14 nm) for the electrochemical production of ethylene from carbon dioxide. A high ethylene Faradaic efficiency of 83.2% is achieved. It is proved that the nanoscaled defects can enrich the reaction intermediates and hydroxyl ions on the electrocatalyst, thus promoting C-C coupling for ethylene formation.

Converting Metal-Organic Framework Particles from Hydrophilic to Hydrophobic by an Interfacial Assembling Route.

Here, we propose to modify the hydrophilicity of metal-organic framework (MOF) particles by an interfacial assembling route, which is based on the surface-active nature of MOF particles. It was found that hydrophilic UiO-66-NH2 particles can be converted to hydrophobic particles through an oil-water interfacial assembling route. The underlying mechanism for the conversion of UiO-66-NH2 was investigated by X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. It was revealed that the close assembly of UiO-66-NH2 particles at the oil-water interface strengthens the coordination between organic ligands and metal ions, which results in a decrease in the proportion of hydrophilic groups on UiO-66-NH2 particle surfaces. Hydrophobic UiO-66-NH2 particles show improved adsorption capacity for dyes in organic solvents compared with pristine UiO-66-NH2 particles. It is expected that the interfacial assembling route can be applied to the synthesis of different kinds of MOF materials with tunable hydrophilicity or hydrophobicity required for diverse applications.

Pickering emulsions stabilized by a metal-organic framework (MOF) and graphene oxide (GO) for producing MOF/GO composites.

Herein we demonstrate the formation of a novel kind of Pickering emulsion that is stabilized by a Zr-based metal-organic framework (Zr-MOF) and graphene oxide (GO). It was found that the Zr-BDC-NO2 and GO solids assembling at the oil/water interface can effectively stabilize the oil droplets that are dispersed in the water phase. Such a Pickering emulsion offers a facile route for fabricating Zr-MOF/GO composite materials. After removing water and oil by freeze drying from Pickering emulsions, the Zr-MOF/GO composites were obtained and their morphologies, structures and interaction properties were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction and Fourier transform infrared spectrometry, respectively. The influences of the concentration of GO and Zr-MOF on the emulsion microstructures and the properties of the MOF/GO composites were studied. Based on experimental results, the mechanisms for the emulsion formation by Zr-MOF and GO and the as-synthesized superstructures of the Zr-MOF/GO composite were proposed. It is expected that this facile and tunable route can be applied to the synthesis of different kinds of MOF-based or GO-based composite materials.

Interfacial assembly and hydrolysis for synthesizing a TiO2/metal-organic framework composite.

Herein we propose an interfacial assembly and hydrolysis route for fabricating TiO2/UiO-67 composites. The UiO-67 assembles at the water-oil interface serving as a stabilizer of the emulsion. TiO2 nanoparticles are loaded on UiO-67 by hydrolysis of the precursor TBT (tetra-n-butyl titanate) at the water-oil interface. By such a strategy, hollow capsules structured by UiO-67 and decorated by ultra-small TiO2 nanoparticles were produced. The newly-constructed composite combines the CO2 adsorption properties of UiO-67 and the photocatalytic activity of TiO2, showing high activity for the photocatalytic reduction of CO2 to formic acid. Such a composite with a novel structure provides a promising route for the preparation of new compound materials.

High internal ionic liquid phase emulsion stabilized by metal-organic frameworks.

The emulsification of metal-organic frameworks (MOFs) for the two immiscible phases of water and ionic liquid (IL) was investigated for the first time. It was found that Ni-BDC (BDC = 1,4-dicarboxybenzene) can emulsify water and ILs and favor the formation of high internal phase emulsions (HIPEs) under certain experimental conditions. The microstructures of the HIPEs were characterized by confocal laser scanning microscopy using a fluorescent dye Rhodamine B, which proves that the HIPEs are the IL-in-water type. Further results reveal that the HIPE forms during the IL-in-water to water-in-IL emulsion inversion. The possibilities of the HIPE formation by other MOFs (Cu-BDC and Zn-BDC) were explored and the mechanism for HIPE formation was discussed. The MOF-stabilized HIPE was applied to the in situ synthesis of a MOF/polymer composite by HIPE polymerization. The macroporous MOF/polyacrylamide network and MOF/polystyrene microspheres were obtained from the HIPEs, respectively.

Micellization of long-chain ionic liquids in deep eutectic solvents.

The aggregation behavior of the ionic liquid (IL) 1-alkyl-3-methylimidazolium chloride with different alkyl chain lengths in a deep eutectic solvent (DES, composed of choline chloride and glycerol in a 1 : 2 mole ratio) was studied for the first time. The critical micellar concentration, micellar size and intermolecular interactions in IL/DES solutions were investigated by different techniques including the fluorescence probe technique, small angle X-ray scattering and Fourier transform infrared spectroscopy. The solvophobic effect dominates the micellization of CnmimCl in DES and the intermolecular hydrogen-bond interaction plays a positive role to promote micelle formation. The micellar solutions were utilized for the synthesis of the water-unstable metal-organic framework Cu3(BTC)2 (BTC = 1,3,5-benzenetricarboxylate) at room temperature. X-Ray diffraction, scanning electron microscopy, transmission electron microscopy and nitrogen adsorption-desorption isotherms confirm the formation of crystalline Cu3(BTC)2 nanocrystals with mesoporous structures. The morphologies and porosity properties of Cu3(BTC)2 nanocrystals can be modulated by varying the concentration of CnmimCl.

Metal-Organic Framework for Emulsifying Carbon Dioxide and Water.

Forming emulsions of carbon dioxide (CO2 ) and water can largely expand the utility of CO2 . Herein we propose for the first time the utilization of a metal-organic framework (MOF) for emulsifying CO2 and water. Owing to the hybrid composition, MOF particles can easily assemble at the CO2 /water interface to create a rigid protective barrier around the dispersed droplet. The MOF-stabilized CO2 and water emulsion has exceptional stability compared to those emulsions stabilized by surfactants or other solids. Moreover, the CO2 and water emulsion stabilized by MOF is "tunable" due to the designable features of MOFs and adjustable character of CO2 . Such a novel kind of emulsion composed of CO2 , water, and MOF provides a facile route for constructing MOF superstructures with many advantages. The macroporous networks and hollow capsules of different kinds of MOFs have been successfully derived from CO2 and water emulsions.

Water-in-Supercritical CO2 Microemulsion Stabilized by a Metal Complex.

Herein we propose for the first time the utilization of a metal complex for forming water-in-supercritical CO2 (scCO2 ) microemulsions. The water solubility in the metal-complex-stabilized microemulsion is significantly improved compared with the conventional water-in-scCO2 microemulsions stabilized by hydrocarbons. Such a microemulsion provides a promising route for the in situ CO2 reduction catalyzed by a metal complex at the water/scCO2 interface.

Formation of controllable hydrophilic/hydrophobic drug delivery systems by electrospinning of vesicles.

Novel multifunctional poly(ethylene oxide) (PEO) nanofibrous membrane, which contains vesicles constructed by mixed surfactant cetyltrimethylammonium bromide (CTAB)/sodium dodecylbenzenesulfonate (SDBS), has been designed as dual drug-delivery system and fabricated via the electrospinning process. 5-FU and paeonolum, which are hydrophilic and hydrophobic anticancer model drugs, can be dissolved in vesicle solution's bond water and lipid bilayer membranes, respectively. The physicochemical properties of the electrospun nanofibrous membrane were systematically studied using scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared (FTIR), and X-ray diffraction (XRD). Drug release behaviors of the electrospun nanofibrous membrane fabricated with different molar ratio of CTAB/SDBS vesicle solution were investigated. The result showed that the releasing amount of hydrophilic drug presented an ascending release manner, while the hydrophobic one showed a descending release behavior with increasing of the molar ratio of CTAB/SDBS. Moreover, the release amount of drugs from drug delivery system can be controlled by the molar ratio of CTAB/SDBS in the vesicle solution easily and conveniently. The distinct properties can be utilized to encapsulate environmental demanding and quantificational materials.

Dual stimuli-responsive self-assembly transition in zwitterionic/anionic surfactant systems.

Temperature and pH responsiveness is important for biological applications in protein reconstitution, gene delivery and controlled drug release. The temperature and pH dual responsive self-assembly transition, vesicle-to-micelle transitions (VMTs) and micelle-to-vesicle transitions (MVTs), in dodecyl sulfonatebetaine (DSB)/sodium bis(2-ethylhexyl) sulfosuccinate (AOT) aqueous solution are investigated. Various experimental techniques including cryogenic transmission electronic microscopy, UV-vis spectroscopy, fluorescence spectroscopy, conductivity, and zeta potential were employed to verify the transformation process. Encapsulation of calcein was further applied in this study. The results showed that the self-assembly transition in DSB/AOT aqueous solution is reversible and can be controlled by temperature and pH. It is anticipated that utilizing simple stimuli methods to realize unique self-assembly behaviour in dilute aqueous solution may offer new possibilities in cancer diagnosis and therapy.

Temperature-induced vesicle to micelle transition in cationic/cationic mixed surfactant systems.

Temperature-induced vesicle to micelle transition (VMT), which has rarely been reported in cationic/cationic mixed surfactant systems, was systemically studied in a didodecyldimethylammonium bromide (DDAB)/dodecyltrimethylammonium chloride (DTAC) aqueous solution. We investigated the effect of temperature on DDAB/DTAC aqueous solutions by means of turbidity, conductivity, cryo-TEM, a UV-vis spectrophotometer, and a steady-state fluorescence spectrometer. It was found that increasing temperature could induce the transformation from the vesicle to the micelle in this cationic/cationic mixed surfactant system. The degree of transformation can be easily controlled by the operation temperature. Additionally, by adjusting the proportion of the mixed cationic/cationic systems and employing cationic surfactants with different chain-lengths, we were able to conclude that the hydrophobic tail length of the surfactant affects the aggregation behavior of cationic/cationic mixed surfactant systems as a function of temperature. It is universal to induce the transformation from the vesicle to the micelle by temperature in cationic/cationic mixed surfactant systems. A possible mechanism for the temperature-induced VMT was proposed based on the experimental results.

Improved photocatalytic performance of covalent organic frameworks by nanostructure construction.

Here, we demonstrate for the first time the construction of covalent organic framework (COF) capsules with nanostructured surfaces, which combine advantages of highly accessible surface area, excellent light absorbance, and efficient separation of photogenerated electron-hole pairs. The COF capsules exhibit high activity and selectivity for photocatalytic oxidation under mild conditions.

Hierarchically macro-meso-microporous metal-organic framework for photocatalytic oxidation.

The macro-meso-microporous and defective metal-organic framework constructed by transition metal Zn and 2,2'-bipyridine-5,5'-carboxylate was synthesized in CO2-expanded solvent. It shows high photocatalytic activity and selectivity for the oxidation of amines to imines under mild conditions, i.e., air as an oxidant, room temperature, and involving no photosensitizer or cocatalyst.

Improved photocatalytic performance of metal-organic frameworks for CO2 conversion by ligand modification.

Here we demonstrate that the utilization of 2,4,6-tris(4-pyridyl)pyridine (tpy) for metal-organic framework modification can greatly improve the photocatalytic performance for CO2 reduction. The electron-donating nature of tpy enables the charge transfer effect, which induces strong CO2 binding affinity, facilitates *COOH formation and promotes CO2-to-CO conversion.

Cu x Ni y alloy nanoparticles embedded in a nitrogen-carbon network for efficient conversion of carbon dioxide.

The electrocatalytic conversion of CO2 to CO using non-noble metal catalysts under mild conditions is of great importance. Achieving the combination of high activity, selectivity and current density by developing electrocatalysts with desirable compositions and structures is challenging. Here we prepared for the first time Cu x Ni y alloy nanoparticles embedded in a nitrogen-carbon network. Such an electrocatalyst not only well overcomes the disadvantages of single Cu and Ni catalysts but has a high CO2 adsorption capacity. Outstandingly, the catalyst can effectively convert CO2 into CO with a maximum faradaic efficiency of 94.5% and current density of 18.8 mA cm-2 at a low applied potential of -0.60 V (versus reversible hydrogen electrode, RHE). Moreover, the catalyst is very stable during long-term electrolysis owing to the stabilization of the nitrogen-carbon network.

Bipyridyl-Containing Cadmium-Organic Frameworks for Efficient Photocatalytic Oxidation of Benzylamine.

Metal-organic frameworks (MOFs) have attracted increased research attention in photocatalysis due to their great potential in light harvest and conversion. However, the organic transformations as photocatalyzed by MOFs under mild conditions yet remain a challenge. Herein, three bipyridyl-containing cadmium-organic frameworks Cd(dcbpy) (dcbpy = 2,2'-bipyridine-5,5'-dicarboxylate), Cd(bdc)(bpy) (bdc = 1,4-benzenedicarboxylate; bpy = 2,2'-bipyridyl), and Cd(bdc)(2Me-bpy) (2Me-bpy = 4,4'-dimethyl-2,2'-bipyridyl) were synthesized for the first time. The bpy-containing Cd-MOFs have strong light harvest abilities and suitable photocatalysis energy potentials, making them highly active and selective for the photo-oxidation of benzylamine to N-benzylbenzaldimine under mild conditions, i.e., using atmospheric air as oxidant, at room temperature, and in the absence of any photosensitizer or cocatalyst. It provides an efficient, economical, and green way for the direct oxidation of amines to produce imines.

Manganese acting as a high-performance heterogeneous electrocatalyst in carbon dioxide reduction.

Developing highly efficient electrocatalysts based on cheap and earth-abundant metals for CO2 reduction is of great importance. Here we demonstrate that the electrocatalytic activity of manganese-based heterogeneous catalyst can be significantly improved through halogen and nitrogen dual-coordination to modulate the electronic structure of manganese atom. Such an electrocatalyst for CO2 reduction exhibits a maximum CO faradaic efficiency of 97% and high current density of ~10 mA cm-2 at a low overpotential of 0.49 V. Moreover, the turnover frequency can reach 38347 h-1 at overpotential of 0.49 V, which is the highest among the reported heterogeneous electrocatalysts for CO2 reduction. In situ X-ray absorption experiment and density-functional theory calculation reveal the modified electronic structure of the active manganese site, on which the free energy barrier for intermediate formation is greatly reduced, thus resulting in a great improvement of CO2 reduction performance.