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.

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.

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.

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.

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.

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.

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.

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.

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.

Room-Temperature Synthesis of Covalent Organic Framework (COF-LZU1) Nanobars in CO2 /Water Solvent.

The development of facile, rapid, low-energy, environmentally benign routes for the synthesis of covalent organic frameworks (COFs) is of great interest. This study concerns the utilization of water containing dissolved CO2 as a solvent for the room-temperature synthesis of COF. The as-synthesized particles, denoted COF-LZU1, combine advantages of good crystallinity, nanoscale size, and high surface area, which suggests promising application as a support for heterogeneous catalysts. Moreover, this versatile CO2 -assisted method is also applicable for the room-temperature synthesis of Cu-COF-LZU1. This method gives rise to new opportunities for fabricating COFs and COF-based materials with different compositions and structures.

Photocatalytic CO2 Transformation to CH4 by Ag/Pd Bimetals Supported on N-Doped TiO2 Nanosheet.

To develop photocatalysts with desirable compositions and structures for improving the efficiency and selectivity of CO2 conversion to CH4 under mild conditions is of great importance. Here, we design an effective photocatalyst of bimetal (Ag/Pd) nanoalloys supported on nitrogen-doped TiO2 nanosheet for CO2 conversion. Such a novel photocatalyst combines multiple advantages of abundant Ti3+ ions, oxygen vacancies, and substitutional nitrogen that are favorable for catalyzing CO2 reduction. It was found that CO2 could be efficiently transformed to CH4 under mild conditions, i.e., in aqueous solution and at atmospheric pressure and room temperature. The maximum production rate of CH4 can reach 79.0 µmol g-1 h-1. Moreover, the Ag/Pd bimetals supported on N-doped TiO2 nanosheet exhibit high selectivity to CH4. The as-synthesized photocatalyst can be well recycled for CO2 reduction.

Highly selective and efficient reduction of CO2 to CO on cadmium electrodes derived from cadmium hydroxide.

A non-noble cadmium electrode was synthesized via an electrolysis strategy, which can electroreduce carbon dioxide into carbon monoxide with high selectivity and efficiency. The partial current density for CO can reach up to 59.0 mA cm-2 at a Faradaic efficiency of 99.2% using 1-butyl-3-methylimidazolium hexafluorophosphate/acetonitrile as the electrolyte.

MIL-125-NH2@TiO2 Core-Shell Particles Produced by a Post-Solvothermal Route for High-Performance Photocatalytic H2 Production.

Metal-organic frameworks (MOFs) have proven to be an interesting class of sacrificial precursors of functional inorganic materials for catalysis, energy storage, and conversion applications. However, the controlled synthesis of MOF-derived materials with desirable compositions, structures, and properties still remains a big challenge. Herein, we propose a post-solvothermal route for the outer-to-inner loss of organic linkers from MOF, which is simple, rapid, and controllable and can be operated at temperature much lower than that of the commonly adopted pyrolysis method. By such a strategy, the MIL-125-NH2 particles coated by TiO2 nanosheets were produced, and the thickness of TiO2 shell can be easily tuned. The MIL-125-NH2@TiO2 core-shell particles combine the advantages of highly active TiO2 nanosheets, MIL-125-NH2 photosensitizer, plenty of linker defects and oxygen vacancies, and mesoporous structure, which allows them to be utilized as photocatalysts for the visible-light-driven hydrogen production reaction. It is remarkable that the hydrogen evolution rate by MIL-125-NH2@TiO2 can be enhanced 70 times compared with the pristine MIL-125-NH2. Such a route can be easily applied to the synthesis of different kinds of MOF-derived functional materials.

One-step synthesis of ultrathin α-Co(OH)2 nanomeshes and their high electrocatalytic activity toward the oxygen evolution reaction.

Herein, we demonstrate for the first time the one-step synthesis of ultrathin α-Co(OH)2 nanomeshes by an imidazole-directed route. The α-Co(OH)2 nanomeshes combine the advantages of ultrathin thickness (3 nm), small mesopores (3.7 nm), large specific surface area (181.1 m2 g-1) and high surface oxygen vacancy density, which exhibit excellent electrocatalytic performance for the oxygen evolution reaction.

Solvent Impedes CO2 Cycloaddition on Metal-Organic Frameworks.

The catalytic performance of metal-organic frameworks (MOFs) for the synthesis of cyclic carbonate from carbon dioxide and epoxides has been explored under solvent and solvent-free conditions, respectively. It was found that MOF catalysts have significantly improved catalytic activities in solvent-free CO2 cycloaddition reactions than those in solvent. The mechanism was discussed with regard to the competition of solvent with substrate to adhere MOF catalysts during the reaction process.

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.

Metal-Organic Framework-Stabilized CO2/Water Interfacial Route for Photocatalytic CO2 Conversion.

Here, we propose a CO2/water interfacial route for photocatalytic CO2 conversion by utilizing a metal-organic framework (MOF) as both an emulsifier and a catalyst. The CO2 reduction occurring at the CO2/water interface produces formate with remarkably enhanced efficiency as compared with that in conventional solvent. The route is efficient, facile, adjustable, and environmentally benign, which is applicable for the CO2 transformation photocatalyzed by different kinds of MOFs.

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.

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.