Developing Insoluble Polyoxometalate Clusters to Bridge Homogeneous and Heterogeneous Water Oxidation Photocatalysis.

Cluster catalysts are attractive for their atomically precise structures, defined compositions, tunable coordination environments, uniform active sites, and their ability to transfer multiple electrons, but they suffer from poor stability and recyclability. Here, we report a general approach to the direct insolubilization of a water soluble polyoxometalate (POM) [{(B-α-PW9 O34 )Co3 (OH)(H2 O)2 (O3 PC(O)-(C3 H6 NH3 )PO3 )}2 Co]14- (Co7 ) and formation of a series of POM-based solid catalysts with the counter-cations Ag+ , Cs+ , Sr2+ , Ba2+ , Pb2+ , Y3+ , and Ce3+ . They exhibit improved catalytic activities for visible-light-driven water oxidation following the trend CsCo7 >SrCo7 >AgCo7 >CeIII Co7 >BaCo7 >YCo7 >PbCo7 . While CsCo7 exhibits mainly homogeneous catalysis, the others are predominantly heterogeneous catalysts. An optimal oxygen yield of 41.3 % and a high apparent quantum yield (AQY) of 30.6 % for SrCo7 is obtained, which is comparable to that of the parent homogeneous POM. Band gap structures, UV/Vis spectra, and real-time laser flash photolysis experiments collectively suggest that easier electron transfer from the solid POM catalyst to the photosensitizer promotes photocatalytic water oxidation performance. These solid POM catalysts exhibit good stability, which is directly confirmed by a combination of Fourier-transform infrared spectroscopy, electron microscopy, X-ray diffraction patterns, Raman spectroscopy, X-ray photoelectron spectroscopy, five cycles of tests, and poisoning experiments.

Recent developments in photocatalytic production of hydrogen peroxide.

Hydrogen peroxide (H2O2), an environmentally friendly strong oxidant and energy carrier, has attracted widespread attention in photocatalysis. Artificial photosynthesis of H2O2 using water and oxygen as raw materials, solar energy as an energy source, and semiconductor materials as catalysts is considered a promising technology. In the past few decades, encouraging progress has been made in the photocatalytic production of H2O2. Therefore, we summarize the research achievements in this field in recent years. This review first briefly introduces the reaction pathway, detection techniques and evaluation metrics. Then, the recent advances in photocatalysts are highlighted. Furthermore, the existing challenges and possible solutions in this field are presented. At last, we look forward to the future development direction of this field. This review provides valuable insights and guidance for efficient photocatalytic H2O2 production.

Different concentrations of hyaluronic acid eye drops for dry eye syndrome: a systematic review and Meta-analysis.

AIM: To compare high or low concentration of hyaluronic acid eye drops (HY) for dry eye syndromes (DES). METHODS: Randomized controlled trials (RCTs) comparing various concentrations of HY were searched in PubMed, Embase, Web of Science, Cochrane, SinoMed, CNKI, Wanfang Database, CQVIP, and Chinese journals databases between inception and July 2023. Pooled standardized mean differences (SMD) or weighted mean difference (WMD) with 95% confidence intervals (CI) from RCTs evaluating Schirmer's I test (SIT), corneal fluorescein staining score (CFS), tear breakup time (TBUT), DES score (DESS), and Ocular Surface Disease Index (OSDI) were calculated. Sensitivity analysis, Egger's test and Meta-regression analysis were performed for all indicators. RESULTS: We conducted a Meta-analysis of 10 RCTs that met the inclusion criteria, involving 1796 cases. High-concentrations group significantly improved the outcome of CFS according to random effects modelling (SMD, -3.37; 95%CI, -5.25 to -1.48; P=0.0005). The rest of the results were not statistically significant, including indicators such as SIT, TBUT, DESS and OSDI. CONCLUSION: For dry eyes with positive corneal staining, a high concentration of HY is recommended, whereas in other cases, a high concentration of HY does not offer a more pronounced advantage over a low concentration of HY in the treatment of dry eyes.

Immobilization of Metal-Organic Framework MIL-100(Fe) on the Surface of BiVO4: A New Platform for Enhanced Visible-Light-Driven Water Oxidation.

The development of new dual functional photocatalysts is highly desirable for conversion and storage of solar energy. Herein, we first constructed hierarchical structure MIL-100(Fe)@BiVO4 in situ growing MIL-100(Fe) nanoparticles (NPs) on the surface of decahedron BiVO4 under mild hydrothermal conditions. The as-synthesized hybrid nanostructure is unambiguously determined using a series of characterization methods. These results demonstrate that the ultra-tiny MOF MIL-100(Fe) particles are immobilized on the surface of decahedron BiVO4 and the composite exhibits a strong interaction between BiVO4 and MIL-100(Fe). This hybrid material MIL-100(Fe)@BiVO4 is employed as a photocatalyst for water oxidation reaction and demonstrates higher O2 production activity in comparison with bare BiVO4. The best performance obtained at the optimal mass percentage of MIL-100(Fe) (8.0 wt %) reaches 333.3 µmol h-1 g-1 of the O2 evolution rate irradiated with visible light, which is almost 4.3 times higher than bare BiVO4 (77.3 µmol h-1 g-1). The enhanced water oxidation performance is due to the more efficient interfacial electron-hole transfer between MIL-100(Fe) and BiVO4, which is verified by the results of various photo-electrochemical characterizations. Moreover, the as-prepared composite MIL-100(Fe)@BiVO4 also displays excellent stability for visible-light-driven water oxidation. This study affords a rational strategy for the controllable construction by loading metal-organic frameworks on a semiconductor surface, which is a good reference for other artificial photosystems.

A stable iron-containing polyoxometalate coupled with semiconductor for efficient photocatalytic water oxidation under acidic condition.

A robust water oxidation system using BiVO4 as light-harvesting material and iron-containing polyoxometalate Fe11 as cocatalyst is constructed, in which an apparent quantum efficiency of 25.3% and a turnover frequency (TOFinitial) of 173 h-1 are obtained. Most importantly, the iron-containing polyoxometalate remains stable and intact during the reaction process through the pH adjustment strategy and plays a true molecular cocatalyst role in the semiconductor photocatalytic water oxidation system.

FeO x Derived from an Iron-Containing Polyoxometalate Boosting the Photocatalytic Water Oxidation Activity of Ti3+-Doped TiO2.

The development of efficient and stable catalyst systems using low-cost, abundant, and nontoxic materials is the primary demand for photocatalytic water oxidation. Distinguishing the true active species in a heterogeneous catalytic system is important for construction of efficient catalytic systems. Herein, hydrothermally synthesized Ti3+ self-doped TiO2, labeled as Ti3+/TiO2, was first used as a light absorber in a powder visible light-driven photocatalytic water oxidation reaction. When an iron-containing polyoxometalate Na27[Fe11(H2O)14(OH)2(W3O10)2(α-SbW9O33)6] (Fe11) was used as a cocatalyst, an amorphous layer of active species was wrapped outside the initial Ti3+/TiO2 nanorod and the in situ formed composite was labeled as F/Ti3+/TiO2. When the composite F/Ti3+/TiO2 was tested as a photocatalytic water oxidation catalyst, dramatically improved oxygen evolution performance was achieved. The composite F/Ti3+/TiO2 showed an oxygen evolution rate of 410 µmol/g/h, which was about 11-fold higher than that of prism Ti3+/TiO2. After 24 h of illumination, an O2 yield of 36.4% was achieved. The contrast experiments, high-resolution transmission electron microscopy, and X-ray photoelectron spectroscopy characterization demonstrated that FeO x is the true cocatalyst that enhanced the oxygen evolution activity of TiO2. A recycling experiment proved that the composite F/Ti3+/TiO2 has favorable stability in the oxygen production process.