Magnetic recyclable ZnO/SrFe12O19 photocatalyst for effective photodegradation of rhodamine B under simulated sunlight

This work develops a novel magnetic photocatalysts ZnO/SrFe₁₂O₁₉ (ZS) synthesized with hydrothermal process. The introduction of SrFe₁₂O₁₉ not only enhances the photocatalytic behavior of ZnO towards Rhodamine B (RhB) decomposition, but also reinforces the recycling stability. Especially, ZS-5 composite exhibits the optimal photocatalytic performance, and the RhB decomposition reaches 99.5% after being exposed to simulative sunlight for 70 min, which is obviously superior to that of bare ZnO. Furthermore, the ZS-5 can be recovered from RhB solution by an extra magnet space and reused. After five recycles, the RhB removal efficiency can still be maintained over 90%. Such prominent photocatalytic property and stability of ZS-5 are associated with the greatly improved detachment efficiency of photoexcited carriers in a magnetic field. This study could provide a new-type recyclable photocatalyst that can effectively purify dye wastewater for convenient recovery.     

Hydrogel photocatalysts for efficient energy conversion and environmental treatment

Photocatalysts have attracted great research interest owing to their excellent properties and potential for simultaneously addressing challenges related to energy needs and environmental pollution. Photocatalytic particles need to be in contact with their respective media to exhibit efficient photocatalytic performances. However, it is difficult to separate nanometer-sized photocatalytic materials from reaction media later, which may lead to secondary pollution and a poor recycling performance. Hydrogel photocatalysts with a three-dimensional (3D) network structures are promising support materials for photocatalysts based on features such as high specific surface areas and adsorption capacities and good environmental compatibility. In this review, hydrogel photocatalysts are classified into two different categories depending on their elemental composition and recent progresses in the methods for preparing hydrogel photocatalysts are summarized. Moreover, current applications of hydrogel photocatalysts in energy conversion and environmental remediation are reviewed. Furthermore, a comprehensive outlook and highlight future challenges in the development of hydrogel photocatalysts are presented.     

二氧化钛固载杂多酸催化剂的制备及其光催化性能研究

采用浸渍法以TiO2为载体制备了固载型杂多酸光催化剂--H3PW12O40/TiO2,H8SiW12O42/TiO2,H7PMo12O42/TiO2.通过Hammett指示剂与紫外光谱相结合的方法测定固体杂多酸催化剂的酸度,分别考察杂多酸种类、浸渍时间、浸渍浓度、烧结方式、烧结温度对催化剂酸度的影响,并对所制备的催化剂进行了红外光谱和光催化活性测试.结果表明,杂多酸固载到TiO2的表面,得到了催化活性较TiO2更强的复合杂多酸光催化剂,其对酸性大红3R的降解率从纯TiO2的79%提高到91%.以磷钨酸水溶液浸渍TiO2,浸渍浓度为0.10 mol·L-1 ,浸渍时间为28 h,烘干温度为120℃,微波炉焙烧功率为650 W,烧结时间为40 min制得的催化剂活性最高.在HPA-TiO2光催化系统中,杂多酸显著加速电子从TiO2表面到O2分子的传递,改变了TiO2光催化反应历程,从而提高光催化效率.     

Metal Single-Atom Cocatalyst on Carbon Nitride for the Photocatalytic Hydrogen Evolution Reaction: Effects of Metal Species

Single-atom (SA) catalysts exhibit high activity in various reactions because there are no inactive internal atoms. Accordingly, SA cocatalysts are also an active research fields regarding photocatalytic hydrogen (H₂) evolution which can be generated by abundant water and sunlight. Herein, it is investigated whether 10 transition metal elements can work as an SA on graphitic carbon nitride (g-C₃N₄; i.e., gCN), a promising visible-light-driven photocatalyst. A method is established to prepare SA-loaded gCN at high loadings (weight of ≈3 wt.% for Cu, Ni, Pd, Pt, Rh, and Ru) by modulating the photoreduction power. Regarding Au and Ag, SAs are formed with difficulty without aggregation because of the low binding energy between gCN and the SA. An evaluation of the photocatalytic H₂-evolution activity of the prepared metal SA-loaded gCN reveals that Pd, Pt, and Rh SA-loaded gCN exhibits relatively high H₂-evolution efficiency per SA. Transient absorption spectroscopy and electrochemical measurements reveal the following: i) Pd SA-loaded gCN exhibits a particularly suitable electronic structure for proton adsorption and ii) therefore they exhibit the highest H₂-evolution efficiency per SA than other metal SA-loaded gCN. Finally, the 8.6 times higher H₂-evolution rate per active site of Pd SA is achieved than that of Pd-nanoparticles cocatalyst.     

Simultaneous CO2 and H2O Activation via Integrated Cu Single Atom and N Vacancy Dual-Site for Enhanced CO Photo-Production

Photocatalytic conversion of CO₂ into fuels using pure water as the proton source is of immense potential in simultaneously addressing the climate-change crisis and realizing a carbon-neutral economy. Single-atom photocatalysts with tunable local atomic configurations and unique electronic properties have exhibited outstanding catalytic performance in the past decade. However, given their single-site features they are usually only amenable to activations involving single molecules. For CO₂ photoreduction entailing complex activation and dissociation process, designing multiple active sites on a photocatalyst for both CO₂ reduction and H₂O dissociation simultaneously is still a daunting challenge. Herein, it is precisely construct Cu single-atom centers and two-coordinated N vacancies as dual active sites on CN (Cu₁/N_2CV-CN). Experimental and theoretical results show that Cu single-atom centers promote CO₂ chemisorption and activation via accumulating photogenerated electrons, and the N_2CV sites enhance the dissociation of H₂O, thereby facilitating the conversion from COO* to COOH*. Benefiting from the dual-functional sites, the Cu₁/N_2CV-CN exhibits a high selectivity (98.50%) and decent CO production rate of 11.12 µmol g⁻¹ h⁻¹. An ingenious atomic-level design provides a platform for precisely integrating the modified catalyst with the deterministic identification of the electronic property during CO₂ photoreduction process.     

TiO_2-SiO_2复合气凝胶涂层的制备和光催化性能

利用TiCl4和工业水玻璃为原料,通过溶胶凝胶法制备TiO2-SiO2复合凝胶,用三甲基氯硅烷(TMCS)/乙醇(EtOH)/正己烷(Hexane)混合溶液对湿凝胶进行改性,常压干燥制备了TiO2-SiO2气凝胶,经150℃干燥所得的气凝胶具有多孔结构,获得的气凝胶比表面积达到646～816m2/g,孔体积达到1.52～2.19cm3/g。用乙醇作为分散剂,将气凝胶块体研磨成具有一定黏度的浆料,采用丝网印刷法制成TiO2-SiO2复合气凝胶涂层。利用X射线衍射(XRD)、扫描电镜(SEM)和孔径及比表面积分析仪(BET)对复合气凝胶的结构、形貌和孔性质进行了研究,通过分光光度计法分析了TiO2-SiO2复合气凝胶涂层光催化降解罗丹明B的性能,在可见光下照射4h后降解率达到77%。     

An efficient ZnS-UV photocatalysts generated in situ from ZnS(en)0.5 hybrid during the H2 production in methanol–water solution

Highly active ZnS-UV was obtained in situ from ZnS(en)_0.5 hybrid during the hydrogen formation using a methanol–water solution under UV irradiation. X-ray diffraction patterns and UV spectroscopy for both ZnS-UV and ZnS-400 obtained from the calcination of the ZnS(en)_0.5 hybrid showed similar structural and photophysical properties; however, the efficiency of the ZnS-UV semiconductor was 7 times higher (4825 μmol h⁻¹ g⁻¹) compared to the ZnS-400. The highest H₂ production was obtained using a UV lamp of very low intensity (2.2 mW cm⁻¹) and it is attributed to a quantum size effect caused by the slow elimination of ethylenediamine (en) in the structural ZnS layer during the UV irradiation.     

Kilogram-scale production of highly active chalcogenide photocatalyst for solar hydrogen generation

Solar photocatalytic hydrogen production from water has been regarded as an ideal way addressing world energy and environmental crises. The technology has long relied on the development of an efficient photocatalyst. In addition to its photocatalytic performance, the large-scale production of certain photocatalyst from the viewpoint of particle application remains a challenge yet has received insufficient focus. Herein, we report an efficient and practical batch preparation system based upon hydrothermal method to the scalable production of chalcogenide nanoparticle photocatalyst. Taking the synthesis of Cd_0.5Zn_0.5S (CZS) twinned photocatalyst as an example, the outcome of CZS photocatalyst could reach ～0.8 kg in this batched synthesis, which is about 390 times of the lab-scale production in mass amount. It was found that the twinned structure and visible-light absorption property were well maintained. Although further measurements toward the photocatalytic activity indicate slight decrement on solar H₂ generation compared to the lab-scale synthesized CZS photocatalyst, a high quantum efficiency of about 40.5% at 425 nm remained. The photocatalytic reaction could also stably proceed for 200 h without notable decay of H₂-evolution rate. This work thus provides a powerful means for facile scaling up the chalcogenide nanoparticle photocatalyst at the kilogram level with both high quality and good reproducibility.