Photocatalytic Synthesis of p-Anisaldehyde in a Mini Slurry-Bubble Reactor under Solar Light Irradiation

Dense photocatalyst slurry was employed for the synthesis of p-anisaldehyde under solar light irradiation. An Fe-modified rutile TiO ₂ (Fe-TiO _2, 34.5 m ²/g) photocatalyst was used as a visible-light-responsive photocatalyst. A conventional TiO ₂ (P25, 35 m ²/g) photocatalyst was also examined as a reference catalyst. XRD patterns and diffuse reflectance spectra showed that Fe-TiO ₂ consists of 100 % rutile phase and absorbs more visible light compared to P25, respectively. The catalyst powder was suspended in an ethyl acetate solution of p-methoxytoluene in the mini-reactor, with oxygen bubbling, under a solar simulator, visible light, and UV LEDs. p-anisaldehyde, as a reaction product, was analyzed by sampling using gas-chromatograph. Regardless of the light source, Fe-TiO ₂ always outperformed P25 in terms of both generation rates (GR) of p-anisaldehyde and energy requirements (ER). It was demonstrated that the highly dense Fe-TiO ₂ slurry was efficient for the synthesis under solar light owing to the small size of the reactor. The small amount of Pt and ZrO ₂ cocatalysts significantly enhanced the GR under solar light. By adopting a visible light responsive Fe-TiO ₂ photocatalyst, the mini slurry-bubble reactor under solar light achieved a high GR per catalyst mass (CM), which is one to two orders higher than that reported by most previous studies with high-power lamps.     

High-performance photocatalysts for the selective oxidation of alcohols to carbonyl compounds

With an increase in awareness about the need for green chemistry, there is a shift in focus towards identifying eco-compatible technologies that can improve product yield and eliminate the use or generation of hazardous compounds. An immediate practical example of such an approach is the development of sustainable methods for alcohol oxidation as alternatives to the current processes that are energy intensive and rely on ecotoxic chemicals. In this regard, heterogeneous photocatalysis has been identified as a robust technique to catalyze reactions under benign conditions, which would otherwise require harsh synthesis routes. With the advent of materials sciences and nanotechnology, there has been a tremendous increase in the scope of applicability of photocatalysis in fine chemicals synthesis. Though an attractive choice, much of the fundamental information pertaining to catalyst activity, selectivity and reaction conditions for optimum conversion are still to be investigated for most of these systems. To this end, this review will encompass recent achievements in the selective photocatalytic oxidation of alcohols by harnessing solar radiation as a viable source of energy. The discussion will be arranged based on common types of photocatalysts reported in literature, namely metal oxides (eg, TiO₂ and ZnO, Nb₂O₅), sulphides (eg, CdS, CuS, and Bi₂S₃), and carbonaceous photocatalysts (eg, g-C₃N₄). Several such candidates for photocatalysts will be discussed critically with the aim of providing useful insight into developing selective photocatalysts that can oxidize alcohols via eco-friendly pathways along with high yields.     

Photocatalytic conversion of ethane: status and perspective

Ethane (C₂H₆) is a main component of natural gas and a notable contributor to photochemical pollution and ozone production in the atmosphere. It is important to convert ethane to useful chemicals. The photocatalytic conversion of ethane is promising but challenging. As the first review article in this area, we summarize the recent important progresses in photocatalytic ethane conversion, with an emphasis on (1) homogeneously functionalization and (2) heterogeneously partial oxidation of ethane. Furthermore, the challenges and future directions are provided for the photocatalytic conversion of ethane.     

离子液体水热法辅助合成稀土Ce掺杂ZnO纳米材料的制备及其应用研究

以1-甲基咪唑和氯代正丁烷为原料,合成1-丁基-3-甲基咪唑氯盐离子液体;以醋酸锌[Zn(Ac)2]、硫酸锌(ZnSO4)和氯化锌(ZnCl2)为锌源,在1-丁基-3-甲基咪唑氯盐离子液体和丙氨酸体系中与硝酸铈反应,经水热合成法制备得到Ce掺杂的纳米ZnO。采用扫描电子显微镜(SEM)、紫外-可见光吸收光谱(UV-Vis)、X射线衍射仪(XRD)、X射线光电子能谱分析(XPS)和红外光谱(FT-IR)对产品进行表征。以亚甲基蓝(MB)为目标降解物,采用UV-Vis检测,考察了Ce掺杂的纳米ZnO的光催化活性。研究表明,焙烧温度对光催化的晶体结构和光催化活性产生较大的影响;2%Ce/ZnO、焙烧温度为500℃、催化时间为30 min、亚甲基蓝用量0.05 g、pH值为10时降解率可达99.5%以上。     

A review of hydrogen production processes by photocatalytic water splitting – From atomistic catalysis design to optimal reactor engineering

‘Renewable energy is an essential part of our strategy of decarbonization, decentralization, as well as digitalization of energy.’ – Isabelle Kocher.Current climate, health and economic condition of our globe demands the use of renewable energy and the development of novel materials for the efficient generation, storage and transportation of renewable energy. Hydrogen has been recognised as one of the most prominent carriers and green energy source with challenging storage, enabling decarbonization. Photocatalytic H₂ (green hydrogen) production processes are targeting the intensification of separated solar energy harvesting, storage and electrolysis, conventionally yielding O₂/H₂. While catalysis is being investigated extensively, little is done on bridging the gap, related to reactor unit design, optimisation and scaling, be it that of material or of operation. Herein, metals, oxides, perovskites, nitrides, carbides, sulphides, phosphides, 2D structures and heterojunctions are compared in terms of parameters, allowing for efficiency, thermodynamics or kinetics structure–activity relationships, such as the solar-to-hydrogen (STH). Moreover, prominent pilot systems are presented summarily.     

BiOBr and BiOCl decorated on TiO2 QDs: Impressively increased photocatalytic performance for the degradation of pollutants under visible light

BiOBr and BiOCl were decorated on TiO₂ QDs through n-p-p heterojunctions by a simple strategy and they were applied for degradation of three organic dyes upon visible illumination. The obtained photocatalysts were analyzed via XRD, FESEM, EDX, UV–vis DRS, PL, BET, TEM, HRTEM, FT-IR, EIS, XPS, and transient photocurrent measurements. The TiO₂ QDs/BiOBr/BiOCl nanocomposite with 20% wt. of BiOBr and 30% wt. of BiOCl displayed superior photoability in the degradation of methylene blue, rhodamine B, and fuchsine, which was almost 34.5, 176, and 78.7-times larger than TiO₂ and 27.8, 13.5, and 51.5-folds greater than TiO₂ QDs, respectively. The results show that the construction of intimate n-p-p heterojunctions between BiOBr, TiO₂ QDs, and BiOCl counterparts leads to enhanced visible-light harvesting and improved charge separation, resulted efficiently increased photocatalytic activity. The trapping results proved that h⁺, ^•O₂⁻, and OH^• species have considerable effects on the degradation reaction. We think that the improved efficiency of the ternary TiO₂ QDS/BiOBr/BiOCl photocatalyst is a splendid alternative for the removal of toxic contaminants from wastewater.     

Rice spike-like g-C3N4/TiO2 heterojunctions with tight-binding interface by using sodium titanate ultralong nanotube as precursor and template

A novel rice spike-like g-C₃N₄/TiO₂ nanowire heterojunctions are fabricated by hydrothermal treating Na₂Ti₃O₇ ultralong nanotubes in the presence of g-C₃N₄. The presence of g-C₃N₄ promotes the hydrolysis of Na₂Ti₃O₇ ultralong nanotubes. The partially replaced O of TiO₂ by N from g-C₃N₄ leads to the formation of a tight-binding interface between one dimensional TiO₂ and two dimensional g-C₃N₄, which is crucial for fast and effective transfer of photogenerated electrons in heterostructured photocatalysts. As a result, the g-C₃N₄/TiO₂ nanowire heterojunctions exhibit excellent visible-light photocatalytic activity. The kinetic constant (k) of g-C₃N₄/TiO₂ (0.024?min^?1) for degradation of methylene blue under visible light irradiation is 1.85 and 4 times than that of pure g-C₃N₄ and P25, respectively.     

Construction of hierarchical FeIn2S4/BiOBr S-scheme heterojunction with enhanced visible-light photocatalytic performance for antibiotics degradation

Constructing heterojunction provides a promising tactic to improve the photocatalytic efficiency of catalysts. In this paper, hierarchical FeIn₂S₄/BiOBr heterostructure photocatalysts were prepared by facile two step methods and applied to effectively remove ciprofloxacin (CIP) and tetracycline (TC) under visible light. Compared to single catalyst, FeIn₂S₄/BiOBr hybrids display significantly improved photocatalytic activity. Among the series, 6 wt% FeIn₂S₄/BiOBr shows the optimal photocatalytic performance, where the degradation efficiencies of TC and CIP are 3.15 and 2.88 times greater than pure BiOBr, respectively. Such an improvement could arise from the S-scheme heterojunctions and unique hierarchical structures, which brings stronger light absorption, higher photoexcited charge separation efficiency and superior redox ability. Furthermore, 6 wt% FeIn₂S₄/BiOBr composite exhibits excellent stability and reusability. Radical capture experiments and EPR analyses uncover that O₂^–, h⁺ and OH are primarily reactive substances during photocatalytic removal of TC. The products of TC were detected by LC-MS analyses and possible decomposition paths are proposed. Eventually, a possible photodegradation mechanism over FeIn₂S₄/BiOBr S-scheme heterojunction is proposed. These findings supply new perspective for the simple synthesis of S-scheme photocatalysts with promising applications in environment remediation.     

Graphitic-C3N4/ZnCr-layered double hydroxide 2D/2D nanosheet heterojunction: Mesoporous photocatalyst for advanced oxidation of azo dyes with in situ produced H2O2

In this study the constructional modification of Graphitic carbon nitride nanosheet (GCN-ns) has been made with the aid of ZnCr layered double hydroxide (ZC-LDH) in a unique 2D-2D structure to enhance its visible light absorption. Optical and morphological study presents successful incorporation of ZC-LDH on the surface of GCN-ns. Through adjusting of GCN-ns by ZC-LDH lower recombination rate of e^?/h⁺ pairs, longer lifetimes and an increase in contamination reduction was brought out. The binary nanocomposite was employed to effectively degrade Rhodamine B under UV/vis light irradiation. The improvement in photocatalytic abilities was proven to be related to in situ self-production of H₂O₂ on GCN-ns/ZC-LDH surface by Xe light irradiation which in return accounts for additional hydroxide radical generation. Radical quenching experiments specified the main active species involved while the consequent step-scheme (S-scheme) charge transfer mechanism was proposed.