Green synthesis of activated carbon doped tungsten trioxide photocatalysts using leaf of basil (Ocimum basilicum) for photocatalytic degradation of methylene blue under sunlight

Tungsten oxide (WO₃) nanoparticles were prepared hydrothermally by basil leaves extract, and Activated Carbon (AC) was prepared by the carbonization of date pits. Moreover, 1, 2 and 3% of AC doped WO₃ nanoparticles have been fabricated under hydrothermal conditions. The obtained samples have been characterized by using different techniques such as x-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), simultaneous thermogravimetric analysis (TG-DTGA), fourier transform infrared (FT-IR), BET surface area, and Ultra-Violet spectroscopy (UV–Vis). It was observed that band-gap energy of the fabricated materials decreases by increasing AC amount. Similarly, BET surface area and porosity results showed increasing the content of AC, surface area, pore size and pore volume were decreased. The functional groups, determined by FT-IR, played a significant role in the photocatalytic performance. The photocatalytic performance of fabricated samples was used for the degradation of methylene blue (MB) at neutral pH under visible light radiations, and it is observed that WO₃/3%AC photocatalyst showed the highest degradation of MB. Both, capped phytochemicals of basil extract and the nanocomposites, were improved the photocatalytic performance, about 94% photodegradation was observed within 25 min under the reaction conditions. The photocatalyst was stable and about 85% and 81% photodegradation of MB were found under the two times of reusability tests.     

Facile synthesis of Z-scheme NiO/α-MoO3 p-n heterojunction for improved photocatalytic activity towards degradation of methylene blue

In this article, Z-scheme NiO/α-MoO₃ p-n heterojunction is successfully synthesized by a facile hydrothermal route. The phase and nanostructures are researched through a series of characterizations, such as XRD, SEM, TEM, EDX, XPS and DRS. It is confirmed that the NiO nanoparticles are deposited homogeneously on one dimensional α-MoO₃ nanobelts and p-n heterojuction is constructed at the interface of α-MoO₃ and NiO. Photocatalytic activity of the as-synthesized photocatalysts is investigated by photodegradation of methylene blue (MB) under simulated solar light irradiation. Compared with bare α-MoO₃, the NiO/α-MoO₃ p-n heterojunction exhibits significantly improved photocatalytic activity and photostability for MB degradation. The improvement in the photocatalytic performance can be attributed to the optimization of the charge transport pathway offered by Z-scheme heterojunctions, which can promote the effective separation of electron-hole pairs. The results indicate that Z-scheme NiO/α-MoO₃ p-n heterojunction is a novel and efficient photocatalyst with potential application for the removal of organic contaminant in wastewater.     

Surface domain potential difference-mediated efficient charge separation on a defective ZnIn2S4 microsphere photocatalyst

Low-efficiency charge separation in metal sulfides is a major obstacle to realizing high photocatalytic performance. Herein, we propose the concept of a similar surface domain potential difference between adjacent microdomains with and without surface S vacancies on ZnIn₂S₄ to mediate charge separation. Defective ZnIn₂S₄ microspheres (DZISNPs) are prepared through a solvothermal method combined with a low-temperature hydrogenation surface engineering strategy. The as-prepared DZISNPs with a narrowed bandgap of 2.38 eV possess a large specific surface area of 178.5 m² g^?1, a pore size of 6.89 nm, and a pore volume of 0.36 cm³ g^?1, which further improves the visible light absorption. The resultant DZISNPs exhibit excellent visible light activity (2.15 mmol h^?1 g^?1), which is ～two-fold higher than that of the original DZISNP. The experimental results and DFT calculations reveal that the enhanced property can be a result of the surface S vacancy-induced surface domain potential difference, promoting the spatial separation of electrons and holes. Furthermore, the long-term stability of the DZISNPs indicates that the formation of surface S vacancies can inhibit the photocorrosion of ZnIn₂S₄. This strategy provides new insights for fabricating highly efficient and stable sulfide photocatalysts.     

Photocatalytic removal of tetracycline by a Z-scheme heterojunction of bismuth oxyiodide/exfoliated g-C3N4: performance,mechanism, and degradation pathway

Antibiotics, once being released into the environment, become recalcitrant organic pollutants, which pose a potential risk to ecological balance and human health. In this study, a Z-scheme heterojunction of bismuth oxyiodide (BiOI)/exfoliated g-C₃N₄ (BiOI/ECN hereafter) was synthesized by the combination of thermal exfoliation of g-C₃N₄ and chemical precipitation of BiOI for efficient photocatalytic degradation of tetracycline in aqueous solutions under visible light irradiation. The optimized BiOI/ECN delivered an outstanding degradation rate at circa 0.0705 min^?1, which was 10 times higher than that of the bulk g-C₃N₄. The photocatalytic degradation efficiency of tetracycline remained almost unchanged in a pH range of 3–11, and the BiOI/ECN displayed an excellent photostability upon recycled usage. The photocatalytic mechanism of tetracycline was ascribed to the main reactive oxidation species of photogenerated holes and superoxide radicals. In addition, the possible degradation pathways of tetracycline were investigated by HPLC-MS to identify intermediates. The toxicity of photocatalytic-generated intermediates of tetracycline was found significantly alleviated according to the calculation of quantitative structure–activity relationship prediction. This work not only provides an attractive photocatalyst for the removal of tetracycline but also opens a new avenue for rational design of Z-scheme heterojunction composites for tetracycline degradation.     

Steering spatially separated dual sites on nano-TiO2 through SMSI and lattice matching for robust photocatalytic hydrogen evolution

Spatial isolation of different functional sites at the nanoscale in multifunctional catalysts for steering reaction sequence and paths remains a major challenge. Herein, we reported the spatial separation of dual-site Au and RuO₂ on the nanosurface of TiO₂ (Au/TiO₂/RuO₂) through the strong metal-support interaction (SMSI) and the lattice matching (LM) for robust photocatalytic hydrogen evolution. The SMSI between Au and TiO₂ induced the encapsulation of Au nanoparticles by an impermeable TiO_x overlayer, which can function as a physical separation barrier to the permeation of the second precursor. The LM between RuO₂ and rutile-TiO₂ can increase the stability of RuO₂/TiO₂ interface and thus prevent the aggregation of dual-site Au and RuO₂ in the calcination process of removing TiO_x overlayer of Au. The photocatalytic hydrogen production is used as a model reaction to evaluate the performance of spatially separated dual-site Au/TiO₂/RuO₂ catalysts. The rate of hydrogen production of the Au/TiO₂/RuO₂ is as high as 84 μmol h⁻¹ g⁻¹ under solar light irradiation without sacrificial agents, which is 2.5 times higher than the reference Au/TiO₂ and non-separated Au/RuO₂/TiO₂ samples. Systematic characterizations verify that the spatially separated dual-site Au and RuO₂ on the nanosurface of TiO₂ can effectively separate the photo-generated carriers and lower the height of the Schottky barrier, respectively, under UV and visible light irradiation. This study provides new inspiration for the precise construction of different sites in multifunctional catalysts.     

基于纳米二氧化钛的光催化自清洁面料研究进展

由于市场需求的多样化,近年来功能性服装已经成为越来越多人的选择。自清洁服装因其具有免洗、节水、节能、环境友好等特点而受到广泛关注。纳米二氧化钛(TiO_2)由于其优异的光致催化降解污染物性能、紫外屏蔽性能以及优异的抗菌性能成为制备多功能自清洁面料的最佳选择。本文介绍了纳米TiO_2的光催化降解污染物、紫外屏蔽和抗菌机理,总结了光催化自清洁面料目前面临的主要问题以及其研究进展,并对光催化自清洁面料的前景进行了展望。     

Achieving UV and visible-light photocatalytic activity enhancement of AgI/BiOIO3 heterostructure:Decomposition for diverse industrial contaminants and high mineralization ability

Heterostructure photocatalyst fabrication is of great significance for promoting the photoreactivity and solar-energy utilization efficiencies. In this work, AgI/BiOIO_3 heterostructure photocatalysts are synthesized by a facile in-situ crystallization of AgI on BiOIO_3. The photocatalytic performance is first surveyed by decomposition of model dye methyl orange(MO) separately with illumination of UV light and visible-light(λ 420 nm). It indicates that AgI/BiOIO_3 shows highly improved photocatalytic activity regardless of the light source, which should be attributed to the matchable band energy levels between AgI and BiOIO_3, benefiting the efficient charge separation. Notably, AgI/BiOIO_3 shows a universal photocatalytic activity for treating diverse antibiotics and phenols, including tetracycline hydrochloride,chlortetracycline hydrochloride, 2,4-dichlorophenol(2,4-DCP), phenol and bisphenol A(BPA), and the strong mineralization ability of AgI/BiOIO_3 was also demonstrated. Additionally, the different mechanisms under UV and visible light irradiation are investigated in detail. This work provides a new reference for design and manipulation of high-performance nonselective heterostructure photocatalyst for environmental purification.     

硫氰根选择性吸附在g-C_3N_4/Ag表面增强其光催化制氢性能(英文)

作为一种无金属的新型半导体材料,g-C_3N_4因具有稳定的物理化学性质及合适的能带结构而引起人们的关注.理论上g-C_3N_4完全满足水分解的电势条件.然而研究发现,g-C_3N_4材料本身的光催化性能并不好,这主要是由于半导体材料被光激发后生成的自由电子和空穴还没来得及到达材料表面参与反应,就在材料体相内发生复合,导致电子参与有效光催化制氢反应的几率大大降低.同时还发现,将少量的贵金属,如Pt,Au,Pd作助催化剂修饰在该半导体表面,其光催化性能明显提高.但由于这些贵金属储量非常稀少,价格昂贵,导致它们的使用受到一定限制.而Ag作为一种价格远低于Pt,Au,Pd的贵金属,也得到了广泛的研究.研究表明,金属Ag储存电子的能力很好,因此可以有效地将半导体上生成的光生电子快速转移到Ag上面去,从而达到电子空穴快速分离的目的.但是在光催化制氢过程中,Ag吸附H~+的能力较弱,致使电子与H~+反应的诱导力较弱,使得Ag释放电子的能力较差.因此可以通过提高Ag表面对H~+的吸附强度,以加速Ag的电子释放,通过表面修饰来提高Ag助剂的光催化活性.研究发现,Ag纳米粒子表面与含硫化合物之间存在很强的亲和力.硫氰根离子(SCN~–)具有很强的电负性,容易吸附溶液中H~+离子,并且也易吸附在Ag纳米粒子的表面.因此可以利用Ag与SCN~–的作用来增强Ag释放电子的能力.本文采用光还原法将Ag沉积在g-C_3N_4半导体材料表面,然后通过在制氢牺牲剂中加入KSCN溶液,利用SCN~-与Ag的亲和力来提高光生电子参与光催化反应的效率.结果表明,在SCN~-存在的情况下,g-C_3N_4/Ag的光催化制氢性能显著提高.当制氢溶液中SCN~–浓度为0.3 mmol L~(–1)时,材料的光催化制氢性能达最大,为3.89μmol h~(–1),比g-C_3N_4/Ag性能提高5.5倍.基于少量的SCN~–就能明显提高g-C_3N_4/Ag材料的光催化性能,我们提出了一个可能性的作用机理:金属银和SCN~-协同作用,即银纳米粒子作为光生电子的捕获和传输的一种有效的电子传递介质,而选择性吸附在银表面的SCN~-作为界面活性位点有效地吸附溶液中的质子以促进产氢反应,二者协同作用,加速了g-C_3N_4-Ag–SCN~-三物种界面之间电荷的传输、分离及界面催化反应速率,有效抑制了g-C_3N_4主体材料光生电子和空穴的复合,因而g-C_3N_4/Ag–SCN复合材料的光催化制氢性能提高.考虑到其成本低、效率高,SCN~–助催化剂有很大的潜力广泛应用于制备高性能的银修饰光催化材料.     

半导体电极的平带电位

平带电位(E_(fb))是半导体/电解质溶液体系的重要概念,是半导体电极在平带状态时的电极电位,它是半导体电极特有的可以实验测定的物理量。利用Mott-Schottky曲线以及光电化学等方法可以测定平带电位,判断半导体的类型以及估算半导体的载流子浓度,其数值可用于推测半导体的能级结构,确定半导体材料的价带或导带能级位置。这对于与太阳能开发利用相关的半导体光催化和光电化学研究都是非常重要的。本文分析了半导体电极的能带弯曲及影响因素,首次提出半导体界面层内费米能级弯曲,阐明半导体电极平带电位的物理意义及其测定方法,以帮助初学者理解和应用平带电位。     

贵金属负载的棒状ZnO复合光催化剂的制备及其提升的光催化性能

以水热制备的ZnO纳米棒为基底,通过乙二醇液相还原法负载不同贵金属颗粒(Pt、Pd、Ru)构筑贵金属负载的ZnO纳米棒复合光催化剂。实验结果表明在制备条件相同时,Pt/ZnO样品中Pt颗粒尺寸较小,分布均匀;Pd/ZnO样品中Pd颗粒尺寸较大且团聚严重;Ru/ZnO样品则几乎没有Ru颗粒负载。在紫外光照射下降解亚甲基蓝的反应中,Pt/ZnO表现出最高的光催化性能,Pd/ZnO样品次之,而Ru/ZnO则表现出与ZnO纳米棒相似的光催化活性;表明小尺寸和大小均匀的贵金属颗粒对ZnO纳米棒的催化性能有着显著的提升作用。对Pt/ZnO来说,当Pt载量为3.2%时Pt/ZnO催化剂的光催化活性最高。