S型异质结光催化材料研究进展

光催化反应可将太阳能转化为可储存的化学能源，被认为是缓解能源危机和解决环境问题的有效途径之一。然而，由于光生载流子低的转移和分离效率，实际的光化学转换效率提升受到了限制。新兴的S型异质结光催化剂由于其在空间上实现了光生载流子的有效转移分离并展现出强的氧化还原能力，在太阳燃料制备和环境治理领域受到了广泛关注和研究。本文综述了S型异质结光催化剂的发展历程和设计原理、光生载流子转移机制以及在能源和环境等领域的应用。最后，提出了S型异质结光催化剂的发展前景和面临的挑战。     

ZnO/ZnS异质结构纳米材料的制备及其光催化还原Cr(VI)的研究

伴随着全球经济的高速发展,能源短缺和环境恶化问题引来了诸多的关注,就目前的研究结果来说,利用太阳能进行光催化还原是最好的解决途径,而宽禁带半导体ZnO是一直被人们广泛关注的光催化材料。本研究采用化学沉淀法制备得到花状ZnO,并以其为基底成功制得复合的ZnO/ZnS异质结构纳米材料。采用XRD、SEM、PL等一系列表征手段,研究了ZnO/ZnS复合纳米材料的晶相结构、形貌以及其光生载流子的分离效率,并测试了ZnO/ZnS复合纳米材料在全光照射下对Cr(VI)的光还原能力。研究结果表明,制得的ZnO/ZnS复合光催化剂在光照90min后对Cr(VI)的还原率高达97%,是纯相ZnO的1.3倍。     

S型光催化剂的电子转移机理研究进展

光催化技术是减轻能源危机和环境污染的有效技术之一。由于光生电子–空穴对的快速复合,单组分光催化剂的光催化效率不高。新型S型异质结光催化剂可以实现光生载流子的有效分离,同时具备强氧化还原能力,因此受到了广泛的关注和研究。对S型异质结光催化剂电子转移机理的深入理解有利于设计出更高效的光催化剂。通过选择合适的表征技术可以有效揭示S型异质结光催化剂的电子转移机理。因此,本文综述了直接和间接表征S型异质结光催化剂电子转移机理的技术。对于每种表征技术,首先对基本原理进行简述,然后通过代表性示例加以证明。研究S型异质结光催化剂电子转移机理可以加深对S型异质结光催化剂的理解,为进一步优化光催化系统提供极大帮助。     

g-C3N4的改性策略以及g-C3N4/Ti3C2异质结研究进展

石墨相氮化碳（g-C₃N₄）禁带宽度约为2.7 eV,具有可见光响应能力。由于其良好的热和化学稳定性,且形貌和化学结构可调,在光催化领域应用广泛。但由于其带隙宽,对可见光响应范围窄,且光生载流子的复合率高,导致其光催化效率低,可通过改性来改善。本文综述了对g-C₃N₄形貌调控、掺杂和构建异质结等改性策略,以及g-C₃N₄/Ti₃C₂异质结的作用机理、制备方法和在光催化析氢、有机物降解及合成等领域的应用。     

g-C3N4同型异质结复合光催化剂的制备及性能研究

石墨相氮化碳(g-C_3N_4)由于其合适的带隙和较高的物理化学稳定性等,被认为是一种有应用前景的光催化材料。然而,纯相g-C_3N_4的光催化性能和应用受到光生电子空穴易复合和比表面积相对较低等原因的限制。本文使用两种合适的前驱体(三聚硫氰酸与硫脲)共聚合有望优化高温煅烧过程中的缩聚过程,抑制团聚的发生,提高比表面积,同时形成的同型异质结能有效抑制光生载流子的再复合。在可见光照射下,形成的g-C_3N_4同型异质结复合光催化剂的活性明显高于单一的g-C_3N_4样品。显著增强的光催化活性主要归因于比表面积增大、活性位点增多和光生载流子再复合的有效抑制。     

p-n异质结光催化剂的制备及性能的研究进展

p-n异质结光催化剂材料因其具有特殊的能带结构和载流子输送特性,在光催化领域得到重视.本文重点介绍各种类型的P-n异质结光催化剂的研究现状,并对未来的研究方向进行了展望.     

p-n异质结ZnO/HRP催化剂的制备及其光催化性能研究

p型半导体红磷(HRP)和n型半导体ZnO复合后形成p-n型异质结复合半导体催化剂ZnO/HRP。以Cr(Ⅵ)为模型污染物,研究了ZnO质量分数对催化剂光催化还原性能的影响。结果发现,ZnO/HRP复合光催化剂的光催化还原速率随ZnO质量分数的增加而增大,当ZnO的质量分数为0. 25%时,ZnO/HRP复合光催化剂展现出最强的光还原性,其降解速率常数k为5. 5×10~(-2)min~(-1),是HRP的14. 8倍。光催化机理探究发现,Zn O和HRP复合形成异质结后,可抑制光生电子和空穴的复合,增强光响应性,从而提高了HRP的光催化活性。     

Ag/g-C_3N_4/ZnO复合光催化剂的制备及光催化性能

合成了一种新型的三项的异质结光催化剂Ag/g-C_3N_4/ZnO,银离子在光照下沉积在g-C_3N_4/ZnO的异质结上,通过Ag的表面离子共振,不仅提高了可见光的吸收,同时也作为一种很好的电子受体促进光生电子的转移。在g-C3N4和ZnO的界面,光生电子从g-C3N4的导带转移到ZnO的导带上,阻止了光生电子空穴对的复合。因此三项异质结的Ag/g-C_3N_4/ZnO复合材料显示出了最高的光催化活性。     

Ag/g-C_3N_4/ZnO复合光催化剂的制备及光催化性能

合成了一种新型的三项的异质结光催化剂Ag/g-C_3N_4/ZnO,银离子在光照下沉积在g-C_3N_4/ZnO的异质结上,通过Ag的表面离子共振,不仅提高了可见光的吸收,同时也作为一种很好的电子受体促进光生电子的转移。在g-C3N4和ZnO的界面,光生电子从g-C3N4的导带转移到ZnO的导带上,阻止了光生电子空穴对的复合。因此三项异质结的Ag/g-C_3N_4/ZnO复合材料显示出了最高的光催化活性。     

石墨烯基异质结光催化复合材料的研究进展

石墨烯具有低成本、高电子迁移率、透光率、比表面积与稳定性的特点,近年来在光催化领域作为助催化剂研究广泛.随着研究人员对石墨烯性质的深入研究,基于不同电子结构设计不同石墨烯基异质光催化复合材料,正成为光催化领域所关注的热点,但各类异质结的设计较不明朗.基于异质结设计理论与石墨烯电子结构,本文主要综述了石墨烯基肖特基异质结...     

Boron-Doped Graphene/ZnO Nanoflower Heterojunction Composite with Superior Photocatalytic Activity

The boron-doped graphene (BG) is synthesized successfully by one pot reduce-doping of graphene oxide (GO) with borane tetrahydrofuran (BH₃·THF) and the novel BG/ZnO p–n heterojunction composite between p-type BG and n-type ZnO is obtained via a simple hydrothermal method. The samples are characterized by scanning electron microscopy, the Raman spectroscopy and the UV–Vis diffuse spectroscopy. The results confirm the formation of p–n junction between BG and ZnO. The photodegradation of MB demonstrate that the BG/ZnO composite has superior photocatalytic activity under UV–Vis or visible irradiation. The photocatalytic activity k value of BG/ZnO p–n heterojunction composite is 3.1 and 4.5 times as that of r-GO/ZnO and pure ZnO under white light and is 1.8 and 3.9 times under visible light, respectively. The superior photocatalytic activity of the BG/ZnO composite is ascribed to the formation of p–n heterojunction. The p–n heterojunction can promote the separation of electron/hole pairs and inhibit the recombination of electrons in conduction band and holes in valence band by transferring holes from the valence band of n-type ZnO to the valence band of p-type BG.     

阴极共电沉积制备ZnO/α-FeOOH复合膜及其光催化活性(英文)

利用阴极共电沉积法,在铟锡氧化物涂层玻璃基体上成功制备了ZnO/α-FeOOH复合膜。用X射线衍射和X射线能量散射谱分别对其晶相和化学组成进行了表征,以Cr(VI)的光催化还原作为探针反应评价了其光催化活性。结果表明:与单一的ZnO膜相比,不论是在紫外光还是紫外-可见光照射下,ZnO/α-FeOOH复合膜均呈现出更高的光催化活性。紫外光照射下,ZnO/α-FeOOH复合膜催化活性的提高主要应归因于异质结界面上光生电荷的有效分离,而掺杂到ZnO中的Fe(III)的电子捕获效应在紫外-可见光条件下也发挥着重要作用。     

A visible-light-active BiFeO<Subscript>3</Subscript>/ZnS nanocomposite for photocatalytic conversion of greenhouse gases

Given the changes in environmental conditions in the world, photocatalytic conversion of greenhouse gases is of great interest today. Our aim was to increase the photocatalytic efficiency of BiFeO₃/ZnS (p-n heterojunction photocatalyst) by varying the molar ratio of ZnS to perovskite structure of BiFeO₃ using hydrothermal synthesis. The results of X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), FT-IR spectroscopy showed the small crystal size and suitable distribution of ZnS particles on the BiFeO₃ structure. The results of UV-visible, and photoluminescence (PL) spectroscopy analyses showed the good behavior of p-n heterostructure in absorption of visible light and lowering electron-hole recombination. The best visible light photocatalytic efficiency of CO₂ reduction, 24.8%, was obtained by an equimolar ratio of BiFeO₃/ZnS.     

CuO/ZnO叠层复合薄膜的制备及其光催化活性

分别通过光还原和电还原在以氧化铟锡玻璃为基体的ZnO上沉积Cu和Cu2O,后经400℃空气中热处理,制备了两种CuO/ZnO叠层复合薄膜。用X射线衍射、扫描电子显微镜和X射线能量散射谱分别对复合薄膜的晶相、形貌和化学组成进行表征。以橙黄II在模拟自然光照射下的光催化降解作为探针反应评价其光催化活性。结果表明：由Cu/ZnO经400℃下焙烧1h转化的CuO/ZnO叠层复合薄膜具有更高的光催化活性,反应1h后,橙黄II的降解率比由Cu2O/ZnO经400℃下焙烧1h转化的CuO/ZnO提高了14%。对CuO/ZnO叠层复合薄膜光催化活性提高的原因也进行了讨论。     

Attachment of ZnO nanoparticles onto layered double hydroxides microspheres for high performance photocatalysis

In this study, ZnO nanoparticles were successfully deposited on the surface of ZnMgAl–CO₃–LDHs microspheres to form ZnO/ZnMgAl–CO₃–LDHs heterojunction photocatalysts by coprecipitation process. The samples were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and UV–vis diffuse reflectance spectroscopy. The results show that ZnO nanoparticles with diameters about 10–80 nm are tightly grown on the nanosheets of the ZnMgAl–CO₃–LDHs microspheres. Compared with the pristine ZnMgAl–CO₃–LDHs microspheres and pure ZnO, the photocatalytic activity of the heterojunction ZnO/ZnMgAl–CO₃–LDHs photocatalyst is significantly enhanced towards the degradation of phenol under UV light irradiation. The enhancement of the photocatalytic activity of the heterojunction catalysts can be ascribed to their improved light absorption property and the lower recombination rate of the photoexcited electrons and holes during the photocatalytic reaction. The optimal molar ratio of ZnO/ZnMgAl–CO₃–LDHs for the photocatalysis is 3. The heterojunction photocatalyst ZnO/ZnMgAl–CO₃–LDHs may be a promising photocatalyst for future application in water treatment due to its excellent performance in degradation of phenol.     

溶剂热法制备Ag/ZnO纳米复合材料及其光催化性能的研究

用溶剂热法制备了Ag/ZnO纳米复合材料,用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、能量色散谱点(EDS)分析了复合材料的表面形貌及结构.以亚甲基蓝为模拟污染物,在紫外光照射下考察了纳米Ag/ZnO复合材料的光催化活性.结果表明,一定量银沉积能有效地改善ZnO时亚甲基蓝的光催化降解性能.     

Innovative synthesis of a novel ZnO/ZnBi2O4/graphene ternary heterojunction nanocomposite photocatalyst in the presence of tragacanth mucilage as natural surfactant

Developing interfacial connections is one of the breakthrough strategies to improve the photocatalytic activity of graphene/p-n heterojunction systems. Herein, natural tragacanth mucilage, for the first time, was employed as cost-effective and ecofriendly surfactant to prepare highly efficient ZnO–ZnBi₂O₄/graphene hybrid photocatalyst. The results indicated that the methylene blue (MB) photocatalytic degradation efficiency of ZnO–ZnBi₂O₄/graphene-mucilage heterojunction, containing 10 wt% ZnBi₂O₄ and 1 wt% graphene, was ～1.2, 1.4, 3.1 and 8.3 times higher than that of ZnO–ZnBi₂O₄/graphene, ZnO–ZnBi₂O₄, ZnBi₂O₄ and ZnO samples, respectively. This significant improvement in the photocatalytic performance could be mainly ascribed to the desirable advantages of using natural mucilage as surfactant, including uniform distribution of ZnO–ZnBi₂O₄ nanoparticles on the surface of graphene sheets, increasing of the effective surface area, and improving of the charge carriers separation. Based on the trapping experiments, electron spin resonance and photoelectrochemical Mott-Schottky tests, direct Z-Scheme charge transfer mechanism with hydroxyl radicals as main active species was suggested for photocatalytic degradation of MB on the ZnO–ZnBi₂O₄/graphene-mucilage nanocomposite. This study provides a new insight to fabricate more homogeneous and close contact interfaces in graphene-based hybrid photocatalytic systems for environmental remediation.     

ZnO/碳纳米管复合光催化材料对抗生素的光催化降解

采用溶胶法合成了ZnO/碳纳米管复合光催化材料,采用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、紫外-可见漫反射吸收光谱(UV-Vis)等手段对复合催化剂进行了表征。以氙灯(250～800 nm)为光源,盐酸四环素为降解对象,评价样品的光催化活性。比较ZnO/CNTs复合材料和纯ZnO对抗生素的降解能力,并考察光催化剂的重复利用能力。结果表明,通过溶胶法得到了在碳纳米管表面均匀、致密包覆ZnO颗粒的复合材料。由于ZnO/CNTs材料良好的吸附性能,其光催化活性高于纯ZnO,在300 W氙灯光源下反应2 h,对盐酸四环素的降解率达82.38%,同时复合材料显示了抑制ZnO光蚀的能力。     

Synthesis of LAS/ZnO/ZnWO4 3D rod-like heterojunctions with efficient photocatalytic performance: Synergistic effects of highly active site exposure and low carrier recombination

A photocatalytic nano-material containing LAS/ZnO/ZnWO₄ 3D rod-like heterojunctions was successfully synthesized using hydrothermal and mechanical force solid phase methods. Its phase, morphology, specific surface, and electrochemical characteristics, as well as the degraded performance under ultraviolet light of the sample pollutant RhB in its presence, were all investigated. Compared with pure ZnO, pure ZnWO₄ and ZnO/ZnWO₄ composites, LAS/ZnO/ZnWO₄ (LZ_xZW_1-x) composites have a smaller particle size, larger specific surface area, stronger photoelectric chemical properties and better photocatalytic performance. Notably, the rate of degradation of RhB by LZ_0.92ZW_0.08 reaches 98.0% in 30 min, which is 100%, 500% and 25% higher than that found with pure ZnO, pure ZnWO₄ and ZnO/ZnWO₄, respectively. This is because the n-n heterojunction of ZnO/ZnWO₄ loads well on schizolytic luffa sponge (LAS) with its large specific surface area. More active sites are exposed at the heterojunction, increasing the probability of contact between pollutants and the semiconductor composites, and vacancy defects of C atoms are present in LAS, acting as the capture center for photogenerated carriers. This facilitates the transfer of photogenerated electrons or holes at the ZnO/ZnWO₄ heterojunction and reduces the rate of recombination of photogenerated carriers. Capitalizing on this idea of two-factor coupling and synergistic enhancement of photocatalyst performance can help make treatment of environmental pollution more efficient.     

Enhanced CO2 photocatalytic conversion into CH3OH over visible‐light‐driven Pt nanoparticle-decorated mesoporous ZnO–ZnS S-scheme heterostructures

In the present contribution, the design and fabrication of Pt nanoparticle-decorated mesoporous ZnO–ZnS heterostructures were described and used effectively for photocatalytic CO₂ conversion to yield CH₃OH. TEM images of the mesoporous Pt/ZnS–ZnO heterostructure demonstrated spherical ZnO NPs ~20 nm, and Pt NPs ~3 nm were well dispersed on the porous ZnS–ZnO heterostructure. The formation of CH₃OH over the Pt/ZnS–ZnO heterostructure was 78, 39 and 20 times larger than that bare ZnS, ZnO NPs and ZnS–ZnO, respectively. The optimal Pt/ZnO–ZnS heterostructure exhibited a high CH₃OH formation rate of 81.1 μmolg^-1h^-1, which is about 44, 22 and 20 times larger than that of bare ZnS (1.86 μmolg^-1h^-1), ZnO (3.72 μmolg^-1h^-1), and ZnO–ZnS (4.15 μmolg^-1h^-1), respectively. The significantly enhanced reduction of CO₂ was imputed to the synergistic effects of the ZnO–ZnS heterostructure and the incorporation of Pt NPs. The synthesized photocatalyst provides a new transfer route through which carriers can migrate to the outer surface as well as pore channels of the mesoporous ZnO–ZnS, therefore significantly minimizing the transfer distance for carriers, inhibiting photoinduced electron-hole recombination, and diminishing the mobility resistance, as determined using photoluminescence, photocurrent response, and electrochemical impedance spectra measurements.