Enhanced photocatalytic performance of carbon quantum dots/BiOBr composite and mechanism investigation

Novel CQDs/BiOBr composite photocatalysts are constructed via a simple hydrothermal synthesis and show superior activity in photocatalytic degradation of organic pollutants.     

聚胺界面修饰改善碳量子点可见光光敏化性能

在新兴能源的存储与转化技术中,碳量子点作为新一代光吸收组分得到越来越广泛的关注。然而目前关于对碳量子点复合体系界面的改性,进而有效提高碳量子点光敏化性能的研究还较少。在本研究工作中,我们通过一种简单的静电自组装的方法构建催化体系,碳量子点能够很好地分散在枝状聚乙烯亚胺修饰的二氧化钛表面,其中碳量子点在复合体系中质量分数约为5%(w, mass fraction)时,展现出最优的可见光还原对硝基苯胺的活性。整体活性相比没有经过修饰的二氧化钛/碳量子点复合体系以及作为参比的枝状聚乙烯亚胺修饰的二氧化硅/碳量子点复合体系均有较明显的提高。结构与光谱研究表明,碳量子点与聚乙烯亚胺修饰的二氧化钛形成了较好的界面接触;进一步通过对比二氧化硅复合体系与二氧化钛复合体系表明,枝状聚乙烯亚胺可作为电子传输通道,能够有效地促进光生电子的分离与传递。因此,得益于良好的界面接触与有效地光生载流子的传递,相比未修饰的复合体系,枝状聚乙烯亚胺修饰的二氧化钛/碳量子点展现出更好地光催化反应活性。此研究工作中界面优化的手段,可将二氧化钛/碳量子点复合体系进一步拓展到其他宽带隙半导体光催化体系并设计构建有效的碳量子点基的半导体光吸收体系。     

A Review on Carbon Quantum Dot Based Semiconductor Photocatalysts for the Abatement of Refractory Pollutants

Photocatalysis is a green approach frequently utilised to eliminate a variety of environmentally hazardous refractory pollutants. Accordingly, the modification of semiconductor photocatalysts with Carbon Quantum Dots (CQDs) is of great importance for the treatment of such pollutants due to their attractive physical and chemical properties. CQDs are a perfect candidate to handle photocatalysts of high-performance since they operate as co-catalysts and as visible light harvesters. The higher separation rate of electron-hole pairs in the photocatalytic system is attributable to better photodegradation efficiency. This review classifies CQD based photocatalysts as pure, doped and composite materials and discusses the specific advantages of CQDs in visible light-driven photocatalysis. In this work, the versatile roles of CQDs in CQD-based photocatalytic systems are thoroughly discussed and summarised.     

Multifarious roles of carbon quantum dots in heterogeneous photocatalysis

As a new member of carbon material family, carbon quantum dots(CQDs) have attracted tremendous attentions for their potentials in the heterogeneous photocatalysis applications. Due to the unique microstructure and optical properties, the roles of CQDs played in the CQDs-based photocatalytic systems have been found to be diverse with the continuous researches in this regard. Herein, we provide a concise minireview to elaborate the multifarious roles of CQDs in photocatalysis, including photoelectron mediator and acceptor, photosensitizer, photocatalyst, reducing agent for metal salt, enhancing adsorption capacity and spectral converter. In addition, the perspectives on future research trends and challenges are proposed, which are anticipated to stimulate further research into this promising field on designing a variety of efficient CQDs-based photocatalysts for solar energy conversion.     

Photocatalytic carbon dioxide reduction by photocatalyst innovation

The photocatalytic conversion of carbon dioxide into sustainable fuel methanol using carbon quantum dots is highlighted in this paper. The multifaceted roles of carbon quantum dots in photocatalytic reactions and future directions of CQD materials are outlined.     

Graphene/inorganic nanocomposites: Evolving photocatalysts for solar energy conversion for environmental remediation

Current energy crisis and environmental issues, including depletion of fossil fuels, rapid industrialization, and undesired CO₂ emission resulting in global warming has created havoc for the global population and significantly affected the quality of life. In this scenario the environmental problems in the forefront of research priorities. Development of renewable energy resources particularly the efficient conversion of solar light to sustainable energy is crucial in addressing environmental problems. In this regard, the synthesis of semiconductors-based photocatalysts has emerged as an effective tool for different photocatalytic applications and environmental remediation. Among different photocatalyst options available, graphene and graphene derivatives such as, graphene oxide (GO), highly reduced graphene oxide (HRG), and doped graphene (N, S, P, B-HRG) have become rising stars on the horizon of semiconductors-based photocatalytic applications. Graphene is a single layer of graphite consisting of a unique planar structure, high conductivity, greater electron mobility, and significantly very high specific surface area. Besides, the recent advancements in synthetic approaches have led to the cost-effective production of graphene-based materials on a large-scale. Therefore, graphene-based materials have gained considerable recognition for the production of semiconducting photocatalysts involving other semiconducting materials. The graphene-based semiconductors photocatalysts surpasses electron-holes pairs recombination rate and lowers the energy band gap by tailoring the valence band (VB) and conduction band (CB) leading to the enhanced photocatalytic performance of hybrid photocatalysts. Herein, we have summarized the latest developments in designing and fabrication of graphene-based semiconducting photocatalysts using a variety of commonly applied methods such as, post-deposition methods, in-situ binding methods, hydrothermal and/or solvothermal approaches. In addition, we will discuss the photocatalytic properties of the resulting graphene-based hybrid materials for various environmental remediation processes such as; (i) clean H₂ fuel production, photocatalytic (ii) pollutants degradation, (iii) photo-redox organic transformation and (iv) photo-induced CO₂ reduction. On the whole, by the inclusion of more than 300 references, this review possibly covered in detail the aspects of graphene-based semiconductor photocatalysts for environmental remediation processes. Finally, the review will conclude a short summary and discussion about future perspectives, challenges and new directions in these emerging areas of research.     

基于碳量子点的光电器件应用新进展

碳量子点(CQDs)作为一种新型荧光碳纳米材料,由于其较高的电子迁移率、较长的热电子寿命、极快的电子取出速度,可调的带隙宽度、较强的稳态荧光等独特的光电性质和可溶液加工、成本低廉的特点,使得CQDs在光电器件领域具有广阔的应用前景,近年来受到人们的广泛关注,重要的研究成果不断涌现。本文首先简要介绍了CQDs的合成方法、化学结构及其光电性质,然后总结了CQDs在发光二极管(LEDs)、太阳能电池(SCs)和光电探测器(PDs)等光电器件领域的研究进展,最后对CQDs的发展方向进行了展望。     

Chemical Regulation of Carbon Quantum Dots from Synthesis to Photocatalytic Activity

Carbon quantum dots (CQDs) were synthesized by heating various carbon sources in HNO₃ solution at reflux, and the effects of HNO₃ concentration on the size of the CQDs were investigated. Furthermore, the oxygen‐containing surface groups of as‐prepared CQDs were selectively reduced by NaBH₄, leading to new surface states. The experimental results show that the sizes of CQDs can be tuned by HNO₃ concentration and then influence their photoluminescent behaviors; the photoluminescent properties are related to both the size and surface state of the CQDs, but the photocatalytic activities are determined by surface states alone. The different oxygen‐containing groups on the surface of the CQDs can induce different degrees of the band bending upward, which determine the separation and combination of the electron–hole pairs. The high upward band bending, which is induced by C?O and COOH groups, facilitates separation of the electron–hole pairs and then enhances high photocatalytic activity. In contrast, the low upward band bending induced by C? OH groups hardly prevents the electron–hole pairs from surface recombination and then exhibits strong photoluminescence. Therefore, both the photocatalytic activities and optical properties of CQDs can be tuned by their surface states.     

Rational design of ternary NiS/CQDs/ZnIn2S4 nanocomposites as efficient noble-metal-free photocatalyst for hydrogen evolution under visible light

The NiS/CQDs nanocomposite (CQDs represents carbon quantum dots), with a mass ratio of NiS/CQDs to be 1.19:1 based on the ICP result, was obtained via a facile hydrothermal method from a mixture of CQDs, Ni(OAc)₂ and Na₂S. The self-assembly of ZnIn₂S₄ microspheres on the surface of NiS/CQDs was realized under microwave conditions to obtain a ternary NiS/CQDs/ZnIn₂S₄ nanocomposite. The as-obtained NiS/CQDs/ZnIn₂S₄ nanocomposite was fully characterized, and its photocatalytic hydrogen evolution under visible light irradiation was investigated. The ternary NiS/CQDs/ZnIn₂S₄ nanocomposite showed superior photocatalytic activity for hydrogen evolution than ternary CQDs/NiS/ZnIn₂S₄, which was obtained by deposition of NiS in the preformed CQDs/ZnIn₂S₄. The superior photocatalytic performance of ternary NiS/CQDs/ZnIn₂S₄ is ascribed to the introduction of CQDs, which act as a bridge to promote the vectorial transfer of photo-generated electrons from ZnIn₂S₄ to NiS. This result suggests that the rational design and fabrication of ternary CQDs-based systems are important for the efficient photocatalytic hydrogen evolution. This study provides a strategy for developing highly efficient noble-metal-free photocatalysts for hydrogen evolution using CQDs as a bridge to promote the charge transfer in the nanocomposite.     

Constructing a novel Ag nanowire@CeVO4 heterostructure photocatalyst for promoting charge separation and sunlight driven photodegradation of organic pollutants

Exploiting efficient and recyclable photocatalysts is a vital matter for environmental purification.Herein,cerium vanadate（CeVO₄） sub-microspheres and silver nanowire（AgNW）@CeVO₄ with core-shell architecture as photocatalysts are rationally constructed by hydrothermal approach.The AgNW@CeVO₄ photocatalyst obtained by depositing CeVO₄ on the surface of Ag NWs possess one dimensional continuous structure,which expand the optical absorption range and redu...     

Visible‐Light Photocatalytic Hydrogen Production Activity of ZnIn2S4 Microspheres Using Carbon Quantum Dots and Platinum as Dual Co‐catalysts

ZnIn₂S₄ microspheres (ZIS MSs) were for the first time decorated with carbon quantum dots (CQDs) and platinum nanoparticles (NPs) as dual co‐catalysts of for photocatalytic H₂ production. The ZIS MSs co‐loaded with CQDs and Pt exhibited a high photocatalytic H₂ production rate of 1032.2 μmol h^?1 g^?1 with an apparent quantum efficiency of 2.2 % (420 nm) in triethanolamine aqueous solution under visible‐light irradiation, which was much higher than the respective photocatalytic rates of pure ZIS, Pt loaded ZIS, and CQDs‐decorated ZIS. Such a great enhancement was attributed to the integrative effect of good crystallization, enhanced light absorption, high electrical conductivity of CQDs, and the vectorial electron transfer from ZIS to CQDs and Pt NPs (ZIS→CQDs→Pt).     

Graphene-based semiconductor photocatalysts

Graphene, a single layer of graphite, possesses a unique two-dimensional structure, high conductivity, superior electron mobility and extremely high specific surface area, and can be produced on a large scale at low cost. Thus, it has been regarded as an important component for making various functional composite materials. Especially, graphene-based semiconductor photocatalysts have attracted extensive attention because of their usefulness in environmental and energy applications. This critical review summarizes the recent progress in the design and fabrication of graphene-based semiconductor photocatalysts via various strategies including in situ growth, solution mixing, hydrothermal and/or solvothermal methods. Furthermore, the photocatalytic properties of the resulting graphene-based composite systems are also discussed in relation to the environmental and energy applications such as photocatalytic degradation of pollutants, photocatalytic hydrogen generation and photocatalytic disinfection. This critical review ends with a summary and some perspectives on the challenges and new directions in this emerging area of research (158 references).     

野酸枣氮掺杂荧光碳量子点高灵敏检测Hg2+

以天然产物野酸枣和色氨酸为原料,通过水热法一步合成量子产率为16.9%的氮掺杂荧光碳量子点。该碳量子点具有良好的水溶性和耐光性,在高盐环境中也呈现出了较高的稳定性。应用荧光光谱、透射电子显微镜(TEM)、傅里叶变换红外光谱(FTIR)和X射线光电子能谱(XPS)对碳量子点进行了表征。此外,Hg^2+能够有效地猝灭碳量子点的荧光,猝灭机理为电子转移的动态猝灭。基于此,可将碳量子点作为荧光探针检测Hg^2+。方法对Hg^2+的检测范围为1~50 nmol/L,检出限为0.26 nmol/L,能够应用于实际水样中Hg2+含量的测定。     

Enhanced Photoelectrocatalytic Activity of BiOI Nanoplate–Zinc Oxide Nanorod p–n Heterojunction

The development of highly efficient and robust photocatalysts has attracted great attention for solving the global energy crisis and environmental problems. Herein, we describe the synthesis of a p–n heterostructured photocatalyst, consisting of ZnO nanorod arrays (NRAs) decorated with BiOI nanoplates (NPs), by a facile solvothermal method. The product thus obtained shows high photoelectrochemical water splitting performance and enhanced photoelectrocatalytic activity for pollutant degradation under visible light irradiation. The p‐type BiOI NPs, with a narrow band gap, not only act as a sensitizer to absorb visible light and promote electron transfer to the n‐type ZnO NRAs, but also increase the contact area with organic pollutants. Meanwhile, ZnO NRAs provide a fast electron‐transfer channel, thus resulting in efficient separation of photoinduced electron–hole pairs. Such a p–n heterojunction nanocomposite could serve as a novel and promising catalyst in energy and environmental applications.     

Photocatalytic degradation of amoxicillin by carbon quantum dots modified K2Ti6O13 nanotubes: Effect of light wavelength

Novel carbon quantum dots modified potassium titanate nanotubes (CQDs/K₂Ti₆O₁₃) composite was synthesized and exhibited high photocatalytic activity for degradation of amoxicillin under UV and visible lights with nine wavelengths. Better amoxicillin removal was achieved at lower wavelength irradiation due to its higher photo energy.     

二氧化钛基Z型光催化剂综述(英文)

TiO_2具有无毒、耐腐蚀、高稳定和低成本等特点,已被广泛应用于光催化领域.然而,TiO_2的禁带较宽,只能吸收仅占太阳光4%的紫外光部分,从而严重限制了TiO_2光催化材料对太阳光的有效应用.目前很多方法被用来提高TiO_2光催化效率,如金属/非金属掺杂、贵金属负载、异质结构建和与碳材料复合等,这些策略在提高光催化剂的光催化效率中,涉及到如何兼顾太阳光利用和光生空穴和电子氧化还原能力两者之间的平衡.通常,半导体禁带宽度越窄,半导体的光谱响应范围越宽、太阳光利用越多,但光生空穴和电子氧化还原能力越弱.因此,想要提高TiO_2的光催化性能,应考虑以下两个方面的平衡:即降低带隙宽度,拓展半导体的光谱响应范围;与之同时使价带电位更正,导带电位更负之间的平衡.然而,这两个点是相互矛盾的,因此很难在单组分光催化剂中同时实现这两点.然而,Z型光催化剂可以同时满足这两点要求,即:降低半导体的带隙,同时使导带更负,价带更正,因为Z光催化系统利用了两种半导体的优势,其电荷转移机制类似于自然界中绿色植物的光合作用,其中的载流子传输途径包括两步激发,类似于英文字母"Z",Z型光催化剂因此而得名.Z型光催化剂既能保留较高还原能力的光生电子和又能保留较高氧化能力的光生空穴,由于Z型光催化剂特有的优点,在光催化领域的应用越来越广泛.本文综述了TiO_2基Z型光催化剂的最新研究进展,其中包括:Z型光催化机理、应用范围和光催化活性改进方法.Z型光催化剂分为传统液相Z型光催化体系,全固态Z型光催化体系,以及最近几年发展起来的直接Z型光催化体系.它们的主要应用包括:光催化分解水产氢、二氧化碳还原制备太阳燃料、有机污染物光催化降解.论文进一步讨论了提高TiO_2基Z型光催化剂性能的方法,包括pH值调控、电子导体选择、助催化剂使用、掺杂改性、组织形貌控制、两种半导体质量比优化等.最后,提出了TiO_2基Z型光催化剂今后面临的挑战和发展前景展望.     

Black Tungsten Nitride as a Metallic Photocatalyst for Overall Water Splitting Operable at up to 765 nm

Semiconductor photocatalysts are hardly employed for overall water splitting beyond 700 nm, which is due to both thermodynamic aspects and activation barriers. Metallic materials as photocatalysts are known to overcome this limitation through interband transitions for creating electron–hole pairs; however, the application of metallic photocatalysts for overall water splitting has never been fulfilled. Black tungsten nitride is now employed as a metallic photocatalyst for overall water splitting at wavelengths of up to 765 nm. Experimental and theoretical results together confirm that metallic properties play a substantial role in exhibiting photocatalytic activity under red‐light irradiation for tungsten nitride. This work represents the first red‐light responsive photocatalyst for overall water splitting, and may open a promising venue in searching of metallic materials as efficient photocatalysts for solar energy utilization.     

基于等离子体的新型光催化剂的合成及应用进展

近年来,等离子体光催化剂由于其优异的光吸收和光催化性能,被研究者们认为是解决能源紧缺和环境污染问题的最理想候选者之一。本文从其催化机理进行探讨,按照催化剂的组成将等离子体光催化剂分类。最后对等离子体光催化剂在环境污染和能源等领域的应用进行综述,并对其未来发展方向提出了展望。     

Morphology-Controlled Synthesis and Applications of Silver Halide Photocatalytic Materials

Semiconductor photocatalysis is considered to be one of the most promising technologies to solve the worldwide environmental and energy issues. In recent years, silver halide (AgX)-based photocatalytic materials have received increasing research attention owing to its excellent visible light-driven photocatalytic performances in the applications of organic pollutant degradation, H₂/O₂ generation, and disinfection. AgX-based materials used in photocatalytic fields can be classified into three categories: AgX (Ag/AgX), AgX composites, and supported AgX materials. For the AgX (Ag/AgX) photocatalysts, it has been widely accepted that the final photocatalytic performances of photocatalysts are severely dependent on their morphological structures as well as exposed crystal facets. As a result, considerable efforts have been devoted to fabricating different morphological AgX photocatalysts as well as exploring the relationship between the morphological structures and photocatalytic performances. In this review, we mainly introduce the recent developments made in fabricating morphology and facet-controllable AgX (Ag/AgX) photocatalytic materials. Moreover, this review also deals with the photocatalytic mechanism and applications of AgX (Ag/AgX) and supported AgX materials.     

Carbon-based H2-production photocatalytic materials

Photocatalytic hydrogen production from water splitting is of promising potential to resolve the energy shortage and environmental concerns. During the past decade, carbon materials have shown great ability to enhance the photocatalytic hydrogen-production performance of semiconductor photocatalysts. This review provides a comprehensive overview of carbon materials such as CNTs, graphene, C₆₀, carbon quantum dots, carbon fibers, activated carbon, carbon black, etc. in enhancing the performance of semiconductor photocatalysts for H₂ production from photocatalytic water splitting. The roles of carbon materials including supporting material, increasing adsorption and active sites, electron acceptor and transport channel, cocatalyst, photosensitization, photocatalyst, band gap narrowing effect are explicated in detail. Also, strategies for improving the photocatalytic hydrogen-production efficiency of carbon-based photocatalytic materials are discussed in terms of surface chemical functionalization of the carbon materials, doping effect of the carbon materials and interface engineering between semiconductors and carbon materials. Finally, the concluding remarks and the current challenges are highlighted with some perspectives for the future development of carbon-based photocatalytic materials.