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.     

可用于环境修复的半导体光催化剂及其改性策略研究进展

多相光催化技术作为一种直接利用太阳光降解多种污染物的先进氧化工艺在环境修复领域的研究中引起了广泛关注.在多相光催化过程中,半导体材料在太阳光的激发下,其强大的氧化/还原能力可快速高效降解各种污染物.研究者通常根据环境中污染物的状态和种类选择合适的半导体材料及修饰策略,构建高效多相光催化体系,探究光催化材料在环境修复中的...     

Bi2WO6基光催化剂在环境和能源领域的最新研究进展

随着全球经济的快速发展与人口的日益膨胀,随之而来的能源消耗与环境污染也日益成为一个严峻的挑战.半导体光催化技术能够将低密度的太阳能转化为高密度的化学能,此外它能够通过产生活性自由基来降解空气或水中的污染物,因此在解决上述问题中具有巨大潜力,被认为是有着广阔前景的绿色无污染的能源转化和环境修复手段.在过去几十年的研究中,...     

生物炭负载纳米零价铁的制备及其在环境修复中的研究进展[1]

纳米零价铁（nZVI）作为一种高效还原性修复材料被广泛应用于多种污染物的去除,但易团聚、易被氧化失活的缺陷使其应用受到局限。近年来,研究者们通过将nZVI负载在多孔生物炭（BC）上来改善其本身缺陷,以期提高其应用潜力。本文综述了近年来nZVI/BC的制备方法及优缺点,总结分析了nZVI/BC对水体、土壤和沉积物中多种有机和无机污染物的去除效果和机理。同时综述了不同老化方法对nZVI/BC稳定性和反应活性的影响。在此基础上,在改进nZVI/BC制备技术、应用范围的拓展、潜在的生态和健康风险、探索老化过程和老化机制等方面进行了展望,旨在为nZVI/BC的理论研究和工程实践提供借鉴和参考。     

Recent advances in kaolinite-based material for photocatalysts

The composite catalytic materials based on the mineral kaolinite are considered to be a potential approach for solving global energy scarcity and environmental pollution, which have excellent catalytic performance, low cost and excellent chemical stability. However, pure kaolinite does not have visible light absorption ability and cannot be used as a potential photocatalytic material. Fortunately, the unique physical and chemical properties of kaolinite can be acted as a good semiconductor carrier. Herein, this paper firstly presents the mineralogical characteristics of kaolinite. Next, kaolinite-based photocatalysts (such as TiO₂/kaolinite, g-C₃N₄/kaolinite, g-C₃N₄/TiO₂/kaolinite, ZnO) are discussed in detail from the formation of heterostructures, synthesis-modification methods, photocatalytic mechanisms, and electron transfer pathways. Furthermore, the specific role of kaolinite in photocatalytic materials is summarized and discussed. In addition, the photocatalytic applications of kaolinite-based photocatalysts in the fields of water decomposition, pollutant degradation, bacterial disinfection are reviewed. However, the modification of kaolinite is hard, the manufacture of a large number of kaolinite-based photocatalysts is difficult, the cost of doping noble metals is expensive, and the utilization rate of visible light is low, which limits its application in industrial practice. Finally, this paper presents some perspectives on the future development of kaolinite-based photocatalysts.     

Green chemical conversion of large-scale aluminosilicates into zeolites for environmental remediation under carbon-neutral pressure

This minireview summarized the recent progress of converting the typical classes of large-scale aluminosilicates into zeolite materials for environmental remediation. The representative zeolite structures that can be directly converted from large-scale aluminosilicates via green chemistry approaches are addressed. The environmental remediation mechanisms on employing these zeolites for environmental remediation have been recapped. The present research gap and future research perspectives under carbon-neutral pressure via green chemistry principle on this topic are also discussed.     

Recent advances in analytical methodologies based on mass spectrometry for the environmental analysis of halogenated organic contaminants

Halogenated organic contaminants, including legislated and potential persistent organic pollutants and their precursors, represent a major environmental concern due to their hazardous effects in humans and wildlife as well as their ability to bioaccumulate through the food chain, their high resistance to environmental degradation, and their long-range atmospheric transport potential. The monitoring of these compounds in the environment at ultra-trace concentration levels requires highly selective and sensitive analytical methodologies. The lack of reference step-by-step methods led to a high number of reliable determinations depending on analytes, the complexity of the sample, and available instrumentation. Thus, this review article is mainly focused on the last advances in the analytical methodologies for the determination of halogenated organic contaminants. Methodologies regarding sample treatment, chromatographic separation, and mass spectrometry analysis have been reviewed to finally highlight the future perspectives for the improvement of the analytical determinations of these compounds and the throughput of environmental control laboratories in this field.     

具有异质结的铋系光催化剂研究进展

由于人类面临的能源危机与环境污染问题日益严重,光催化技术作为最有可能解决这两大问题的技术而备受关注。其中,光催化剂是光催化技术的核心。开发具有宽光谱响应、高载流子分离效率的光催化剂既是研究热点也是难点。铋系光催化剂具有较强的可见光吸收能力。但是,提高铋系光催化剂对入射光的吸收效率、降低光生载流子复合效率仍是提高其光催化活性的关键。目前主要通过以下策略来解决这些问题：(1)贵金属负载,(2)半导体复合,(3)金属/非金属掺杂,(4)碳材料修饰,(5)铋金属负载等。最后还简要探讨了具有异质结的铋系光催化剂的发展趋势及其潜在应用。
　　采用贵金属负载于铋系光催化剂(构建肖特基结),可以通过等离子体共振效应拓宽铋系光催化剂的光吸收范围,同时贵金属还能有效转移半导体上的光生电子,促进光生载流子的有效分离。但是,采用贵金属负载存在昂贵、容易发生团聚等不足。通过半导体之间构建紧密异质结,不仅可以调节所制备复合催化剂的能带结构,满足不同光催化反应的要求,而且由于内电场的存在可以促进光生载流子定向转移,从而提高光生载流子的分离效率。除此之外,通过杂原子掺杂可以在原子层面上构建异质结结构,也能有效抑制光生载流子的复合。近年来,通过与具有较好导电性能的碳材料复合,可以快速转移铋系半导体上产生的光子,提高光催化剂的活性和量子效率。铋纳米颗粒具有与贵金属类似的性能,通过采用铋金属对铋系半导体进行负载也可以发生等离子体共振效应,从而可以提高铋系半导体的活性。最后,作者展望了铋系半导体复合光催化剂发展的三个重要方向：(1)创制非化学计量比的铋系半导体复合光催化材料;(2)通过与还原能力更强的半导体构建复合光催化材料,实现光催化 CO2还原制备有机物和光催化全解水的应用中去;(3)充分利用铋系半导体化合物具有较强氧化能力的优点,将其应用于光催化有机物合成中,比如光催化甲苯类有机物选择性氧化等。     

可见光铋系光催化剂的研究进展

当前工业发展导致了严重的能源和环境危机,光催化为这一难题提供了有效的解决方案.然而在实际应用中,传统氧化物光催化剂宽的带隙限制了它的可见光吸收,于是窄带隙光催化剂成为了研究的热点.其中铋系光催化剂以其高的可见光光催化活性引起了人们的广泛关注.因此本文介绍了铋系光催化剂的种类、制备、形貌、复合、性能等方面的研究现状,并展望了含铋可见光催化剂发展前景.     

ZnO修饰提升花状BiOBr的可见光催化降解罗丹明B性能

以Bi(NO₃)₃·5H₂O、Zn(CH₃COO)₂·2H₂O和NaBr为前驱体,采用简单溶剂热法制备BiOBr/ZnO三维花状微纳米复合材料。采用X射线衍射、扫描电子显微镜、X射线光子能谱、N₂吸附-脱附、光致发光和电子顺磁共振等分析技术对其理化性质进行了表征。通过可见光催化降解罗丹明B(RhB)的实验测试了复合材料的光催化性能。结果表明ZnO含量为5%的BiOBr/ZnO光催化活性最优,RhB降解率在50 min后达到98.3%,其降解速率常数是纯ZnO和BiOBr的6.3倍和3.4倍,并且具有较高的稳定性。复合材料光催化性能增强的可能原因为ZnO的引入增强了可见光的吸收和光生载流子的电荷分离效率。     

Recent advances in bismuth vanadate-based photocatalysts for photoelectrochemical water splitting

Photoelectrochemical(PEC) technology is considered to be a promising approach for solar-driven hydrogen production with zero emissions. Bismuth vanadate(BiVO_4) is a kind of photocatalytic material with strong photoactivity in the visible light region and appropriate band gap for PEC water splitting.However, the solar-to-hydrogen efficiency(STH) of BiVO_4 is far away from the 10% target needed for practical application due to its poor charge separation ability. Therefore, this review attempts to summarize the strategies for improving the photocurrent density and especially hydrogen production of BiVO_4 materials through PEC techniques in the last three years, such as doping nonmetal and metal elements, depositing noble metals, constructing heterojunctions, coupling with carbon and metalorganic framework(MOF) materials to further enhance the PEC performance of BiVO_4 photoanode. This review aims to serve as a general guideline to fabricate highly efficient BiVO_4-based materials for PEC water splitting.     

In-situ polymerization for PPy/g-C3N4 composites with enhanced visible light photocatalytic performance

Polypyrrole-modified graphitic carbon nitride composites (PPy/g-C₃N₄) are fabricated using an in-situ polymerization method to improve the visible light photocatalytic activity of g-C₃N₄. The PPy/g-C₃N₄ is applied to the photocatalytic degradation of methylene blue (MB) under visible light irradiation. Various characterization techniques are employed to investigate the relationship between the structural properties and photoactivities of the as-prepared composites. Results show that the specific surface area of the PPy/g-C₃N₄ composites increases upon assembly of the amorphous PPy nanoparticles on the g-C₃N₄ surface. Owing to the strong conductivity, the PPy can be used as a transition channel for electrons to move onto the g-C₃N₄ surface, thus inhibiting the recombination of photogenerated carriers of g-C₃N₄ and improving the photocatalytic performance. The elevated light adsorption of PPy/g-C₃N₄ composites is attributed to the strong absorption coefficient of PPy. The composite containing 0.75 wt% PPy exhibits a photocatalytic efficiency that is 3 times higher than that of g-C₃N₄ in 2 h. Moreover, the degradation kinetics follow a pseudo-first-order model. A detailed photocatalytic mechanism is proposed with ·OH and ·O₂^? radicals as the main reactive species. The present work provides new insights into the mechanistic understanding of PPy in PPy/g-C₃N₄ composites for environmental applications.     

Recent advances of boron-doped diamond electrochemical sensors toward environmental applications

The electrocatalytic properties of boron-doped diamond (BDD) electrodes have been considered for a variety of sensing applications. The unusual electrochemical properties of BDD include a large potential window, a small background current, and better resistance to fouling than other carbon-based electrodes. The use of BDD for remediation and environmental sensing applications has recently attracted the interest of the sensor research community. This review focuses on recent developments that involve the use of BDD as an environmentally friendly sensing material for environmental analysis. The electrochemical properties of boron-doped diamond that has undergone surface modification (e.g., with metals or enzymes) will be considered. Recent achievements involving the use of BDD electrodes for detecting pesticides, mycotoxins, peroxides, and phenolic compounds are considered.     

表面相结结构在促进光催化电荷分离中的应用

二十世纪八十年代以来,特别是近十年,光催化研究在利用可再生能源太阳能的道路上飞速发展。越来越多的研究表明,相结结构的构筑是有效提高半导体光催化剂性能的重要策略。其中, TiO2作为重要的模型光催化剂,其相关研究成果呈现出指数增长的趋势。本综述围绕TiO2模型光催化剂,主要介绍TiO2表面相结的研究成果,包括TiO2表面相的表征、锐钛矿：金红石TiO2相结用于光催化产氢研究、TiO2相结在光催化中作用的最新认识等。在表征方面,通过表面灵敏的紫外拉曼光谱研究了TiO2相变过程中表面相结构的变化,结合可见拉曼以及XRD表征揭示了TiO2独特的相变过程,即相变始于锐钛矿粒子的界面处,小粒子逐渐团聚为大粒子,致其相变从大粒子体相开始最终扩展到整个粒子。使用CO, CO2探针红外光谱,根据锐钛矿和金红石表面吸附物种的差异,进一步证实了锐钛矿：金红石表面相结结构,为紫外拉曼光谱的表面表征特性提供坚实证据。同时,利用发光光谱观察到锐钛矿晶相的可见发光带和金红石晶相的近红外发光带,并基于此给出了TiO2材料表面相结结构的荧光表征新方法。此外荧光光谱还提供了锐钛矿、金红石相中载流子动力学信息,揭示了束缚态在光催化中的作用。在光催化应用方面,观察到混相结构TiO2较单独锐钛矿及金红石相具有更高的光催化产氢活性,通过在较大金红石颗粒上担载纳米锐钛矿粒子,证明了相结结构在提高光催化活性中的核心作用,并首次提出了锐钛矿：金红石表面异相结结构概念,推断其对电荷分离的促进作用是最终提高反应活性的原因。之后将此概念应用到改善商品TiO2(P25)光催化活性中,通过可控热处理精细调控P25的表面相结构,在光催化重整生物质衍生物产氢实验中,成功将P25光催化产氢活性提高3?5倍。之后发展了新的TiO2表面控制方法,通过加入Na2SO4等相变控制剂,延缓了TiO2从锐钛矿向金红石的相变过程,在较高温度下实现TiO2相结结构的调控,最终可将P25光催化重整甲醇制氢的活性提高6倍,同时通过高分辨电镜清晰观察到锐钛矿：金红石相结的原子层生长接触。在相结作用机理方面,多种时间分辨光谱技术以及理论计算被用作探索锐钛矿：金红石相结处的电子转移机理。通过时间分辨红外光谱对TiO2表面相结结构作用的研究,特别是利用锐钛矿、金红石不同的瞬态吸收光谱特征,证明了锐钛矿：金红石相结处的载流子转移过程,存在锐钛矿向金红石的电子转移过程。模型光催化剂TiO2相结的研究成果,加深了对光催化机理的认识,促进新型高效光催化体系的设计合成。     

Zeolitic imidazolate framework-67 (ZIF-67) rhombic dodecahedrons as full-spectrum light harvesting photocatalyst for environmental remediation

The inferior utilization efficiency of light is the main obstacle to the practical application of traditional photocatalysts such as TiO₂ and ZnO. In this regard, the development of novel photocatalysts with the capability of harvesting full spectrum light (from ultraviolet (UV) to near-infrared (NIR)) energy is a promising solution for solar energy conversion and environmental remediation. Here, we report the discovery of a single material that can harvest UV, visible (VIS), and NIR radiations to decompose heavy metal contaminants in aqueous solution. Zeolitic imidazolate framework-67 (ZIF-67) rhombic dodecahedrons were synthesized through a facile solution approach and employed in the reduction of Cr(VI) under UV−VIS−NIR pulsed laser irradiation, which was generated from the fundamental, second and third harmonics of Nd:YAG laser, respectively. The nanostructures showed efficient Cr(VI) reduction under UV, VIS and NIR laser irradiation and the measured reduction efficiency (%) was 71.22%, 69.52%, and 40.79%, respectively after 120 min. A possible explanation for the photocatalytic activity in Cr(VI) reduction was proposed. This is the first study of its kind where pulsed laser and ZIF-67 rhombic dodecahedrons capable of harvesting full spectrum light energy have been employed for the removal of Cr(VI) from water. The extraordinary capacity of harvesting full-spectrum light and long-term stability make ZIF-67 a potential photocatalyst for environmental remediation.     

Recent advances in biosensor techniques for environmental monitoring

Biosensors for environmental applications continue to show advances and improvements in areas such as sensitivity, selectivity and simplicity. In addition to detecting and measuring specific compounds or compound classes such as pesticides, hazardous industrial chemicals, toxic metals, and pathogenic bacteria, biosensors and bioanalytical assays have been designed to measure biological effects such as cytotoxicity, genotoxicity, biological oxygen demand, pathogenic bacteria, and endocrine disruption effects. This article is intended to discuss recent advances in the area of biosensors for environmental applications.     

Recent advances in Cu-based nanocomposite photocatalysts for CO_2 conversion to solar fuels

CO_2 conversion via photocatalysis is a potential solution to address global warming and energy shortage.Photocatalysis can directly utilize the inexhaustible sunlight as an energy source to catalyze the reduction of CO_2 to useful solar fuels such as CO, CH_4, CH_3OH, and C_2H_5OH. Among studied formulations, Cubased photocatalysts are the most attractive for CO_2 conversion because the Cu-based photocatalysts are low-cost and abundance comparing noble metal-based catalysts. In this literature review, a comprehensive summary of recent progress on Cu-based photocatalysts for CO_2 conversion, which includes metallic copper, copper alloy nanoparticles(NPs), copper oxides, and copper sulfides photocatalysts, can be found. This review also included a detailed discussion on the correlations of morphology, structure, and performance for each type of Cu-based catalysts. The reaction mechanisms and possible pathways for productions of various solar fuels were analyzed, which provide insight into the nature of potential active sites for the catalysts. Finally, the current challenges and perspective future research directions were outlined, holding promise to advance Cu-based photocatalysts for CO_2 conversion with much-enhanced energy conversion efficiency and production rates.     

碳纳米管@碳化硅同轴异质结纳米管非金属光催化剂产氢性能（英文）

近年来,光催化裂解水产氢(H2)引起了广泛的关注.储量丰富,环境友好的非金属无机半导体β-SiC(立方相碳化硅)具有适当的带隙(Eg=2.4 eV,ECB=?0.9 V),是一种潜在的光催化剂.受限于SiC光催化剂内部光生电子-空穴对的快速复合,SiC光催化剂的效率较低.已有的关于SiC光催化剂改性的报道主要包括构建纳米SiC,构建SiC异质结,构建碳/SiC材料杂化材料.进一步的研究表明,SiC与碳材料之间通过紧密的界面接触形成了肖特基结,能将SiC表面的光生电子快速转移,抑制光生电子-空穴对的快速复合,从而提高光催化分解水产氢的活性.另一方面,碳纳米管(CNTs)具有良好的电子导电性,一维有序的管腔所形成的电子快速传导路径.因此,将半导体光催化剂与CNTs复合,是一种制备先进的光催化剂的有效策略.本文利用Si蒸气与CNTs之间的气-固反应,在CNTs表面原位生长SiC纳米包覆层,成功地制备了一维同轴核-壳CNTs@SiC纳米管.高分辨率透射电子显微镜图像表明,SiC与CNTs之间是通过Si-C共价键原子接触,并得到X射线光电子能谱的证实.将一部分CNTs@SiC纳米管在空气中750 oC煅烧2 h以除去CNTs,得到纯SiC纳米颗粒作为对比组.紫外-可见吸收光谱表明,CNTs能够促进SiC对光的吸收.荧光发射光谱(PL),瞬态荧光寿命测试,瞬态光电流测试以及交流阻抗(EIS)测试表明,CNTs能够促进SiC表面光生电子的传输与分离,有利于提升光催化效率.以0.1 mol/L Na2S溶液作为牺牲剂,在模拟太阳光(A.M 1.5)照射下,CNTs@SiC纳米管(不额外负载Pt等贵金属作为助剂)的产氢速率为118.5μmol g^-1 h^-1,是纯SiC纳米颗粒(21.1μmol g^-1 h^-1)的5.62倍.经过20 h的光照测试,CNTs@SiC纳米管的光催化性能无明显衰减;X射线衍射测试与扫描电子显微镜图像表明,CNTs@SiC纳米管的结构与形貌反应前后几乎无变化.莫特-肖特基测试表明,CNTs的费米能级比SiC低,因此SiC表面的光生电子能够快速地转移到CNTs,并且CNTs的良好导电性与一维有序的管腔所形成的长的电子传导路径能够进一步地增加电子寿命,促进光生电子参与光催化反应.另外,通过原子连接的同轴核-壳CNTs@SiC纳米管提供了大量且有效的电子传输路径.因此,与纯SiC纳米晶等同类材料相比,无机非金属CNTs@SiC纳米管具有更强的光催化氢活性.