纳米催化材料在污染物中的应用

随着新型催化材料的不断研发,纳米催化剂得到了广泛的研究并推动了催化科学的发展。本文介绍了纳米催化材料的特点、制备方法及主要用途。简述了近年来纳米催化材料在催化降解应用中的研究进展。本文最后对纳米光催化材料在可控合成以及不同催化过程中的可能应用进行了展望与总结。

复合材料CdS／Al-HMS的制备及可见光催化降解污染物制氢活性研究

采用模板法、离子交换法、沉淀法和浸渍法等多步反应合成了系列CdS/Al-HMS和负载的Pt/CdS/Al- HMS光催化复合材料;利用XRD、TEM、XRF及UV-Vis漫反射光谱等分析技术对其进行了表征;研究结果表明:CdS的复合量是影响CdS/Al-HMS复合材料结构的主要因素.当CdS复合量较低时,形成掺杂复合材料;当CdS复合量较高时,形成纳米复合材料.载6%Pt后的CdS/Al-HMS光催化复合材料降解甲酸的最高产氢速率为22.3mL/h,420nm处的表观量子产率为12%.

催化降解水中有机污染物生成CO_2的测定

设计了一套简易的装置和改进的方法来检测催化降解有机污染物过程中最终矿化所产生二氧化碳的量.利用四氮杂卟啉铁(FePz(dtn)4)负载在离子交换树脂上来活化分子氧降解了水中难降解的有机污染物对硝基苯甲酸(NBA).采用饱和的氢氧化钡溶液来吸收有机物降解反应中所产生的二氧化碳,同时用沉淀分离滴定法来测定生成二氧化碳的量,即可计算出有机污染物降解的矿化率,其方法误差为4.2%.实验表明:在可见光光照7h后,对硝基苯甲酸碱性溶液中的矿化率可达到11.3%.

异戊烯装置选择性加氢催化剂的污染物

甲基叔戊基醚(TAME)生产中,用于醚化反应的原料中含有双烯烃,在醚化前需通过加氢处理将其脱除。而原料中所含胺类、游离水和硫对催化剂的活性会产生一定的影响,受其污染的催化剂经热氢气处理后可以恢复活性。试验证实,游离水和硫为暂时毒物,胺类为活性抑制剂。

单质磷基半导体材料的制备及其光催化应用

磷元素广泛存在于生物体和自然界中,因其晶体结构多变而存在多种同素异形体。单质磷包含白磷(WP)、红磷(RP)、黑磷(BP)、蓝磷(BuP)、紫磷(VP)。二维单层BP的首次合成引起了人们对单质磷基半导体材料(Phosphorus-based Semi-conductor Materials,PSCM)的广泛关注。PSCM具有可调节的带隙、较高的光生载流子迁移率和光热转化效率,并且拥有良好的生物相容性和可降解性,因此在能源、环境、生物医学等新兴领域有着广阔的应用前景,尤其是在光催化领域。首先详细阐明了PSCM的不同制备方法及相互转化过程,并归纳比较了其晶体与能带结构;然后还对PSCM在光催化产氢、光催化CO_(2)/CO还原、光催化降解污染物、光热治疗等典型光催化领域的研究进行了系统综述;最后对今后PSCM在光催化领域中的研究重点和方向做出展望,为新型PSCM的制备及其高效光催化应用提供重要指导和新的见解。

Preparation of three-dimensional interconnected mesoporous anatase TiO_2-SiO_2 nanocomposites with high photocatalytic activities

In this article, we report the preparation of a three-dimensional（3D） interconnected mesoporous anatase TiO2-SiO2 nanocomposite. The nanocomposite was obtained by using an ordered two-dimensional（2D） hexagonal mesoporous anatase 70 TiO2-30 SiO2-950 nanocomposite（crystallized at 950 °C for 2 h） as a precursor, NaO H as an etchant of SiO2 via a ＂creating mesopores in the pore walls＂ approach. Our strategy adopts mild conditions of creating pores such as diluted NaO H solution, appropriate temperature and solid/liquid ratio, etc. aiming at ensuring the integrities of mesopores architecture and anatase nanocrystals. XRD, TEM and N2 sorption techniques have been used to systematically investigate the physico-chemical properties of the nanocomposites. The results show that the intrawall mesopores are highly dense and uniform（average pore size 3.6 nm）, and highly link the initial mesochannels in a 3D manner while retaining mesostructural integrity. There is no significant change to either crystallinity or size of the anatase nanocrystals before and after creating the intrawall mesopores. The photocatalytic degradation rates of rhodamine B（RhB, 0.303 min^–1） and methylene blue（MB, 0.757 min^–1） dyes on the resultant nanocomposite are very high, which are 5.1 and 5.3 times that of the precursor; even up to 16.5 and 24.1 times that of Degussa P25 photocatalyst, respectively. These results clearly demonstrate that the 3D interconnected mesopores structure plays an overwhelming role to the increments of activities. The 3D mesoporous anatase TiO2-SiO2 nanocomposite exhibits unexpected-high degradation activities to RhB and MB in the mesoporous metal oxide-based materials reported so far. Additionally, the nanocomposite is considerably stable and reusable. We believe that this method would pave the way for the preparation of other 3D highly interconnected mesoporous metal oxide-based materials with ultra-high performance.

金属有机骨架材料固定化酶的研究进展

金属有机骨架材料(MOFs)凭借其较高的比表面积和孔体积、可设计和调控的孔径及结构,以及化学和热稳定性等特点,克服了传统固定化酶载体的孔径尺寸不可控、制备成本高、酶浸出、产物稳定性差等不足,近年来成为一类新型酶固定化载体。首先,本文分类总结了MOFs固定化酶的合成策略,包括后合成包装和从头合成封装(仿生矿化、共沉淀和机械化学封装);然后进一步介绍了多级孔MOFs的孔道设计策略及其固定化酶体系。这种具备分级孔道结构的MOFs用于固定化酶既可以保证酶的较高负载率,又能提高酶催化底物的扩散速率;此外,本文还介绍了MOFs共固定化多酶体系及具有类酶特性的仿生MOFs固定化酶方面的研究。MOFs特有的孔道结构可以大大缩短酶与底物之间的扩散距离,同时充分利用了酶级联反应的中间产物,可以显著提高酶催化活性;文章最后总结了MOFs固定化酶复合材料在生物传感和污染物催化净化领域的主要应用,提出了MOFs固定化酶研究中的一些瓶颈问题,以期为该材料的进一步研究和未来产业化提供借鉴和参考。

TiO_2纳米管复合列阵材料的制备及其应用研究进展

阳极氧化制备的TiO2纳米管列阵由于具有独特的、高度有序的列阵结构,制备工艺简单,成本低廉,已经发展成为重要的无机功能材料。在TiO2纳米管内外复合其它纳米材料以构成一种特殊的异质结复合结构可以提高其性能,拓展其应用空间。本文基于国内外最新研究进展,系统综述了采用金属、半导体、有机物对TiO2纳米管列阵修饰而得的复合纳米材料,及其化学、电化学和物理的方法;并介绍其在光催化降解污染物、太阳能电池、生物传感器方面的潜在应用,提出了未来的发展方向。

Hydrogen producing water treatment through mesoporous TiO2 nanofibers with oriented nanocrystals

The development of well-defined TiO2 nanoarchitectures is a versatile strategy to achieve high-efficiency photocatalytic performance.In this study,mesoporous TiO2 nanofibers consisting of oriented nanocrystals were fabricated by a facile vapothermal-assisted topochemical transformation of preformed H-titanate nanobelts.The vapothermal temperature is crucial in tuning the microstructures and photocatalytic redox properties of the resulting mesoporous TiO2 nanofibers.The microstructures were characterized with XRD,TEM,XPS and nitrogen adsorption-desorption isotherms,etc.The photocatalytic activities were evaluated by photocatalytic oxidation of organic pollutant(Rhodamine B as an example)as well as photocatalytic reduction of water to generate hydrogen(H2).The nanofibers vapothermally treated at 150°C showed the highest photocatalytic activity in both oxidation and reduction reactions,2 times higher than that of P25.The oriented alignment and suitable mesoporosity in the resulting nanofiber architecture were crucial for enhancing photocatalytic performances.The oriented alignment of anisotropic anatase nanocrystals shall facilitate faster vectorial charge transportation along the nanofibers architecture.And,the suitable mesoporosity and high surface area would also effectively enhance the mass exchange during photocatalytic reactions.We also demonstrate that efficient energy-recovering photocatalytic water treatments could be accomplished by a cascading oxic-anoxic process where the dye is degraded in the oxic phase and hydrogen is generated in the successive anoxic phase.This study showcases a novel and facile method to fabricate mesoporous TiO2 nanofibers with high photocatalytic activity for both clean energy production and environmental purification.

Bifunctional S-scheme g-C3N4/Bi/BiVO4 hybrid photocatalysts toward artificial carbon cycling

Although both the aerobic photocatalytic oxidation of organic pollutants into CO2 and the anaerobic photocatalytic reduction of CO2 into solar fuels have been intensively studied,few efforts have been devoted to combining these carbon-involved photocatalytic oxidation-reduction processes together,by which an artificial photocatalytic carbon cycling process can be established.The key challenge lies in the exploitation of efficient bifunctional photocatalysts,capable of triggering both aerobic oxidation and anaerobic reduction reactions.In this work,a bifunctional ternary g-C3N4/Bi/BiVO4 hybrid photocatalyst is successfully constructed,which not only demonstrates superior aerobic photocatalytic oxidation performance in degrading an organic pollutant(using the dye,Rhodamine B as a model),but also exhibits impressive photocatalytic CO2 reduction performance under anaerobic conditions.Moreover,a direct conversion of Rhodamine B to solar fuels in a one-pot anaerobic reactor can be achieved with the as-prepared ternary g-C3N4/Bi/BiVO4 hybrid photocatalyst.The excellent bifunctional photocatalytic performance of the g-C3N4/Bi/BiVO4 photocatalyst is associated with the formation of efficient S-scheme hybrid junctions,which contribute to promoting the appropriate charge dynamics,and sustaining favorable charge potentials.The formation of the S-scheme heterojunction is supported by scavenger studies and density functional theory calculations.Moreover,the in-situ formed plasmonic metallic Bi nanoparticles in the S-scheme hybrid g-C3N4/Bi/BiVO4 photocatalyst enhances vectorial interfacial electron transfer.This novel bifunctional S-scheme g-C3N4/Bi/BiVO4 hybrid photocatalyst system provides new insights for the further development of an integrated aerobic-anaerobic reaction system for photocatalytic carbon cycling.

Novel SiO2 nanoparticle-decorated BiOCl nanosheets exhibiting high photocatalytic performances for the removal of organic pollutants

Novel SiO2/BiOCl composites were fabricated by decorating BiOCl nanosheets with SiO2 nanoparticles via a simple hydrothermal process. The as-prepared pure BiOCl and SiO2/BiOCl composites were intensively characterized by various techniques such as XRD, FT-IR, SEM/TEM, BET, UV-vis, DRS, XPS, and photocurrent measurements. The SiO2/BiOCl composite nanosheets displayed high photocatalytic activity and excellent stability in the degradation of organic pollutants such as phenol, bisphenol A (BPA), and rhodamine B (RhB). With respect to those over bare BiOCl, the degradation rates of RhB, BPA, and phenol over 1.88% SiO2/BiOCl increased 16.5%, 29.0%, and 38.7%, respectively. Radical capturing results suggested that h^+ is the major reactive species and that hydroxyl (·OH) and superoxide (·O2^-) radicals could also be involved in the degradation of organic pollutants. The enhanced photocatalytic performances of SiO2/BiOCl composites can be mainly attributed to the improved texture and the formation of intimate SiO2/BiOCl interfaces, which largely promoted the adsorption of organic pollutants, enhanced the light harvesting, and accelerated the separation of e^– and h^+.

Chemical deactivation of Cu-SAPO-18 deNO_x catalyst caused by basic inorganic contaminants in diesel exhaust

Contaminants(K,Na,Ca,and Mg)were introduced into Cu-SAPO-18 via incipient wetness impregnation to investigate their effect on the selective catalytic reduction of NOx with NH3(NH3-SCR)over Cu-SAPO-18.After the introduction of contaminants into Cu-SAPO-18,the quantity of acidic sites and Cu^2+ species in catalyst decreases owing to the replacement of H^+ and Cu^2+ by K^+,Na^+,Ca^2+,and Mg^2+.Furthermore,the loss of isolated Cu^2+ induces the generation of CuO and CuAl2O4-like phases,which causes further loss in the Brunauer-Emmett-Teller surface area of the catalyst.Consequently,the deNOx performance of the contaminated Cu-SAPO-18 catalysts drops.Such decline in NH3-SCR performance becomes more pronounced by increasing the contaminant contents from 0.5 to 1.0 mmol/gcatal.In addition,the deactivation influence of the contaminants on Cu-SAPO-18 is presented in the order of K>Na>Ca>Mg,which is consistent with the order of reduction of acidic sites.To a certain degree,the effect of the acidic sites on the deactivation of Cu-SAPO-18 might be more significant than that of isolated Cu2+ and the catalyst framework.Moreover,kinetic analysis of NH3-SCR was conducted,and the results indicate that there is no influence of contaminants on the NH3-SCR mechanism.

A review on TiO_2-based Z-scheme photocatalysts

TiO2‐based Z‐scheme photocatalysts have attracted considerable attention because of the low recombination rate of their photogenerated electron–hole pairs and their high photocatalytic efficiency.In this review,the reaction mechanism of Z‐scheme photocatalysts,recent research progress in the application of TiO2‐based Z‐scheme photocatalysts,and improved methods for photocatalytic performance enhancement are explored.Their applications,including water splitting,CO2reduction,decomposition of volatile organic compounds,and degradation of organic pollutants,are also described.The main factors affecting the photocatalytic performance of TiO2‐based Z‐scheme photocatalysts,such as pH,conductive medium,cocatalyst,architecture,and mass ratio,are discussed.Concluding remarks are presented,and some suggestions for the future development of TiO2‐based Z‐scheme photocatalysts are highlighted.

Highly efficient UV-visible-infrared photothermocatalytic removal of ethyl acetate over a nanocomposite of CeO_(2) and Ce-doped manganese oxide

A unique nanocomposite of CeO_(2)nanoparticles and Ce-doped manganese oxide nanofibers having a crystalline cryptomelane-type octahedral molecular sieve(KMn_(8)O_(16)·nH_(2)O,abbreviated as OMS-2)structure(denoted CeO_(2)-CeOMS-2)was prepared by the reaction of Ce(NO_(3))3 and KMnO_(4)at 90°C.CeO_(2)-CeOMS-2 shows extremely high photothermocatalytic activity,very low selectivity for acetaldehyde(an unfavorable byproduct),and excellent durability for ethyl acetate removal under UV-visible-infrared(UV-vis-IR)irradiation.In striking contrast,pure CeO_(2),pure OMS-2,and TiO_(2)(P25)showed much lower photothermocatalytic activities and higher selectivities for acetaldehyde.The CO_(2)production rate within the first five minutes(r CO2)of reaction with CeO_(2)-CeOMS-2 was as high as 1102.5μmol g-1 min-1,which is 137,17,and 30-times higher than those of pure CeO_(2),pure OMS-2,and TiO_(2)(P25),respectively.CeO_(2)-CeOMS-2 also shows good photothermocatalytic activity under vis-IR(λ>420 or 560 nm)irradiation.Further,even under vis-IR(λ>830 nm)irradiation,efficient photothermocatalytic activity was achieved.In addition,the catalytic activity of CeO_(2)-CeOMS-2 is far superior to those of pure CeO_(2)and OMS-2,which is attributed to the fact that Ce doping significantly improves the lattice oxygen activity of OMS-2.The high photothermocatalytic activity of CeO_(2)-CeOMS-2 arises from the synergy between the photocatalytic effect of the CeO_(2)nanoparticles and light-driven thermocatalysis of the Ce-doped OMS-2.The novel photoactivation of Ce-doped OMS-2,which is unlike that of conventional photocatalysis on semiconductor photocatalysts,further promotes the catalytic activity because the surface oxygen activity of Ce-doped OMS-2 is promoted upon UV-vis-IR or vis-IR(λ>560 nm)irradiation.

A review on heterogeneous photocatalysis for environmental remediation:From semiconductors to modification strategies

Heterogeneous photocatalysis,an advanced oxidation process,has garnered extensive attention in the field of environmental remediation because it involves the direct utilization of solar energy for the removal of numerous pollutants.However,the application of heterogeneous photocatalysis in environmental remediation has not achieved the expected consequences due to enormous challenges such as low photocatalytic efficiencies and high costs of heterogeneous photocatalysts in large-scale practical applications.Furthermore,pollutants in the natural environment,including water,air,and solid phases,are diverse and complex.Therefore,extensive efforts should be made to better understand and apply heterogeneous photocatalysis for environmental remediation.Herein,the fundamentals of heterogeneous photocatalysis for environmental remediation are introduced.Then,potential semiconductors and their modification strategies for environmental photocatalysis are systematically presented.Finally,conclusions and prospects are briefly summarized,and the direction for the future development of environmental photocatalysis is explored.This review may provide reference directions toward understanding,researching,and designing photocatalytic remediation systems for various environmental pollutants.

Kinetics of Photocatalytic Degradation of Methylene Blue over TiO_2 Particles in Aqueous Suspensions

The kinetics of photodegradation of methylene blue over UV light illuminated titania particles in aqueous suspensions has been studied with different initial methylene blue concentrations and TiO2 particle sizes. The degradation rate increases with the decrease of initial concentration and particle size. A quasi-experienced model for photodegradation rate is derived based mainly on the coinstantaneous effects of different initial concentrations and particle sizes. The mathematical relationships of model parameters with initial concentration and particle size are given. The model results of the photodegradation rate of methylene blue are coincident with the experimental data.

Design of metal-organic frameworks(MOFs)-based photocatalyst for solar fuel production and photo-degradation of pollutants

Metal organic frameworks(MOFs)is a research hotspot in the solar fuel production and photo-degradation of pollutants field due to high surface area,rich metal/organic species,large pore volume,and adjustability of structures and compositions.Therefore,in this review,we first summarized the design factors of photocatalytic materials based on MOF from the perspective of"star"MOF.The modification strategies of MOFs-based photocatalysts were discussed to improve its photocatalytic activity and specific applications were summarized as well,including photocatalytic CO_(2)reduction,photocatalytic water splitting and photo-degradation of pollutants.Finally,the advantages and disadvantages of MOFs-based photocatalysts were discussed,the current challenges were highlighted,and suggestions for future research directions were proposed.

Enhanced photocatalytic performance of MoS_2 modified by AgVO_3 from improved generation of reactive oxygen species

In this work, an efficient AgVO3/MoS 2 composite photocatalyst was successfully synthesized via a hydrothermal method. The photocatalytic activity of the as-prepared photocatalyst was evaluated by using it for assessing the degradation of different organic pollutants under visible-light irradiation. The composite 3%-AgVO3/MoS 2 catalyst demonstrated a significantly enhanced photocatalytic activity compared to the pure compounds（AgVO3 and MoS2）. The reason behind the excellent photocatalytic performance was the modification of MoS 2 by AgVO3 to facilitate O2 adsorption/activation. In addition, the composite catalyst facilitates the two-electron oxygen reduction reaction whereby H2O2 is generated on the surface of MoS 2 to produce additional reactive oxygen species（ROSs）. ESR coupled with the POPHA fluorescence detection method and a free radical capture experiment were used to elucidate the mechanism of formation of the ROSs, including ·OH, ·O2- and H2O2. Furthermore, the generation of additional ROSs could accelerate electron consumption, leaving behind more holes for the oxidation of organic pollutants. A possible photocatalytic mechanism of the composite is also discussed.

Gold-loaded graphene oxide/PDPB composites for the synchronous removal of Cr(Ⅵ) and phenol

The construction of novel inorganic‐organic hybrid nanomaterials for synchronous photocatalyticremoval of heavy metal ions and organic pollutants has received significant attention.We successfullysynthesized gold‐loaded graphene oxide/PDPB(polymer poly(diphenylbutadiyne))composites(Au‐GO/PDPB)through a facile mechanical agitation and photoreduction method.The compositeswere characterized by XPS and TEM images,which confirmed the presence of GO and Au nanoparticleson the PDPB.The as‐prepared Au‐GO/PDPB composites displayed enhanced photocatalytic activity compared with that of pure PDPB for the synchronous photoreduction of hexavalent chromium(Cr(VI))and photo‐oxidation of phenol.We also determined the optimal loading mass of GO and Au nanoparticles on the PDPB;the Au1‐GO2/PDPB(2.0wt%GO and1.0wt%Au)composite displayed the best photocatalytic activity among all the catalysts.Our study provides a facile way to prepare inorganic‐organic composites for the synchronous photocatalytic removal of heavy metal ions and organic pollutants.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.

Preparation of Photocatalytic TiO_2 and TiO_2-SiO_2 Particles and Application to Degradation of Trace Organics in Aqueous Solution

TiO2 and TiO2-SiO2 photocatalysts were prepared by sol-gel and supercritical CO2 fluid drying method and characterized by X-ray diffraction (XRD), transmission electron microscope (TEM), etc. Their catalytic properties were tested through the photocatalytic degradation of phenol and aniline in wastewater. The results show that the developed fluidized photocatalytic reactor (FPR) and TiO2 catalyst had better performance in degrading pollutants as compared with slurry photocatalytic reactor (SPR) and commercial TiO2 catalyst. The composition and crystal form of TiO2-SiO2 composite oxide had obvious influence on catalytic effect and TiO2-SiO2 photocatalysts showed better catalytic activity and stability.