A High Efficient Electrocatalytic Activity of Metal-organic Frameworks ZnO/Ag/ZIF-8 Nanocomposite for Electrochemical Detection of Toxic Heavy Metal Ions

A novel electrochemical sensor on ZIF-8 nanocomposites (Ag/ZnO/ZIF-8) was developed to analyze the mercury ions (Hg²⁺). The ZIF-8 materials are one of the 3-dimensional porous metal-organic frameworks with highly accessible pores and great surface area. The ZIF-8 nanocomposites were prepared through simple sol-gel methods and their physio-chemical properties were characterized via different analytical analyses. As a result of cyclic voltammetry, Ag/ZnO/ZIF-8 exhibited a better electrocatalytic behavior towards the detection of mercury ions (Hg²⁺). Furthermore, the composite modified electrode was then inspected as a sensor for DPV detection of mercury ions. The nanocomposite sensor performed a wide linear range from 0.5 μM to 140 μM with a low detection limit of 40 nM, and high sensitivity of 56.06 μA μM⁻¹ cm⁻². Moreover, the ZIF-8 composite sensor showed a higher selectivity toward the detection of mercury ions (Hg²⁺). The real-time applications of the ZIF-8 composites sensor were inspected in various samples with good sensitivity.     

Facile Synthesis of ZIF-8/ZnO/Polyoxometalate Ternary Composite Materials for Efficient and Rapid Removal of Cationic Organic Dye

In this paper, we develop a facile and convenient two-step strategy for preparation of ZIF-8/ZnO/K₆P₂W₁₈O₆₂ (P₂W₁₈) ternary composite materials for the first time. ZIF-8/ZnO are fabricated by a “direct mixing” synthesis strategy and served as the substrate for subsequent P₂W₁₈ deposition. Then, ZIF-8/ZnO/P₂W₁₈ ternary composite was prepared in P₂W₁₈ aqueous solution through electrostatic interaction process. Further, the composites with different loading of P₂W₁₈ were achieved by reacting with different concentration of P₂W₁₈ aqueous solution. The as-prepared composite materials were characterized and confirmed by powder X-ray diffraction, TEM, EDS, ICP, FT-IR spectra, UV–Vis diffuse reflectance spectroscopy, and electrochemical test. It is noteworthy that the hybrid composites exhibit high efficient activities in the removal of cationic dyes, which could be ascribed to the high adsorption capacity derived from the strong electrostatic interaction between P₂W₁₈ and cationic dyes. Based on the investigation, the composites have potential application for waste water purification.     

准MIL-53(Fe)光催化剂的合成及其可见光催化降解有机染料性能的提高

以MIL-53（Fe）（以下简称MFe）为原料,通过热解制备了具有多孔结构的准金属-有机骨架（MOFs）MFe-T（T℃代表煅烧温度）光催化剂。在测试的催化剂中,MFe-250表现出最高的光降解性能,在90 min内降解99%亚甲基蓝（MB）。从光电流和电化学阻抗谱的结果来看,MFe-250的电子传输能力超过了MFe。此外,捕获实验表明,在光催化降解MB过程中,羟基自由基（·OH）是必不可少的中间体。此外,还提出了光催化过程的机理。     

Emerging Light-Harvesting Materials Based on Organic Photovoltaic D/A Heterojunctions for Efficient Photocatalytic Water Splitting

Photocatalytic water splitting to hydrogen is a highly promising method to meet the surging energy consumption globally through the environmentally friendly means. As the initial step before photocatalysis, harvesting photons from sunlight is crucially important, thus making the design of photosensitizers with visible even near-infrared (NIR) absorptions get more and more attentions. In the past three years, organic donor/acceptor (D/A) heterojunctions with absorptions extending to 950 nm, have emerged as the new star light-harvesting materials for photocatalytic water splitting, demonstrating exciting advantages over inorganic materials in solar light utilization, hydrogen yielding rate, etc. This Minireview firstly gives a brief discussion about the principle processes and determining factors for photocatalytic water splitting with organic photovoltaic D/A heterojunction as photosensitizers. Thereafter, the current progress is summarized in details by introducing typical and excellent D/A heterojunction-based photocatalytic systems. Finally, not only the great prospects but also the most challenging issues confronted by organic D/A heterojunctions are indicated along with a perspective on the opportunities and new directions for future material explorations.     

Covalent Organic Framework Materials for Photo/ Electrocatalytic Carbon Dioxide Reduction北大核心CSCD

Covalent organic frameworks （COFs）are a class of emerging materials connected by covalent bonds,which have high thermal/chemical stability （except boric acid COFs）,permanent porosity,large specific surface area and good crystallinity. In addition,the structure of the monomer unit in COFs is adjustable and can coordinate with many transition metal ions to provide catalytic active sites. These advantages make COFs helpful to catalyze various reactions. Among them,COFs have an excellent catalytic effect on the CO2 reduction reaction（CO2 RR）. This is mainly because the adjustable pore structure of COFs allows them to adsorb a large amount of CO2 and the π-π stacking structure in COFs can promote charge transfer, which can greatly improve the efficiency of CO2 reduction. COFs can be used as photo/ electrocatalysts to efficiently reduce CO2 to CO,CH4 ,HCOOH and other products. This review discusses the important achievements of CO2 RR catalyzed by COFs, including photo/electrocatalytic CO2 RR and photoelectric coupling CO2 RR. In addition,the future development of COFs as CO2 RR catalysts is also prospected. © 2022, Science Press (China). All rights reserved.     

原位构筑溴氧化铋/聚吡咯复合材料用于光催化降解阴离子染料

采用光化学反应法在稀酸条件下制备出薄片状溴氧化铋（BiOBr）,将其分散于含有过硫酸铵和十六烷基三甲基溴化铵的水溶液中,通过吡咯的一步聚合反应原位制备出聚吡咯（PPy）修饰的BiOBr复合材料（BiOBr/PPy）。通过扫描电子显微镜、透射电子显微镜、X射线衍射、拉曼光谱、X射线光电子能谱、紫外可见光谱及荧光光谱等综合表征技术对样品的晶体结构、形貌特征和光电特性等进行测试。结果显示,PPy成功修饰到BiOBr薄片上,BiOBr与PPy接触紧密且相互作用强。与纯BiOBr相比,BiOBr/PPy复合材料具有更强的可见光吸收效率和增强的光催化降解甲基橙（MO）染料活性。通过优化PPy和BiOBr的组合比例,当BiOBr质量分数约为7%时,BiOBr/PPy-2在50 min内对MO （30 mg·L^-1）的降解率为87.3%;另外,循环光催化活性虽有降低但仍高于纯BiOBr和纯PPy （10.4%）。这表明BiOBr与PPy之间较强的相互作用和良好的界面结合可以有效地促进光生电子与空穴的分离效率。反应体系中分离的光生空穴、衍生自由基在染料氧化降解中发挥了重要作用。     

Ag_3PO_4/BiVO_4复合光催化剂的制备及可见光催化降解染料(英文)

结合回流法和原位沉淀法成功制备磷酸银/矾酸铋(Ag3PO4/BiVO4)复合光催化剂.通过X射线衍射(XRD)、场发射扫描电子显微镜(FESEM)、能量色散X射线光谱(EDS)、紫外-可见漫反射光谱(UV-Vis DRS)及光致发光(PL)光谱对制备样品进行表征.XRD和FESEM结果表明成功制备Ag3PO4/BiVO4复合光催化剂.采用节能发光二极管灯(LED)作为可见光光源,在低消耗光催化系统中评价制备样品可见光催化降解染料的活性.当Ag3PO4和BiVO4的组成摩尔比为1:3时,复合Ag3PO4/BiVO4光催化剂呈现出高于纯相Ag3PO4的催化活性,可减少Ag3PO4的使用量.Ag3PO4/BiVO4复合光催化剂在中性溶液中表现出高活性,同时证实其对阳离子染料的光催化降解效果强于阴离子染料.在Ag3PO4/BiVO4系统中,超氧自由基和空穴是主要的活性物种.经过三次循环利用,Ag3PO4/BiVO4复合催化剂的可见光催化活性表现出不同程度的降低,归因于降解过程中产生金属银.     

阳离子镍基MOF自组装CdS/PFC-8催化剂用于可见光光催化选择性苯甲醇氧化耦合产氢（英文）

可见光驱动的光催化制氢与有机氧化合成相结合由于其环境友好性和可持续性而极具吸引力,它可以在温和的条件下同时产生清洁的氢气燃料和高价值化学品,而无需牺牲剂。半导体材料和金属有机骨架(MOFs)材料由于其性能和优势,在光催化领域得到了广泛的应用。在这项工作中,我们通过静电自组装成功合成了一种名为Cd S/PFC-8的新型有效催化剂。其中,PFC-8作为镍基金属有机骨架,Cd S/PFC-8复合材料作为无贵金属催化剂,在可见光下具有优异的光催化制氢和苯甲醇氧化性能。对Cd S/PFC-8复合材料进行了一系列催化表征。X射线衍射(XRD)和扫描电子显微镜(SEM)结果表明了Cd S/PFC-8复合材料的成功合成。X射线光电子能谱(XPS)表明了Cd S纳米棒与PFC-8之间存在一定的界面相互作用。通过紫外-可见漫反射光谱(DRS)、光致发光光谱(PL)和电化学测试对光电性能进行了表征,表明Cd S/PFC-8复合材料的可见光响应和光催化可行性。对不同催化剂的光催化实验结果进行比较,在可见光下,Cd S/PFC-8复合材料将H2的产生与苯甲醇的选择性氧化耦合,表现出显著的H2产率3376μmol...     

简单水热法合成石墨-CdSe复合材料及其光催化降解有机染料(英文)

A graphene-CdSe composite was synthesized by a facile hydrothermal method,and characterized by X-ray diffraction,scanning electron microscopy with energy dispersive X-ray analysis,transmission electron microscopy and UV-vis diffuse reflectance spectrophotometry.The graphene-CdSe composite efficiently catalyzed the photodegradation of methylene blue(MB),methyl orange(MO) and rhodamine B(Rh.B) in aqueous solution under UV or visible light irradiation.The graphene-CdSe composite exhibited a higher photocatalyt...     

Ag3PO4/BiVO4复合光催化剂的制备及可见光催化降解染料

结合回流法和原位沉淀法成功制备磷酸银/矾酸铋(Ag₃PO₄/BiVO₄)复合光催化剂. 通过X 射线衍射(XRD)、场发射扫描电子显微镜(FESEM)、能量色散X射线光谱(EDS)、紫外-可见漫反射光谱(UV-Vis DRS)及光致发光(PL)光谱对制备样品进行表征. XRD和FESEM结果表明成功制备Ag₃PO₄/BiVO₄复合光催化剂. 采用节能发光二极管灯(LED)作为可见光光源, 在低消耗光催化系统中评价制备样品可见光催化降解染料的活性.当Ag₃PO₄和BiVO₄的组成摩尔比为1:3 时, 复合Ag₃PO₄/BiVO₄光催化剂呈现出高于纯相Ag₃PO₄的催化活性,可减少Ag₃PO₄的使用量. Ag₃PO₄/BiVO₄复合光催化剂在中性溶液中表现出高活性, 同时证实其对阳离子染料的光催化降解效果强于阴离子染料. 在Ag₃PO₄/BiVO₄系统中, 超氧自由基和空穴是主要的活性物种. 经过三次循环利用, Ag₃PO₄/BiVO₄复合催化剂的可见光催化活性表现出不同程度的降低, 归因于降解过程中产生金属银.     

BiOBr的可控制备及对废水中卡马西平的有效降解

以Bi(NO₃)₃·5H₂O为原料, 乙醇为介质, KBr和/或十六烷基三甲基溴化铵(CTAB)为溴源, 采用溶剂热法合成了不同结构和性能的BiOBr微纳米材料, 通过 X射线衍射仪(XRD)、 扫描电子显微镜(SEM)、 红外光谱仪(FTIR)、 紫外-可见漫反射光谱(UV-Vis DRS)及比表面积和孔隙度分析仪对产物进行了表征. 结果表明, 溴源(KBr, CTAB)对BiOBr的结晶特性和形貌有重要影响, 其中采用双溴源且KBr与CTAB摩尔比为3∶7时制得的BiOBr(K∶C=3∶7)光催化剂在模拟太阳光下具有最优的光催化性能, 光照20 min后对废水中卡马西平的降解速率常数是以KBr为溴源制备的BiOBr(K)的4.10倍和以CTAB为溴源制备的BiOBr(C)的2.14倍. BiOBr(K∶C=3∶7)优异的光催化活性可归因于其高暴露的(110)晶面、 表面羟基、 疏松的片层状形貌及较大的比表面积和孔体积. 活性物种淬灭实验结果表明, BiOBr(K∶C=3∶7)的光催化活性主要源于光生空穴、 羟基自由基和电子.     

Etched ZIF-8 as a Filler in Mixed-Matrix Membranes for Enhanced CO2/N2 Separation

Zeolite ZIF-8 has been etched with acid to form microporous ZIF-8-E crystals. These were then introduced into a polyethersulfone (PES) membrane matrix to enhance its CO₂/N₂ separation performance. Open through pores of size about 100 nm formed in the ZIF-8 crystals allow the ingrowth of polyethersulfone chains, ensuring a reduction in the number of nonselective voids, thereby achieving better interaction between ZIF-8-E and PES. As a result, the CO₂/N₂ separation performance of the ZIF-8-E/PES membrane increased significantly, showing a CO₂ permeability of 15.7 Barrer and a CO₂/N₂ ideal selectivity of 6.5.     

HPW/PDMAEMA‐b‐PMAA/ZIF‐8 Ternary Lamellar Composite and the Photocatalytic Degradation of Methylene Blue

PDMAEMA‐b‐PMAA block copolymers were prepared by the sequential RAFT polymerization of DMAEMA and tBMA, followed by hydrolysis. Phosphotungstic acid (HPW) was anchored to the PDMAEMA blocks through electrostatic interactions and the as‐obtained HPW/PDMAEMA‐b‐PMAA was added to the synthesis of ZIF‐8. During the formation of ZIF‐8, the PMAA blocks coordinated to the Zn²⁺ ions through their carboxy groups, along with the HPW groups that were anchored to the PDMAEMA blocks. In this way, the block copolymer could consolidate the interactions between HPW and ZIF‐8 and prevent the leakage of HPW. Finally, the HPW/PDMAEMA‐b‐PMAA/ZIF‐8 ternary lamellar composite was obtained and the structure of the HPW/PDMAEMA‐b‐PMAA/ZIF‐8 hybrid material was characterized by using powder X‐ray diffraction (PXRD), X‐ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). As a photocatalyst, the HPW/PDMAEMA‐b‐PMAA/ZIF‐8 ternary lamellar composite showed excellent photoactivity for the degradation of methylene blue (MB). The rate of degradation of MB was 0.0240 min^?1, which was 7.5‐times higher than that of commercially available P25 (0.0032 min^?1). In the presence of H₂O₂, the kinetic degradation parameters of the composite reached 0.0634 min^?1, which was about 19.8‐times higher than that of P25.     

降解水中有机毒物的新型反应体系研究

利用空气中的氧电化学合成H₂O₂,制备具有较高电流效率的空气电极.将空气电极用于构成降解有机毒物的新型反应体系电化学氧化体系、光激发氧化剂氧化体系和光电-Fenton氧化体系.实验测量了H₂O₂在不同体系不同条件下的分解速率,并与相应的传统式体系作了比较.实验测量了苯胺在新型体系中的矿化反应速率,发现H₂O₂的分解速率与苯胺的矿化速率有良好的平行关系,其中H₂O₂分解速率最快的光电-Fenton体系是氧化降解有机分子的最佳体系.通过光电-Fenton体系和光-Fenton体系的比较,揭示了空气电极/溶液界面在光电-Fenton体系中所起的重要作用.初步讨论了苯胺分子在光电-Fenton体系中矿化反应的机制.     

Efficient Degradation of Cellulose in Its Homogeneously Aqueous Solution over 3D Metal-Organic Framework/Graphene Hydrogel Catalyst

Catalytic degradation of cellulose to chemicals is an attracting topic today for the conversion of biomass, and the development of novel catalysts is a key point. Since metal-organic frameworks (MOFs) possess uniform, continuous, and permeable channels, they are valuable candidate as catalysts. Here, a new 3D MOF/graphene catalyst was prepared by in situ growth of the zeolitic imidazolate frameworks (ZIF-8) nanoparticles inside the pore of an as-formed 3D reduced graphene oxide (rGO) hydrogel. The ZIF-8/rGO nanocomposite owns both micropores and mesopores with large specific surface area and plenty of acids sites, which is an idea catalyst for biomass degradation. Cellulose was dissolved in alkaline aqueous solution at first, and then it was degraded efficiently over the new catalyst under hydrothermal condition. The conversion reaches 100% while the main products are formic acid with a maximum yield of 93.66%. In addition, the catalyst can be reused with high activity.     

碳酸氧铋光催化剂的合成与光催化降解有机染料

大学化学综合实验——碳酸氧铋光催化剂的合成与光催化降解有机染料。学生可以熟悉光催化材料合成的方法、材料的结构及形貌的表征手段,以及了解并熟悉纳米材料的光催化原理和光催化实验过程。在掌握基础理论和基本实验技能的同时,培养学生独立思考问题、分析问题和解决问题的能力,尤其是培养他们综合运用知识的能力。     

Large‐Scale Screening and Design of Metal–Organic Frameworks for CH4/N2 Separation

CH₄/N₂ separation is one of the great challenges in gas separation, which is of scientific and practical importance, such as in the upgrading of unconventional natural gas. Unfortunately, the separation performance is still quite low so far mainly due to their very close physical properties. In this work, a high‐throughput computational screening method was performed to develop metal–organic frameworks (MOFs) for efficient CH₄/N₂ separation. General designing rules as well as the correlation between selectivity and our proposed adsorbility (AD) parameter were obtained by carrying out systematic GCMC simulations of the existing 5109 CoRE MOFs. With the aid of this information, five virtual MOFs were screened out from the large database with 303 991 generated MOFs constructed in our previous work, exhibiting much higher selectivities than all the reported values. Among them, the selectivity of Zn‐PYZ‐BPY‐1 can reach over 29.0, about 2.4 times of the highest value reported in the literature. These results may not only suggest promising candidates for CH₄/N₂ separation but also provide useful information for large screening of MOFs for other specific separation mixtures.     

功能化MOFs及MOFs/聚合物复合膜在有机染料和重金属离子吸附分离中的应用

全球工业的发展带来了严重的水污染问题,对含各类有机和无机污染物工业废水的处理也成为了重要研究课题。金属-有机骨架(Metal-Organic Frameworks, MOFs)化合物由于其大比表面积、高孔隙率、有序孔道结构及可调节孔道物理化学性质、热稳定性高、易于合成和丰富的开放活性位点等特点,在诸多领域得到广泛应用,其中在固相吸附/分离领域,特别是吸附水中污染物方面展现出良好应用前景。通过合成后改性、使用含取代基配体原位合成、与特定功能材料复合等方法实现MOFs功能化,可有效增加MOFs材料的吸附活性位点,提高吸附性能和吸附选择性。与MOFs颗粒相比较,MOFs/聚合物复合膜结合了MOFs颗粒的结构与物理化学特性以及聚合物薄膜优秀的分离/载体性能,在有机染料及重金属离子的吸附中表现出优秀的吸附/分离性能。本文重点综述了以染料和重金属离子为代表的有机、无机污染物的吸附去除为目标的MOFs功能化方法,以及MOFs/聚合物复合膜的制备方法,并对未来研究方向和研究前景进行展望。     

A Z‐Scheme Polyimide/AgBr@Ag Aerogel with Excellent Photocatalytic Performance for the Degradation of Oxytetracycline

A novel Z‐scheme polyimide (PI)/AgBr@Ag aerogel photocatalyst has been successfully synthesized by combining an in situ precipitation method and a supercritical drying method. The as‐prepared PI/AgBr@Ag‐50 (50 wt % AgBr@Ag in PI/AgBr@Ag) aerogel photocatalyst exhibited excellent photocatalytic activity for oxytetracycline degradation with a rate constant of 0.025 min^?1, which was 6.9 and 2.6 times higher than that of the PI aerogel or the AgBr@Ag nanoparticles, respectively. More significantly, the PI/AgBr@Ag‐50 aerogel photocatalyst showed stable cycling, which could be attributed to the high mechanical strength and 3D network of the PI aerogel. The introduction of AgBr@Ag on PI with a heterojunction structure efficiently promoted the separation of electron–hole pairs by a Z‐scheme mechanism. The reduced metallic Ag nanoparticles were found to function as centers for the transfer of electrons from AgBr to PI. This work has revealed a new application for the aerogel PI/AgBr@Ag photocatalyst in environmental protection.     

(BiO)2CO3-Bi-TiO2复合纳米纤维制备及其光催化降解抗生素

以静电纺丝制备的TiO₂纳米纤维为基质,葡萄糖为还原剂,在不同的酸碱环境中,采用一步水热法可控合成了异质结型Bi-TiO₂、(BiO)₂CO₃-TiO₂和(BiO)₂CO₃-Bi-TiO₂复合纳米纤维光催化剂。通过X射线粉末衍射(XRD)、X射线光电子能谱(XPS)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、紫外-可见漫反射光谱(UV-Vis DRS)和光致发光光谱(PL)等对样品进行表征。以洛美沙星、环丙沙星和诺氟沙星为目标污染物,研究了TiO₂及其复合纳米纤维的光催化降解性能,并探究其降解反应机理。结果表明,(BiO)₂CO₃-Bi-TiO₂光催化活性最高,模拟太阳光照60 min,对诺氟沙星、洛美沙星和环丙沙星的降解率分别达到93.2%、97.5%和100%。