氧化铜/二氧化硅多孔复合材料的制备及其对亚甲基蓝的吸附性能

采用聚乙二醇（PEG）为模板,通过溶胶凝胶法-水热法制备出CuO/SiO2多孔复合材料,使用FTIR、HRTEM、XRD和BET等技术手段对目标产物进行了表征;研究添加CuO质量及反应温度等反应条件对复合材料的孔结构特征的影响。 用目标产物作为吸附材料,研究了其对有机染料亚甲基蓝的吸附性能,结果表明,CuO/SiO2多孔复合材料对亚甲基蓝具有良好的吸附效果,尤其是含CuO质量分数为15%的样品在用量0.015 g、体系pH=9、搅拌时间为2 h的条件下,对10 mL亚甲基蓝（4 mg/L）的去除率最高可达97.17％。 对吸附的过程和机理进行了初步探讨。     

Composite Material that Comprised Metal–Organic Nanotubes and a Sponge as a High‐Performance Adsorbent for the Extraction of Pharmaceuticals and Personal Care Products from Environmental Water Samples

A composite material that comprised metal–organic nanotubes (MONTs) and a sponge, Cu?MONTs?sponge, was synthesized by using a rapid and convenient surfactant‐assisted dip‐coating method and used as a high‐performance adsorbent for the solid‐phase extraction of pharmaceuticals and personal care products (PPCP) from environmental water samples. By adjusting the surfactant concentration, a composite material that contained metal–organic nanotubes and a macroporous 3D porous sponge was constructed. This modified sponge achieved outstanding reproducibility as an adsorbent, with the adsorption of trace or ultratrace amounts of contaminants. Moreover, this composite material was conveniently recycled and its extraction efficiency only decreased by 6.3–12.1 % after 30 adsorption/desorption cycles. The resulting composite exhibited excellent adsorption capacity for PPCPs, which was attributed to its unique porous structure, natural hydrophobicity, and electrostatic interactions between the metal–organic nanotubes and analyte molecules. This Cu?MONTs?sponge material is an ideal adsorbent for the extraction of trace amounts of PPCPs from environmental water samples.     

复合催化剂α-(Fe，Cu)OOH/RGO的制备、表征及其协同H2O2在可见光下去除环丙沙星性能

采用一步回流法制备了α-(Fe,Cu)OOH/RGO复合催化剂,通过粉末X射线衍射、扫描电子显微镜和X射线光电子能谱等对催化剂进行了表征,并以30 mg·L^-1的环丙沙星(CIP)为目标污染物,研究了不同制备条件下所得催化剂在可见光照射下协同H2O2对CIP的去除效果。结果表明,成功实现了α-(Fe,Cu)OOH纳米棒在石墨烯二维薄片上原位生长,α-(Fe,Cu)OOH/RGO复合材料的可见光吸收边发生红移,禁带宽度从2.02 eV变为1.76 eV。石墨烯复合不但增强了对污染物的吸附能力,而且加快了光生电子的分离、迁移速率,还提高了反应体系中电子的传导效率。当石墨烯复合比例(质量分数)为1%时,复合催化剂的催化性能最佳。当催化剂投加量为0.40 g·L^-1,H2O2浓度为0.10 mol·L^-1时,反应120 min,CIP被全部去除。α-(Fe,Cu)OOH/RGO循环使用5次,对CIP的去除率均在90%以上,表明催化剂具有较强的催化活性和较好的稳定性。     

Cu含量对Pd-Cu/铝土矿CO氧化催化剂结构和性能的影响

利用资源丰富的天然铝土矿经NaOH溶液水热处理后焙烧,获得比表面积达174 m²·g^-1铝土矿载体,制备了双金属Pd-Cu为活性组分的催化剂,金属Pd负载量为0.5%（质量百分数）,以CO氧化反应为探针反应,详细考察了Cu含量的变化对催化剂物化性能的影响。研究发现,Cu的引入有利于提高金属Pd的分散度,同时随着Cu含量的变化,金属Pd与Cu之间以及金属与铝土矿载体之间的相互作用随之改变。催化剂的CO氧化反应性能评价结果表明,Pd和Cu负载量分别为0.5%和4%的样品（PdCu₄/MB）催化反应性能最佳。结合表征结果认为,PdCu₄/MB的高活性归因于良好的Pd和Cu分散度,金属Pd、Cu以及金属与载体之间较强的相互作用。此外,CO-TPD表征结果说明较强的CO吸附能力和从载体中获取氧的能力也有利于提高PdCu₄/MB样品的CO氧化反应性能。     

Porous graphene oxide-based carbon artefact with high capacity for methylene blue adsorption

A three-dimensional porous graphene oxide (PGO) material prepared by hydrothermal method was selected to adsorb methylene blue (MB), which demonstrates a high MB adsorption capacity, up to 1100 mg g^?1 in alkaline solution at room temperature. The influences of different pore structures and different contents of oxygen-containing functional groups on MB adsorption behaviors were studied in detail, which indicated that the high MB adsorption capacity is mainly ascribed to the synergistic effect of the large number of oxygen-containing functional groups and the interconnected 3D porous network. Moreover, based on the investigation on the adsorption kinetics and the effect of pH value on MB adsorption, we propose a two-step adsorption kinetics for PGO, which involved in two interactions between MB molecular and porous graphene oxide-based carbon: electrostatic force and π-π stacking. Besides, the calculation of the activation energies indicates that chemisorption dominates the adsorption for PGO in comparison with physisorption for three-dimensional porous graphene materials which has low adsorption capacity because of the removal of functional groups. The results are of great significance for the design and environmental applications of PGO as a promising adsorbent material for water purification.     

Cu含量对Pd-Cu/铝土矿CO氧化催化剂结构和性能的影响

利用资源丰富的天然铝土矿经NaOH溶液水热处理后焙烧,获得比表面积达174 m²·g^-1铝土矿载体,制备了双金属Pd-Cu为活性组分的催化剂,金属Pd负载量为0.5%（质量百分数）,以CO氧化反应为探针反应,详细考察了Cu含量的变化对催化剂物化性能的影响。研究发现,Cu的引入有利于提高金属Pd的分散度,同时随着Cu含量的变化,金属Pd与Cu之间以及金属与铝土矿载体之间的相互作用随之改变。催化剂的CO氧化反应性能评价结果表明,Pd和Cu负载量分别为0.5%和4%的样品（PdCu₄/MB）催化反应性能最佳。结合表征结果认为,PdCu₄/MB的高活性归因于良好的Pd和Cu分散度,金属Pd、Cu以及金属与载体之间较强的相互作用。此外,CO-TPD表征结果说明较强的CO吸附能力和从载体中获取氧的能力也有利于提高PdCu₄/MB样品的CO氧化反应性能。     

Cu/CuxS-Embedded N,S-Doped Porous Carbon Derived in Situ from a MOF Designed for Efficient Catalysis

The reasonable design of the precursor of a carbon-based nanocatalyst is an important pathway to improve catalytic performance. In this study, a simple solvothermal method was used to synthesize [Cu(TPT)(2,5-tdc)] ⋅ 2H₂O (Cu-MOF), which contains N and S atoms, in one step. Further in-situ carbonization of the Cu-MOF as the precursor was used to synthesize Cu/Cu_xS-embedded N,S-doped porous carbon (Cu/Cu_xS/NSC) composites. The catalytic activities of the prepared Cu/Cu_xS/NSC were investigated through catalytic reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP). The results show that the designed Cu/Cu_xS/NSC has exceptional catalytic activity and recycling stability, with a reaction rate constant of 0.0256 s⁻¹, and the conversion rate still exceeds 90 % after 15 cycles. Meanwhile, the efficient catalytic reduction of dyes (CR, MO, MB and RhB) confirmed its versatility. Finally, the active sites of the Cu/Cu_xS/NSC catalysts were analyzed, and a possible multicomponent synergistic catalytic mechanism was proposed.     

仿生分级结构NiO纳米线/纳米纤维的可控制备及光催化性能

采用静电纺丝技术和"自下而上"的溶液相自组装技术, 制备了具有仿生主次分级结构的三维NiO纳米线/纳米纤维. 采用扫描电子显微镜(SEM)、 X射线衍射仪(XRD)和比表面积分析仪分别对其形貌、 晶型和孔结构进行了表征. 以水体中的有色染料亚甲基蓝为模型污染物, 研究了分级结构NiO纳米线/纳米纤维的光催化性能. 结果表明, 在180 min内, 以分级结构NiO为催化剂时, 亚甲基蓝的降解率达到了97%, 分别是以纳米纤维和纳米粒子为催化剂时的1.24倍和2.16倍.     

Photocatalytic properties of Zinc selenide doped with cobalt oxide nanocomposite

In this work, ZnSe/Co₃O₄ was synthesized by hydrothermal method. The samples were characterized by XRD, SEM, TEM, EDS, XPS, BET, UV–vis techniques. The activity of the composite photocatalytic materials was detected by visible light catalytic degradation of methylene blue (MB). The catalytic effect was the most obvious when the composite ratio was 1:10, with the removal rate reaching to 93.6% of 10 ?mg/L MB within 120 ?min of visible light irradiation. After further analysis of the catalyst, ZnSe/Co₃O₄ has a broader application prospect due to its high efficiency and low price.     

Green synthesis of biodegradable polyurethane and castor oil-based composite for benign transformation of methylene blue

A series of polyurethane (PU), polyethylene glycol (PEG) and castor oil (CO) (ricin) based foams (PU-PEG, PU-PEG₄₀/CO₆₀, PU-PEG₆₀/CO₄₀ and PU-CO) were prepared and their catalytic activity for removal of methylene blue (MB) dye was evaluated. The prepared foams were characterized by FTIR, SEM and TGA analysis. The foams were porous in nature and the thermal stability was improved with CO incorporation. The PU-CO furnished promising catalytic efficiency and PU-PEG, PU-CO, PU-PEG₄₀/CO₆₀ and PU-PEG₆₀/CO₄₀ removed MB dye completely within 33, 5, 12 and 20 min. The removal of MB dye over foams followed second order kinetic model. The reusability of PU-CO showed stability up to 10 runs. Moreover, the phytotoxicity of the treated dye solution was performed, which reduced significantly after dye solution treatment with prepared foams. The prepared PU-CO also showed biodegradable nature under soil natural conditions. The prepared PU based foams showed excellent catalytic potential for the removal of MB dye along with thermal stability and recyclability, which could be a potential class of materials for the remediation of dyes in effluents.     

Preparation of CuO/SiO<Subscript>2</Subscript> Hollow Spheres for Catalytic Oxidation of Phenol

Porous CuO/SiO₂ hollow microspheres were synthesized via an impregnation method using pure SiO₂ hollow microspheres as the supporter, and Cu species as the functional material. The hollow microspheres were characterized by X-ray diffraction, BET surface area, temperature-programmed reduction, transmission electron microscopy, and scanning electron microscopy. The catalytic activities of the CuO/SiO₂ hollow microspheres were investigated via the removal of the total chemical oxygen demand (COD) in the oxidation of phenol solution with air as an oxidant. The influence of various reaction parameters such as the reaction temperature, the partial pressure of O₂, and the initial pH of the solution were studied in detail. The coordination, dispersion and aggregation degree of copper species on porous materials play an important role for the COD removal of the phenol aqueous solution.     

Template‐Synthesized Porous Silicon Carbide as an Effective Host for Zeolite Catalysts

A facile method has been developed for the fabrication of porous silicon carbide (SiC) by means of sintering a mixture of SiC powder and carbon pellets at a relatively lower temperature, that is, 1450 °C, in air. The pore density and the total pore volume of the resulting porous SiC could be tuned by changing the initial SiC/C weight ratio. The structure evolution and the associated property changes during the preparation were examined through X‐ray diffraction, scanning electron microscopy, thermogravimetric analysis, ²⁹Si magic‐angle spinning (MAS) NMR spectroscopy, and mercury‐intrusion porosimetry analyses. Silica and SiO_xC_y ceramics formed in situ during the calcination process acted as binders of the porous SiC grains. The porous SiC can be used as a host for the growth of ZSM‐5 zeolite crystals to form the ZSM‐5/porous‐SiC composite material. After loading another catalytic active component of molybdenum, a novel catalytic material, Mo‐ZSM‐5/porous‐SiC, was obtained, which exhibited improved catalytic activity in the methane dehydroaromatization reaction.     

导电玻璃负载CuO/V_2O_5复合纳米纤维光电极的制备及光电催化性能

以聚乙烯吡咯烷酮(PVP)为高分子模板剂,乙酰丙酮钒(C_(15)H_(21)O_6V)和三水合硝酸铜[Cu(NO_3)_2·3H_2O]为原料,导电玻璃(FTO)为载体,结合溶胶-凝胶法和静电纺丝技术制备了前驱体纤维,经高温焙烧后得到分布均匀、具有纤维结构的导电玻璃负载的CuO/V_2O_5复合光电极(CuO/V_2O_5/FTO).采用热重-差热分析仪(TG-DTA)、X射线衍射仪(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)和X射线光电子能谱仪(XPS)等对材料的结构进行表征,以亚甲基蓝(MB)为目标降解物,探讨了合成产物的光电催化性能.结果表明,CuO与V_2O_5能有效形成异质结构,其光电催化活性均比纯V_2O_5有明显提高,并且改变CuO与V_2O_5的比例对光电催化性能有较大影响,其中n(Cu)∶n(V)=1∶1时降解效率最高,达到96%.     

Enhanced photocatalytic and adsorptive degradation of organic dyes by mesoporous Cu/Al2O3-MCM-41: intra-particle mesoporosity, electron transfer and OH radical generation under visible light

Mesoporous Cu/Al(2)O(3)-MCM-41 composite was synthesized by two step processes; in situ incorporation of high surface area mesoporous Al(2)O(3) (MA) into the framework of MCM-41 (in situ method) followed by impregnation of Cu(II) by incipient wetness method. The interesting thing is that starch was used for the first time as template for the preparation of high surface area MA. To evaluate the structural and electronic properties, these catalysts were characterized by low angle X-ray diffraction (LXRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), UV-vis DRS, FTIR and photoluminescent (PL) spectra. The various cationic dye such as methylene blue (MB), methyl violet (MV), malachite green (MG) and rhodamine 6G (Rd 6G) of high concentration 500 mg L(-1) were degraded and adsorbed very efficiently (100%) using the 5 Cu/Al(2)O(3)-MCM-41 composite within 30 and 60 min, respectively. The high and quick removal of such concerted cationic organic dyes and also mixed dyes (MB+MV+MG+Rd 6G) by means of photocatalysis/adsorption is basically due to the combined effect three characteristics of synthesized mesoporous 5 Cu/Al(2)O(3)-MCM-41 composite. These characteristics are intra-particle mesoporosity, electron transfer and ˙OH radical generation under solar light.     

Removal of Methylene Blue from Aging Water Solutions Treated by a Submerged Arc

Low voltage, low energy submerged pulsed arcs with a pulse repetition rate of 100 Hz, energies of 2.6–192 mJ and durations of 10–40 μs, followed by aging in the dark, were used to decompose 10 mg/l methylene blue (MB) dissolved in 40 ml of water, with the addition of 0.5 % H₂O₂. Electrode pairs composed of Fe/Fe, Ti/Ti, Cu/Cu, Cu/Fe, Fe/Cu, Ti/Fe, Fe/Ti, Cu/Ti and Ti/Cu were used. MB degraded during arc treatment, and during post arc treatment aging. The aging degraded MB faster (by a factor of ~2–3) when the MB solution was subjected to arcing with dissimilar electrodes when one of them was Cu, than for arcing with other used electrode pairs. The impact of the arc treatment time and the electrode materials on the MB removal ratio (C₀–C_ta)/C₀ was determined as a function of aging time t_a, where C₀ and C_ta are the MB concentrations initially and after t_a. For a pulse duration of 10 μs and pulse energies of 2–20 mJ, the MB removal rate increased linearly with treatment time and its growth rate increased with pulse energy. The linear dependence of the MB removal rate on treatment time was violated with pulse duration of 40 μs and pulse energies of 30–200 mJ. Kinetics of the MB degradation during aging of the arc treated solution was well described by the 1st order linear rate equation.     

多孔柿饼状BiOBr光催化剂的简易溶剂热法合成（英文）

以硝酸铋和十六烷基三甲基溴化铵(CTAB)为Bi和Br源,采用聚乙烯吡咯烷酮(PVP)辅助溶剂热法首次成功制备了多孔纳米片聚结的柿饼状溴氧化铋(BiOBr)。通过多种分析技术对分级微米结构BiOBr材料的物化性质进行了表征,并对其在可见光照射下降解亚甲基蓝(MB)的光催化活性进行了评价。结果表明,溶剂热时间和PVP的加入量对产物的颗粒形貌和结晶度有显著影响。当加入0.7 g PVP时,120℃溶剂热处理12 h,可得到多孔纳米片聚结的柿饼状BiOBr样品。多孔柿饼状BiOBr样品的比表面积为4 m2·g^-1,带隙能为2.64 eV,在可见光区具有较强的光吸收性能,具有良好的可见光驱动降解MB的光催化活性和稳定性。我们推断,多孔纳米片聚结的柿饼状BiOBr样品具有优良的可见光催化性能,这与该样品的较高比表面积、多孔结构、低带隙能以及独特的颗粒形貌有关。     

Electrochemical deposition and characterization of NiCu coatings as cathode materials for hydrogen evolution reaction

In this study, NiCu composite coatings were electrochemically deposited on a copper electrode (Cu/NiCu) and characterized by atomic absorption spectroscopy (AAS), scanning electron microscopy (SEM) and scanning electrochemical microscopy (SECM) techniques in view of their possible applications as electrocatalytic materials for the hydrogen evolution reaction (HER). The HER activity of the prepared electrodes were studied in 1 M KOH solution by cathodic current–potential curves and electrochemical impedance spectroscopy (EIS) techniques. It was found that, the NiCu coating has a porous structure and good electrocatalytic activity for the HER in alkaline medium. The HER activity of the Cu/NiCu electrode was higher than uncoated (Cu) and Ni coated (Cu/Ni) copper electrodes. Its catalytic activity was related to the porosity as well as synergistic interaction of Ni and Cu.     

Onion-like graphitic nanoshell structured Fe–N/C nanofibers derived from electrospinning for oxygen reduction reaction in acid media

Hollow onion-like graphitic nanoshell structured Fe–N/C nanofiber (Fe–N/CNF) catalyst with porous morphology was prepared by heat treating as-spun polyacrylonitrile/ferrous oxalate composite nanofibers in ammonia atmosphere for the first time. These porous electrocatalyst showed both excellent catalytic activity for oxygen reduction reaction (ORR) and much better stability than commercial Pt/C catalyst in acid solution. The Fe–N/CNF catalysts developed here could be easily fabricated on a large scale and show high potential in proton exchange membrane fuel cells (PEMFCs).     

Carbon-nanotube/copper composite electrodes for capillary electrophoresis microchip detection of carbohydrates

The preparation of carbon nanotube (CNT)/copper composite electrodes, based on co-mixing CNT and Cu powders within mineral oil, is described. The new composite electrode is used for improved amperometric detection of carbohydrates following their capillary electrophoresis (CE) microchip separations. The CNT/Cu composite electrode detector displays enhanced sensitivity compared to detectors based on copper or CNT alone. The marked catalytic action of the CNT/Cu composite material permits effective low potential (+0.5 V vs. Ag/AgCl) amperometric detection, and is coupled to the renewability, bulk modification and versatility advantages of composite electrodes. The CNT/Cu composite surface also leads to a greater resistance to surface fouling compared to that observed at the copper electrode. Factors affecting the electrocatalytic activity and the CE microchip detection are examined and optimized. The CNT/Cu composite electrode is also shown to be useful for the detection of amino acids as indicated from preliminary results. While the present work has focused on the enhanced CE microchip detection of carbohydrates and amino acids, the CNT/metal-composite electrode route should benefit the detection of other important groups of analytes.     

碳纳米管负载Cu-Co复合氧化物的富氢气氛中CO催化消除

采用超声处理辅助浸渍法制备了多壁碳纳米管负载的Cu-Co复合氧化物催化剂. 利用XRD、TEM、H2-TPR、XPS和Raman光谱等表征了催化剂的结构性质. 在Cu和Co氧化物以及金属氧化物与碳纳米管载体间存在强相互作用. 催化剂在富氢气氛中CO催化消除反应中,与单一Cu或Co催化剂相比,Cu-Co复合氧化物催化剂表现出独特的反应特性,特别是在较高反应温度下可同时结合CO优先氧化和CO甲烷化的反应途径来实现高效CO消除. 当Cu/Co比为1/8时活性最优,可以实现在150-250℃和高反应空速 （120 L/（h·g））富氢气氛中CO的完全消除.