N-doped graphene quantum dot-decorated N-TiO2/P-doped porous hollow g-C_(3)N_(4) nanotube composite photocatalysts for antibiotic photodegradation and H2 production

Exclusive responsiveness to ultraviolet light (~3.2 eV) and high photogenerated charge recombination rate are the two primary drawbacks of pure TiO_(2). We combined N-doped graphene quantum dots (N-GQDs), morphology regulation, and heterojunction construction strategies to synthesize N-GQD/N-doped TiO_(2)/P-doped porous hollow g-C_(3)N_(4) nanotube (PCN) composite photocatalysts (denoted as G-TPCN). The optimal sample (G-TPCN doped with 0.1wt% N-GQD, denoted as 0.1% G-TPCN) exhibits significantly enhanced photoabsorption, which is attributed to the change in bandgap caused by elemental doping (P and N), the improved light-harvesting resulting from the tube structure, and the upconversion effect of N-GQDs. In addition, the internal charge separation and transfer capability of0.1% G-TPCN are dramatically boosted, and its carrier concentration is 3.7, 2.3, and 1.9 times that of N-TiO_(2), PCN, and N-TiO_(2)/PCN(TPCN-1), respectively. This phenomenon is attributed to the formation of Z-scheme heterojunction between N-TiO_(2) and PCNs, the excellent electron conduction ability of N-GQDs, and the short transfer distance caused by the porous nanotube structure. Compared with those of N-TiO_(2), PCNs, and TPCN-1, the H2 production activity of 0.1%G-TPCN under visible light is enhanced by 12.4, 2.3, and 1.4times, respectively, and its ciprofloxacin (CIP) degradation rate is increased by 7.9, 5.7, and 2.9 times, respectively. The optimized performance benefits from excellent photoresponsiveness and improved carrier separation and migration efficiencies. Finally, the photocatalytic mechanism of 0.1% G-TPCN and five possible degradation pathways of CIP are proposed. This study clarifies the mechanism of multiple modification strategies to synergistically improve the photocatalytic performance of 0.1% G-TPCN and provides a potential strategy for rationally designing novel photocatalysts for environmental remediation and solar energy conversion.

Regulation of interlayer channels of graphene oxide nanosheets in ultra-thin Pebax mixed-matrix membranes for CO_(2) capture

For the application of carbon capture by membrane process,it is crucial to develop a highly permeable CO_(2)-selective membrane.In this work,we reported an ultra-thin polyether-block-amide(Pebax)mixedmatrix membranes(MMMs)incorporated by graphene oxide(GO),in which the interlayer channels were regulated to optimize the CO_(2)/N_(2) separation performance.Various membrane preparation conditions were systematically investigated on the influence of the membrane structure and separation performance,including the lateral size of GO nanosheets,GO loading,thermal reduction temperature,and time.The results demonstrated that the precisely regulated interlayer channel of GO nanosheets can rapidly provide CO_(2)-selective transport channels due to the synergetic effects of size sieving and preferential adsorption.The GO/Pebax ultra-thin MMMs exhibited CO_(2)/N_(2) selectivity of 72 and CO_(2) permeance of 400 GPU(1 GPU=106 cm^(3)(STP)·cm^(2)·s^(-1)·cmHg^(-1)),providing a promising candidate for CO_(2) capture.

Fabrication of a novel electrochemical sensor based on MnFe_(2)O_(4)/graphene modified glassy carbon electrode for the sensitive detection of bisphenol A

Manganese ferrite(MnFe_(2)O_(4))has the advantages of simple preparation,high resistivity,and high crystal symmetry.Herein,we have developed an electrochemical sensor utilizing graphene and MnFe_(2)O_(4) nanocomposites modified glassy carbon electrode(GCE),which is very efficient and sensitive to detect bisphenol A(BPA).MnFe_(2)O_(4)/graphene(GR)was synthesized by immobilizing the MnFe_(2)O_(4) microspheres on the graphene nanosheets via a simple one-pot solvothermal method.The morphology and structure of the MnFe_(2)O_(4)/GR nanocomposite have been characterized through scanning electron microscopy(SEM),Fourier transform infrared spectroscopy(FT-IR),X-ray diffraction(XRD)and X-ray photoelectron spectroscopy(XPS).In addition,electrochemical properties of the modified materials are comparably explored by means of cyclic voltammetry(CV),electrochemical impedance spectroscopy(EIS)and differential pulse voltammetry(DPV).Under the optimal conditions,the proposed electrochemical sensor for the detection of BPA has a linear range of 0.8-400μmol/L and a detection limit of 0.0235μmol/L(S/N=3)with high sensitivity,good selectivity and high stability.In addition,the proposed sensor was used to measure the content of BPA in real water samples with a recovery rate of 97.94%-104.56%.At present,the synthesis of MnFe_(2)O_(4)/GR provides more opportunities for the electrochemical detection of BPA in practical applications.

La内嵌graphene/MoS_(2)层的储氢性能研究

运用密度泛函理论研究了La内嵌graphene/MoS_(2)层的储氢性能.由于La的内嵌graphene/MoS_(2)异质结的层间距被拉大.详细研究了氢气分子在La内嵌的graphene/MoS_(2)结构上的吸附行为.结果表明,一个La原子最多可以吸附六个氢气分子,采用GGA/PBE泛函计算得到氢气分子的平均吸附能为0.198 eV.合适的吸附能使得设计材料能够在温和条件下实现可逆存储.重要的是,La原子能够分散地内嵌在graphene/MoS_(2)异质结中,这将为氢气分子提供更多吸附位.研究表明理论上预测La内嵌graphene/MoS_(2)材料是一种潜在的储氢材料.

Hierarchical Reduced Graphene Oxide-MnO_(2)@Polypyrrole Coaxial Nanotube Composite Hydrogel as a Potential Adsorbent for Cr(Ⅵ)Removal

A hierarchical reduced graphene oxide-MnO_(2)@polypyrrole coaxial nanotube composite hydrogel was prepared via oxidative polymerization of pyrrole in the presence of MnO_(2)nanotubes,followed by the hydrothermal treatment of graphene oxide and MnO_(2)@polypyrrole coaxial nanotubes.The stable composite hydrogel with a hierarchical network was composed of one-dimensional MnO_(2)@polypyrrole coaxial nanotube and two-dimensional graphene nanosheet and characterized by scanning electron microscope,Fourier transform infrared spectroscopy,X-ray diffraction,Brunauer-Emmett-Teller surface,and X-ray photoelectron spectroscopy measurements.The composite hydrogel can be used as an efficient adsorbent for Cr(Ⅵ)removal due to the synergistic interaction between graphene and MnO_(2)@polypyrrole and the hierarchical structure of the hydrogel.Moreover,the composite hydrogel is easily separated because of its stable monolith,and it is reusable(76.8%of removal ability remaining after five adsorption-desorption cycles).The simple fabrication and cost-effective separation process together with the excellent absorption performance endow the composite hydrogel with great potential for practical wastewater treatment.

Mixed‑Dimensional Assembly Strategy to Construct Reduced Graphene Oxide/Carbon Foams Heterostructures for Microwave Absorption,Anti‑Corrosion and Thermal Insulation

Considering the serious electromagnetic wave(EMW)pollution problems and complex application condition,there is a pressing need to amalgamate multiple functionalities within a single substance.However,the effective integration of diverse functions into designed EMW absorption materials still faces the huge challenges.Herein,reduced graphene oxide/carbon foams(RGO/CFs)with two-dimensional/three-dimensional(2D/3D)van der Waals(vdWs)heterostructures were meticulously engineered and synthesized utilizing an efficient methodology involving freeze-drying,immersing absorption,secondary freeze-drying,followed by carbonization treatment.Thanks to their excellent linkage effect of amplified dielectric loss and optimized impedance matching,the designed 2D/3D RGO/CFs vdWs heterostructures demonstrated commendable EMW absorption performances,achieving a broad absorption bandwidth of 6.2 GHz and a reflection loss of-50.58 dB with the low matching thicknesses.Furthermore,the obtained 2D/3D RGO/CFs vdWs heterostructures also displayed the significant radar stealth properties,good corrosion resistance performances as well as outstanding thermal insulation capabilities,displaying the great potential in complex and variable environments.Accordingly,this work not only demonstrated a straightforward method for fabricating 2D/3D vdWs heterostructures,but also outlined a powerful mixeddimensional assembly strategy for engineering multifunctional foams for electromagnetic protection,aerospace and other complex conditions.

Reduced graphene oxide aerogel decorated with Mo_(2)C nanoparticles toward multifunctional properties of hydrophobicity,thermal insulation and microwave absorption

Reduced graphene oxide(rGO)aerogels are emerging as very attractive scaffolds for high-performance electromagnetic wave absorption materials(EWAMs)due to their intrinsic conductive networks and intricate interior microstructure,as well as good compatibility with other electromagnetic(EM)components.Herein,we realized the decoration of rGO aerogel with Mo_(2)C nanoparticles by sequential hydrothermal assembly,freeze-drying,and high-temperature pyrolysis.Results show that Mo_(2)C nanoparticle loading can be easily controlled by the ammonium molybdate to glucose molar ratio.The hydrophobicity and thermal insulation of the rGO aerogel are effectively improved upon the introduction of Mo_(2)C nanoparticles,and more importantly,these nanoparticles regulate the EM properties of the rGO aerogel to a large extent.Although more Mo_(2)C nanoparticles may decrease the overall attenuation ability of the rGO aerogel,they bring much better impedance matching.At a molar ratio of 1:1,a desirable balance between attenuation ability and impedance matching is observed.In this context,the Mo_(2)C/r GO aerogel displays strong reflection loss and broad response bandwidth,even with a small applied thickness(1.7 mm)and low filler loading(9.0wt%).The positive effects of Mo_(2)C nanoparticles on multifunctional properties may render Mo_(2)C/r GO aerogels promising candidates for high-performance EWAMs under harsh conditions.

Enabling High-Performance Sodium Battery Anodes by Complete Reduction of Graphene Oxide and Cooperative In-Situ Crystallization of Ultrafine SnO_(2)Nanocrystals

The main bottleneck against industrial utilization of sodium ion batteries(SIBs)is the lack of high-capacity electrodes to rival those of the benchmark lithium ion batteries(LIBs).Here in this work,we have developed an economical method for in situ fabrication of nanocomposites made of crystalline few-layer graphene sheets loaded with ultrafine SnO_(2)nanocrystals,using short exposure of microwave to xerogel of graphene oxide(GO)and tin tetrachloride containing minute catalyzing dispersoids of chemically reduced GO(RGO).The resultant nanocomposites(SnO_(2)@MWG)enabled significantly quickened redox processes as SIB anode,which led to remarkable full anode-specific capacity reaching 538 mAh g^(−1)at 0.05 A g^(−1)(about 1.45 times of the theoretical capacity of graphite for the LIB),in addition to outstanding rate performance over prolonged charge–discharge cycling.Anodes based on the optimized SnO_(2)@MWG delivered stable performance over 2000 cycles even at a high current density of 5 A g^(−1),and capacity retention of over 70.4%was maintained at a high areal loading of 3.4 mg cm^(−2),highly desirable for high energy density SIBs to rival the current benchmark LIBs.

Graphene-based electrodes and catalysts for electroreduction of CO_(2)to low-carbon alcohols

The electrochemical reduction of CO_(2)(CO_(2)ER)into the renewable and sustainable green fuels,such as low-carbon alcohols,is one of several workable strategies.CO_(2)ER can be combined with renewable electricity to transform intermittent energy sources(such as wind,hydro,and solar)into a fuel that can be stored until it is ready to be used.The intrinsic characteristics of the employed catalyst have a significant and substantial effect on the efficiency of CO_(2)ER and the ensuing economic viability.The paradigmatic multicarbon alcohol catalysts should increase the concentration of*CO in the reaction environment,stabilize the key intermediate products during the reaction,and facilitate the C-C coupling interaction.Since graphene has a large surface area and exceptional conductivity,it has been used as a support for active phases(nanoparticles or nanosheets).It is possible for graphene to enhance charge transport and accelerate CO_(2)conversion through its electronic and structural coupling effects.At the interface,a synergy can be produced that improves CO_(2)ER by increasing*CO adsorption,intermediate binding,and stability.This article focuses on recent advancements in graphene-based catalysts that promote CO_(2)ER to alcohols.Likewise,this paper also describes and discusses the key role graphene plays in catalyzing CO_(2)ER into alcohols.Finally,we hope to provide future ideas for the design of graphene-based electrocatalysts.

废烟气脱硝催化剂中TiO_(2)资源化回收实验研究

采用高温碱浸和酸洗的方法对废选择性催化还原(SCR)脱硝催化剂进行处理,研究碱浸和酸洗对催化剂各组分的浸出效果,考察温度对催化剂浸出行为的影响规律。结果表明,碱浸温度的提高促进V和W的浸出,210℃时V和W的浸出率分别为82.38%和74.92%。经高温碱浸和酸洗处理后,Al、Ca、Na等杂质的最高浸出率均可达98%以上,回收TiO_(2)的纯度较高,可用于生产新催化剂。高温碱浸会破坏催化剂的结构,有利于后续HCl处理对杂质的去除,除杂效果优于直接酸洗处理。高温碱浸过程中会生成Na_(2)TiO_(3),经HCl反应并水解后会形成新的TiO_(2)颗粒,形成更多的小孔,比表面积增大。

ATO-TiO_(2)浅色导电粉体的可控制备及性能研究

浅色导电材料因其较低的电阻率,优异的装饰特质迅速发展,运用在传感、电子信息、机械制造、通讯、电磁屏蔽等诸多领域。锑掺杂二氧化锡和二氧化钛(ATO-TiO_(2))纳米复合材料不仅具有半导体性质,并且颜色浅、可染性好,同时具有优异的化学稳定性和热稳定性。然而其制备过程中容易团聚,导致导电性能较差。因此,制备过程中均匀分散,同时兼具优异的导电性能是目前研究需要迫切解决的科学问题。采用共沉淀的方法,制备了ATO-TiO_(2)浅色导电材料,分析了包覆复合过程中不同改性剂、Sb_(x)Sn_(1-x)O_(2)∶TiO_(2)复合比和干燥方式对ATO-TiO_(2)浅色导电材料的物相组成、微观形貌、电学性能等微观结构形貌及宏观理化性能的影响,实现了可控制备并得到了最佳制备的工艺路线。

PBST/TiO_(2)/MgO复合薄膜的制备及性能

采用硅烷偶联剂γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH-570)对TiO_(2)/MgO NPs改性,采用溶液共混法制备了聚丁二酸-共-对苯二甲酸丁二醇酯(PBST)/TiO_(2)/MgO NPs纳米复合薄膜,并探讨了其在食品包装方面的应用。研究了改性TiO_(2)/MgO NPs对PBST基体机械、阻隔、抗菌和保鲜性能的影响。结果表明:复合膜的抗拉强度和水蒸汽透过率分别为29.39MPa和2.43×10^(-11) g·m/(m^(2)·s·Pa),相较PBST基体抗拉强度提高了24.32%,水蒸汽透过率降低了32.37%,且对金黄色葡萄球菌(S.aures)和大肠杆菌(E.coli)抑菌效果显著,分别达到98.7%和97.2%,并对圣女果有良好的保鲜性能,当改性后的TiO_(2)/MgO NPs质量含量为5%时,复合薄膜的性能最佳。

具有增强光催化和抗菌活性的TiO_(2)@Ag-GO复合材料

光催化降解环境中的污染物被认为一种理想的清洁方法,其中二氧化钛(TiO_(2))是目前最有前途的光催化材料之一。但由于能带宽、光生电子与空穴快速复合等特点,限制了其利用效率和范围,开发一种高效的TiO_(2)基光催化复合材料具有重要意义。通过简单的溶胶-凝胶法和一步Marangoni法,将TiO_(2)和Ag纳米颗粒(AgNPs)和氧化石墨烯(GO)有效结合,制备出显著增强光催化活性和抗菌能力的复合材料TiO_(2)@Ag-GO。氧化石墨烯(GO)具有多个催化活性中心,可以高效地进行光催化反应降解污染物。同时,还能提高电荷分离程度,抑制光生电子和空穴复合,提高TiO_(2)光催化活性。AgNPs具有存储电子和促进电荷分离的能力,同时释放的Ag+,赋予材料广谱的抗菌性能。光催化试验抑菌试验结果表明,复合材料能高效降解亚甲基蓝染料,2 h降解率达到74.5%,同时对金黄色葡萄球菌和铜绿杆菌有较强的杀灭作用。这种简易制备的高催化和杀菌功能的TiO_(2)基复合材料在光催化清洁领域有很大的应用潜力。

TiO_(2)/石墨烯基复合材料的制备及光催化降解染料研究

采用改进Hummers法制备氧化石墨烯(GO)和水解法制备的TiO_(2)及溶剂热法制备了还原氧化石墨烯(rGO)和一系列不同浓度的rGO/TiO_(2)纳米复合材料(0、5%、10%、15%、20%质量分数),并对合成产物进行SEM、XRD、XPS、DRS、Raman等表征,研究不同实验条件下纯TiO_(2)和rGO/TiO_(2)复合催化剂对亚甲基蓝染液(MB)的降解效果。结果表明,复合光催化剂中TiO_(2)主要为锐钛矿相,溶剂热合成引入的还原氧化石墨烯(rGO)对TiO_(2)的物相没有产生影响,rGO的引入使得rGO/TiO_(2)吸收带发生一定红移,TiO_(2)禁带宽度由3.23降低至3.09 eV;合成的(15%质量分数)rGO/TiO_(2)具有最佳的光催化效果,光催化活性最高,在100 W高压汞灯照射下70 min对20 mg/L的亚甲基蓝染料的降解率达97.6%;在500 W氙灯光源下照射70 min对20 mg/L亚甲基蓝染料的降解率达到93.2%,(15%质量分数)rGO/TiO_(2)复合光催化剂具有良好的光催化降解性及循环稳定性,5次循环光催化降解后,rGO/TiO_(2)有86.1%的降解效率。表现出了优异的吸附和光催化性能,这可为光催化处理废液提供了一种有效的方法。

Catalytic performance and synthesis of a Pt/graphene-TiO_2 catalyst using an environmentally friendly microwave-assisted solvothermal method

A Pt/graphene‐TiO2catalyst was prepared by a microwave‐assisted solvothermal method and was characterized by X‐ray diffraction,scanning electron microscopy,transmission electron microscopy,cyclic voltammetry,and linear sweep voltammetry.The cubic TiO2particles were approximately60nm in size and were distributed on the graphene sheets.The Pt nanoparticles were uniformly distributed between the TiO2particles and the graphene sheet.The catalyst exhibited a significant improvement in activity and stability towards the oxygen reduction reaction compared with Pt/C,which resulted from the high electronic conductivity of graphene and strong metal‐support interactions.

TiO_2/Graphene多孔微球对亚甲基蓝和乙醛的光催化活性

通过喷雾高温分解的方法制备了TiO_2多孔微球和TiO_2/Graphene多孔微球。石墨烯作为电子受体,能够增强TiO_2电子和空穴的分离效率。另外,石墨烯的引入提高了TiO_2对太阳光的利用率。在太阳光的照射下,TiO_2/Graphene多孔微球对亚甲基蓝具有较高的光催化活性,然而其对乙醛的降解和CO_2的生成均显示了较低的光催化活性。

多孔碳基TiO2纳米复合微粒制备及其降解罗丹明B的研究

以杨絮纤维和硼酸钙(CaB)为模板,以聚多巴胺(PDA)为联结剂及模板制备二氧化钛(TiO2)纳米复合微粒(Catkin/CaB/PDA/TiO2 )。在惰性气氛(Ar)下烧结、腐蚀制备多孔碳基TiO2纳米复合微粒。利用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线衍射(XRD)、同步热分析(TGA)考察样品结构。利用 Belsorp-max物理吸附仪研究样品比表面积。利用紫外可见分光光度计和光致发光光谱(PL)测定样品光降解效率和荧光强度。研究所制备纳米微粒对罗丹明B(RhB)的催化降解性能,发现TiO2的含量、烧结温度、聚多巴胺、硼酸盐等对RhB光降解能力均有影响。所制备复合微粒在40 min内对RhB的降解率可达94.92%。烧结促使杨絮纤维和PDA碳化,所形成的管状碳材料和多孔结构为光生电子向碳化飞絮富集并与活性物种发生氧化还原反应和TiO2纳米粒子的附着和分散提供了保障进一步促进光解效果提升。

MnFe_(2)O_(4)/graphene的制备及其超级电容性能

采用水热法制备了MnFe_(2)O_(4)/石墨烯(MFO/graphene)复合材料。利用XRD、SEM、EDS、循环伏安、计时电位等手段对MFO/graphene的物理与化学性能进行了表征。结果表明:产物为直径约100 nm的MFO颗粒均匀分布于graphene的片层上;MFO/graphene复合材料在3M KOH溶液中表现较好的超级电容特性。由于graphene的引入,提高了MFO材料导电性,进而改善了复合材料的电化学性能,MFO/graphene电极材料在1 A·g^(-1)的电流密度下展现出600 F·g^(-1)的比容量,与MFO相比,比电容提高了近47.1%。

Graphene Quantum Dot‑Mediated Atom‑Layer Semiconductor Electrocatalyst for Hydrogen Evolution

The hydrogen evolution reaction performance of semiconducting 2H-phase molybdenum disulfide(2H-MoS_(2))presents a significant hurdle in realizing its full potential applications.Here,we utilize theoretical calculations to predict possible functionalized graphene quantum dots(GQDs),which can enhance HER activity of bulk MoS_(2).Subsequently,we design a functionalized GQD-induced in-situ bottom-up strategy to fabricate near atom-layer 2H-MoS_(2) nanosheets mediated with GQDs(ALQD)by modulating the concentration of electron withdrawing/donating functional groups.Experimental results reveal that the introduction of a series of functionalized GQDs during the synthesis of ALQD plays a crucial role.Notably,the higher the concentration and strength of electron-withdrawing functional groups on GQDs,the thinner and more active the resulting ALQD are.Remarkably,the synthesized near atom-layer ALQD-SO_(3)demonstrate significantly improved HER performance.Our GQD-induced strategy provides a simple and efficient approach for expanding the catalytic application of MoS_(2).Furthermore,it holds substantial potential for developing nanosheets in other transition-metal dichalcogenide materials.

N-CQDs/N-TiO_(2)复合光催化剂的制备及其催化降解甲基橙性能研究

采用水热法制备了一种新型的复合光催化剂N-CQDs/N-TiO_(2)。利用X射线衍射(XRD)、扫描电镜(SEM)、紫外-可见漫反射(UV-Vis DRS)、固体荧光(PL)与比表面积仪(BET)等手段对其物相、形貌及光吸收性能进行表征,并研究了N-CQDs掺杂质量比对N-CQDs/N-TiO_(2)复合光催化剂对甲基橙光降解性能的影响。结果表明:与纯N-TiO_(2)相比,0.5%N-CQDs/N-TiO_(2)复合光催化剂对甲基橙溶液的降解效率为95.43%,这归因于N-CQDs可促进纯N-TiO_(2)对可见光的吸收,同时也可降低光生电子-空穴对的复合几率。捕获实验结果表明在可见光降解甲基橙过程中主要的活性物质为超氧基团(·O_(2)^(-))和光生空穴(h+),且·O_(2)^(-)占主要地位。