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.

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.

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.

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.

纳米MnO_(2)炭基复合材料的制备及吸附去除水中La(Ⅲ)离子性能研究

稀土是一种珍贵的战略资源,但其开发冶炼过程会产生大量废水并造成严重的环境污染,因此如何高效吸附去除废水中稀土离子被大量研究。通过共沉淀法将纳米MnO_(2)负载至生物炭(Biochar, BC)表面,得到纳米MnO_(2)炭基复合材料(Nano-MnO_(2)Carbon Matrix Composites, MBC),并用于吸附去除废水中的La(Ⅲ)离子。研究通过表征分析材料的物理和化学结构变化,考察了应用环境条件对MBC吸附La(Ⅲ)离子性能的影响,在308 K、pH=6.0条件下,0.55 g/L MBC对20 mg/L La(Ⅲ)离子模拟废水进行吸附处理,24 h后吸附效率达到95.65%。吸附动力学、等温线和热力学研究显示,MBC对La(Ⅲ)离子的吸附过程符合拟一级动力学模型和Langmuir模型,为单分子层吸附,最大吸附质量比可达43.49 mg/g;通过D-R模型计算的Es为23.12 kJ/mol,表明吸附过程偏向于化学吸附,且是自发的吸热过程。MBC经5次循环后,吸附性能仍达到初始吸附质量比的79.18%,MBC作为炭基吸附剂用于吸附水中的La(Ⅲ)离子,展现出一定的应用前景。

MnO_(2)纳米片与带正电荷的AIE分子荧光检测GSH以及IMP门的构建

谷胱甘肽(glutathione,GSH)是由谷氨酸、半胱氨酸和甘氨酸结合而成的含有巯基的三肽,广泛存在于各种生物当中,对生物体内有着重要的作用。因此,能方便、快速、准确的检测GSH在体内的水平十分有必要。MnO_(2)纳米片是一种带负电的、具有氧化性的过渡金属氧化物。将带有负电荷的MnO_(2)纳米片与带有正电荷的两个季铵盐基团的二苯乙烯基蒽衍生物DSAI结合,制备成DSAI/MnO_(2)复合探针。将DSAI/MnO_(2)复合探针加入GSH后,MnO_(2)纳米片被解,DSAI的荧光得到恢复。基于以上现象可定量GSH,并且构建出以MnO_(2)纳米片和GSH为输入的分子逻辑门。

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%。

锰浸出液制备棒状β-MnO_(2)纳米材料

湿法浸出锰矿或锰渣中的锰得到的硫酸锰浸出液中含有钙、镁杂质离子,对后续锰产品的纯度造成很大影响。为深度除硫酸锰浸出液中的Ca^(2+)、Mg^(2+),并最大化利用锰浸出液,可以将净化后的锰浸出液制备成高附加值的MnO_(2)纳米材料。以含钙、镁的硫酸锰浸出液为研究对象,将锰浸出液除钙、镁后,以(NH_(4))_(2)S_(2)O_(8)为氧化剂,采用水热法将净化后的锰浸出液制备成高附加值的MnO_(2)纳米材料,探究溶液的pH、反应温度、反应时间对制备MnO_(2)纳米棒物相和形貌的影响。结果表明:当反应温度为150℃、反应时间为10 h、加入氧化剂用量为理论量、反应pH为1~7的条件下制备出的β-MnO_(2)结晶度最好。

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.

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.

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.

协同组装MnO_(2)/石墨烯薄膜材料及其电化学性能

通过电化学剥离制备石墨烯,同时协同组装制备了3D MnO_(2)/石墨烯电极薄膜材料,电化学性能测试表明,它具有较高的电容量、倍率性能和较好的循环稳定性,在1 A/g的电流密度下具有607 F/g的较高电容量,在循环10 000圈后仍保持94.1%的容量值,未来可以应用到新型电极材料等领域。

焙烧还原电解产物MnO2制备高纯硫酸锰

本文采用同槽电解MnO2,经硫黄焙烧还原制得MnO,MnO和浓硫酸反应制备高纯硫酸锰。探讨MnO2还原制MnO的最佳工艺条件以及MnO制备高纯硫酸锰的最佳工艺条件。结果表明,MnO2还原制MnO的最佳工艺条件为:MnO2与硫黄的物质的量之比为2∶1.6,焙烧时间30min,焙烧温度450℃,MnO产率达到93.5%。制备高纯硫酸锰的最佳工艺条件为:MnO与浓硫酸物质的量之比为1∶1,硫酸锰产率达到87.7%,纯度达到98.2%。本方法能将同槽电解MnO2转化为高纯硫酸锰,实现资源的有效利用。

MnO2@NC纳米带的制备及储锂性能研究

采用水热法成功合成了一种新型氮掺杂碳修饰MnO2纳米带(MnO2@NC)。将该材料作为锂离子电池负极时,在2 A g-1的大电流密度下循环1000次后,其可逆比容量可达310.4 mAh g-1,并展现出卓越的倍率并能。与未改性MnO2相比,MnO2@NC表现出更好的倍率性能、更高的比容量和容量保持率。电化学测试分析表明,MnO2@NC电化学性能提高的原因在于电荷转移电阻的降低、缩短的Li+扩散距离以及更为优异的电极动力学。?

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.

γ-MnO2 nanorods/graphene composite as efficient cathode for advanced rechargeable aqueous zinc-ion battery

Aqueous Zn//MnO2 batteries are emerging as promising large-scale energy storage devices owing to their cost-effectiveness,high safety,high output voltage,and energy density.However,the MnO2 cathode suffers from intrinsically poor rate performance and rapid capacity deterioration.Here,we remove the roadblock by compositing MnO2 nanorods with highly conductive graphene,which remarkably enhances the electrochemical properties of the MnO2 cathode.Benefiting from the boosted electric conductivity and ion diffusion rate as well as the structural protection of graphene,the Zn//MnO2-graphene battery presents an admirable capacity of 301 mAh g^-1 at 0.5 A g^-1,corresponding to a high energy density of 411.6 Wh kg^-1.Even at a high current density of 10 A g^-1,a decent capacity of 95.8 mAh g^-1 is still obtained,manifesting its excellent rate property.Furthermore,an impressive power density of 15 kW kg^-1 is achieved by the Zn//MnO2-graphene battery.

MnO_2@graphene为阴极催化剂的微生物燃料电池产电性能研究

以碳布为阴阳极材料,乙酸钠为底物,MnO_2@graphene为阴极催化剂构建空气阴极单室微生物燃料电池(MFC),研究了阳极液pH、阳极底物初始COD浓度、MFC运行温度等因素对MFC输出电压和产电功率的影响﹒研究结果表明,阳极液pH对MFC产电性能影响最大,而阳极底物初始COD浓度影响最小﹒在阳极液pH为8、MFC运行温度为308 K和阳极底物初始COD浓度为800 mg/L时MFC的产电性能和污水处理最佳﹒在此条件下,MFC对污水中COD的降解率可达98.4%,输出电压和产电功率密度分别可达0.813 V和2 046.9mW/m^2,说明以MnO_2@graphene为阴极催化剂的MFC具有较好的产电性能和污水处理效能﹒

Graphene/ZrO_2复合陶瓷材料的热导性能研究

采用3Y-ZrO_2粉体和石墨烯(Graphene)为原料,利用放电等离子体烧结技术(SPS),烧结制备了Graphene/ZrO_2复合陶瓷材料。利用SEM、HRTEM、XRD、激光热导仪等研究了烧结温度和石墨烯含量对Graphene/ZrO_2复合陶瓷材料的显微结构、物相和热传导性能的影响。研究结果表明,引入石墨烯不但可以抑制ZrO_2晶粒的生长,而且对复合材料的热传导性有着显著的影响;相对于单相ZrO_2陶瓷,随着石墨烯的引入,Graphene/ZrO_2复合陶瓷材料扩散系数反而降低,其原因可以归结于三个方面:首先,石墨烯含量比较低(0.5~1.5wt%),其次,石墨烯与Zr O晶粒界面处产生的强声子散射作用导致热导下降,最后是Graphene/ZrO_2复合陶瓷材料没有完全致密。

锂离子负极材料NiFe_2O_4/Graphene复合材料的制备和电化学性能

通过水热法合成了NiFe2O4/Graphene纳米复合材料,采用XRD和SEM对其晶相结构和形貌进行了表征,并将其作为锂离子电池活性材料组装成模拟电池,考查电化学性能。结果表明NiFe2O4/Graphene复合材料在100mA/g的电流密度下首次放电容量达970mAh/g,循环20次后,容量保持在668mAh/g,相比纯的NiFe2O4,具有较好的循环稳定性,这种优异的电化学性能归因于复合材料的纳米结构和NiFe2O4与Graphene的协同作用。