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.

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.

Graphene/MoS2 heterostructure:a robust mid-infrared optical modulator for Er3+-doped ZBLAN fiber laser

We have prepared the graphene∕MoS2 heterostructure by a hydrothermal method, and presented its nonlinear absorption parameters and application as a nonlinear optical modulator in the mid-infrared region.Using the nonlinear optical modulator, stable passively Q-switched operation of an Er^（3＋）-doped ZrF4-BaF2-LaF3-AlF3-NaF（ZBLAN） fiber laser at ~2.8 μm can be obtained. The Q-switched Er^（3＋）-doped ZBLAN fiber laser can yield per-pulse energy up to 2.2 μJ with the corresponding pulse width and pulse repetition rate of 1.9 μs and 45 kHz, respectively. Our results indicate that the graphene∕MoS2 heterostructure can be a robust optical modulator for pulsed lasers in the mid-infrared spectral range.

MoS2/Ti3C2Tx异质复合材料的制备及电化学性能研究

利用水热法合成了MoS2/Ti3C2Tx异质复合材料,采用SEM、XRD、XPS和电化学工作站对所制样品的形貌、结构、成分和电化学性能进行了表征。结果表明,当Ti3C2Tx引入量为30 mg时,所制MoS2/Ti3C2Tx异质复合电极具有最优的电化学性能和较好的循环稳定性,在1 A/g电流密度下的比电容达到262.54 F/g,且经10 000次循环后仍保持82.1%的初始比电容。

准三维MoS_2/graphene复合材料储锂性能研究

本研究以氧化石墨烯为前驱体,利用钼酸钠和硫脲通过水热法在不同阳离子表面活性剂(C14TAB,C16TAB,C18TAB)的辅助下合成得到MoS_2/GF复合结构。XRD和SEM分析表明,MoS_2/GF复合材料因阳离子表面活性剂的不同而呈现不同的结构和表面形貌;电化学性能测试表明其结构和表面形貌对电极的容量、循环稳定性和倍率性能都有较大影响。相比于C16TAB和C18TAB,C14TAB辅助合成的MoS_2/GF复合结构具有最高的首次放电容量(955 m Ah/g),50次循环后仍保持751 m Ah/g的可逆容量,而且倍率性能更好。本研究揭示MoS_2/GF复合材料电化学性能的提升可归因于其独特的praticle-on-sheet结构以及MoS_2与石墨烯之间的协同作用。

Unsaturated bi-heterometal clusters in metal-vacancy sites of 2D MoS2 for efficient hydrogen evolution

The valence states and coordination structures of doped heterometal atoms in two-dimensional(2D)nanomaterials lack predictable regulation strategies.Hence,a robust method is proposed to form unsaturated heteroatom clusters via the metal-vacancy restraint mechanism,which can precisely regulate the bonding and valence state of heterometal atoms doped in 2D molybdenum disulfide.The unsaturated valence state of heterometal Pt and Ru cluster atoms form a spatial coordination structure with Pt–S and Ru–O–S as catalytically active sites.Among them,the strong binding energy of negatively charged suspended S and O sites for H+,as well as the weak adsorption of positively charged unsaturated heterometal atoms for H*,reduces the energy barrier of the hydrogen evolution reaction proved by theoretical calculation.Whereupon,the electrocatalytic hydrogen evolution performance is markedly improved by the ensemble effect of unsaturated heterometal atoms and highlighted with an overpotential of 84 mV and Tafel slope of 68.5 mV dec^(−1).In brief,this metal vacancy-induced valence state regulation of heterometal can manipulate the coordination structure and catalytic activity of heterometal atoms doped in the 2D atomic lattice but not limited to 2D nanomaterials.

与Si CMOS兼容的Graphene/MoS2异质结全差分光电探测器和读出电路

提出了一种基于Graphene/MoS2异质结的全差分光电探测器。利用标准半导体微纳加工技术,制作了有效区域为2.3μm×10μm的Graphene/MoS2异质结结构,用以产生差分光电流;使用0.18μmCMOS工艺设计了差分放大与恒压控制电路,实现光电流到电压的转换和放大。结果表明:在白光照射下,单个Graphene/MoS2异质结结构光响应度达2435A/W。差分光生电流经过差分放大器后,以电压形式输出,总光响应度加倍。该全差分光探测器基于新型二维材料,对可见光具有较高的灵敏度,在可见光探测和成像领域具有广阔的应用前景。

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%。

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.

Construction of robust coupling interface between MoS2 and nitrogen doped graphene for high performance sodium ion batteries

As a layered inorganic material,MoS2 has recently attracted intensive attention as anode for sodium ion batteries(SIBs).However,this anode is plagued with low electronic conductivity,serious volume expansion and sluggish kinetics,resulting in capacity fading and poor rate performance.Herein,we develop an interface engineering strategy to substantially enhance the sodium storage performance of MoS2 by incorporating layered MoS2 into three dimensional N-doped graphene scaffold.The strong coupling-interface between MoS2 and N-doped graphene scaffold can not only stabilize the MoS2 structure during sodium insertion/extraction processes,but also provide plenty of anchor sites for additional surface sodium storage.The 3D MoS2@N-doped graphene composite as anode for SIBs performs an outstanding specific capacity of 667.3 mA h g^-1 at 0.2 A g^-1,a prolonged stability with a capacity retention of 94.4%after 140cycles and excellent rate capability of 445 mA h g^-1 even at a high rate of 10 A g^-1.We combined experiment and theoretical simulation to further disclose the interaction between MoS2 and N-doped graphene,adsorption and diffusion of sodium on the composite and the corresponding sodium storage mechanism.This study opens a new door to develop high performance SIBs by introducing the interface engineering technique.

Facilitative effect of graphene quantum dots in MoS_2 growth process by chemical vapor deposition

The substrate treatment with seeding promoter can promote the two-dimensional material lateral growth in chemical vapor deposition （CVD） process. Herein, graphene quantum dots （GQDs） as a novel seeding promoter were used to obtain uniform large-area MoS2 monolayer. The obtained monolayer MoS2 films were confirmed by optical microscope, scanning electron microscope, Raman and photoluminescence spectra. Raman mapping revealed that the MoS2 monolayer was largely homogeneous.

MoS2对热压Fe基金刚石钻头胎体性能的影响研究

金刚石钻头是勘探工作中的常见破岩工具,但金刚石热稳定性较差,在钻进过程中会不断产生热量,干旱缺水条件下钻头自冷却对钻进效率的提高具有非常重要的意义。为降低干钻条件下钻头胎体与岩石界面间的摩擦因数从而减少钻进过程中金刚石的热损伤,在热压Fe基金刚石钻头胎体中添加二硫化钼(MoS2),研究MoS2含量对Fe基钻头胎体相对密度、洛氏硬度、抗弯强度以及与白刚玉砂轮干磨时的磨损量和摩擦因数的影响,并用扫描电子显微镜(SEM)和能谱仪(EDS)等测试仪器分析了抗弯强度和摩擦磨损试验后的试样断口和表面的形貌及物相成分。试验结果表明,在试验范围内,Fe基胎体相对密度与MoS2含量关系不大,但是与未添加MoS2的Fe基胎体相比,其相对密度提高了约2.5%,达98%以上。Fe基胎体洛氏硬度随着MoS2含量的增加先增大后减小,在MoS2体积分数为8%时胎体硬度最大,洛氏硬度HRB值达101.3。Fe基胎体抗弯强度随着MoS2含量的增加先增大后减小,在MoS2体积分数为2%时胎体抗弯强度最大,达1140 MPa。Fe基胎体磨损量随着MoS2含量的增加先减小后增大,在MoS2体积分数为4%时磨损量最小,为0.376 g。Fe基胎体与岩石界面间的摩擦因数则随着MoS2含量的增加而逐渐下降,在MoS2体积分数为10%时摩擦因数最小,为0.325。抗弯强度断裂试样断口形貌和物相分析表明,MoS2的加入降低了Fe基胎体显微组织的连续性。摩擦磨损试验后试样形貌分析表明,MoS2的加入降低了摩擦磨损过程中的粘着磨损和塑性变形。研究成果为减少干钻条件下金刚石磨损和热损伤,提高胎体耐磨性,延长钻头寿命奠定了理论基础。

Precisely controlling the twist angle of epitaxial MoS_(2)/graphene heterostructure by AFM tip manipulation

Two-dimensional(2D)moirématerials have attracted a lot of attention and opened a new research frontier of twistronics due to their novel physical properties.Although great progress has been achieved,the inability to precisely and reproducibly manipulate the twist angle hinders the further development of twistronics.Here,we demonstrated an atomic force microscope(AFM)tip manipulation method to control the interlayer twist angle of epitaxial MoS_(2)/graphene heterostructure with an ultra-high accuracy better than 0.1°.Furthermore,conductive AFM and spectroscopic characterizations were conducted to show the effects of the twist angle on moirépattern wavelength,phonons and excitons.Our work provides a technique to precisely control the twist angle of 2D moirématerials,enabling the possibility to establish the phase diagrams of moiréphysics with twist angle.

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。

炭含量对MoS_(2)/GR复合电极材料电化学性能的影响

将Hummers法制备石墨烯产生的副产物经过高温炭化和氢氧化钾(KOH)活化后得到石墨烯残留炭(GR)。以GR、钼酸钠及硫脲为原料,在pH=3的前置溶液中,通过简单的一步水热法制备了二硫化钼/石墨烯残留炭(MoS_(2)/GR)复合电极材料。通过改变GR的加入量(5%、10%、15%),探究其对MoS_(2)/GR电化学性能的影响。采用X射线衍射仪、扫描电子显微镜、电化学工作站对复合电极材料的结构、形貌及电化学性能进行表征和测试。结果表明:GR的加入会降低MoS_(2)的结晶度;随着GR加入量的增加,MoS_(2)/GR的尺寸会逐渐减小。当GR加入量为15%(质量分数)时,制备的样品15MoS_(2)/GR具有最高的比电容(312.0F/g),相较于纯MoS_(2)(110F/g)比电容提升了近3倍,并且在5A/g电流密度下循环1000次后,容量保持率为96.3%,表现出良好的循环稳定性。定量动力学计算表明,15MoS_(2)/GR的储能方式以扩散贡献为主。

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。