High-performance planar heterojunction perovskite solar cells： Preserving long charge carrier diffusion lengths and interracial engineering

We demonstrate that charge carrier diffusion lengths of two classes of perovskites, CH3NH3PbI3-xClx and CH3NH3PbI3, are both highly sensitive to film processing conditions and optimal processing procedures are critical to preserving the long carrier diffusion lengths of the perovskite films. This understanding, together with the improved cathode interface using bilayer-structured electron transporting interlayers of [6,6]-phenyl-C61-butyric acid methyl ester （PCBM）/ZnO, leads to the successful fabrication of highly efficient, stable and reproducible planar heterojunction CH3NH3PbI3-xCl2 solar cells with impressive power-conversion efficiencies （PCEs） up to 15.9%. A 1-square-centimeter device yielding a PCE of 12.3% has been realized, demonstrating that this simple planar structure is promising for large-area devices.     

载气在CVD法制备纳米碳管工艺中的作用

纳米碳管是性能优异的具有准一维特征的纳米材料,CVD法是制备纳米碳管的典型工艺之一。本文以乙炔气体为原料气体、循环失效后的贮氢电极舍金材料作为反应催化剂,研究了在相同反应条件下,CVD法制备纳米碳管过程中载气对纳米碳管形貌和产率的影响。通过对产物TEM观察和TG分析发现,虽然载气不直接参与合成反应但对产物产率和形貌有很大的影响,氢气作为载气可以获得形貌和热稳定性更好的纳米碳管。     

Robust reduction of graphene fluoride using an electrostatically biased scanning probe

We report a novel and easily accessible method to chemically reduce graphene fluoride （GF） sheets with nanoscopic precision using high electrostatic fields generated between an atomic force microscope （AFM） tip and the GF substrate. Reduction of fluorine by the electric field produces graphene nanoribbons （GNR） with a width of 105-1,800 nm with sheet resistivity drastically decreased from 〉1 TΩ.sq.^-1 （GF） down to 46 kΩ.sq.^-1 （GNR）. Fluorine reduction also changes the topography, friction, and work function of the GF. Kelvin probe force microscopy measurements indicate that the work function of GF is 180-280 meV greater than that of graphene. The reduction process was optimized by varying the AFM probe velocity between 1.2 μm.s^-1 and 12 μm.s^-1 and the bias voltage applied to the sample between -8 and -12 V. The electrostatic field required to remove fluorine from carbon is -1.6 V.nm-1. Reduction of the fluorine may be due to the softening of the C-F bond in this intense field or to the accumulation and hydrolysis of adventitious water into a meniscus.     

Flexible thermocells for utilization of body heat

Plastic thermo-electrochemical ceils （thermocells） involving aqueous potassium ferricyanide/ferrocyanide electrolyte have been investigated as an alternative to conventional thermoelectrics for thermal energy harvesting. Plastic thermocells that consist of all pliable materials such as polyethylene terephthalate （PET）, fabrics, and wires are flexible enough to be wearable on the human body and to be wrapped around cylindrical shapes. The performance of the thermocells is enhanced by incorporating carbon nanotubes into activated carbon textiles, due to improved charge transfer at the interface. In cold weather conditions （a surrounding temperature of 5 ℃）, the thermocell generates a short-circuit current density of 0.39 A/m2 and maximum power density of 0.46 mW/m2 from body heat （temperature of 36℃）. For practical use, we have shown that the thermocell charges up a capacitor when worn on a T-shirt by a person. We also have demonstrated that the electrical energy generated from waste pipe heat using a serial array of the thermocells and voltage converters can power a typical commercial light emitting diode （LED）.     

Ageing mechanisms and reliability of graphene-based electrodes

The development of flexible transparent electrodes for next generation devices has been appointed as the major topic in carbon electronics research for the next five years. Among all candidate materials tested to date, graphene and graphene based nanocomposites have shown the highest performance. Although some incipient anti-oxidation tests have been reported, in-deep ageing studies to assess the reliability of carbon-based electrodes have never been performed before. In this work, we present a disruptive methodology to assess the ageing mechanisms of graphene electrodes, which is also extensible to other carbon- based and two-dimensional materials. After performing accelerated oxidative tests, we exhaustively analyze the yield of the electrodes combining nanoscale and device level experiments with Weibull probabilistic analyses and tunneling current simulation, based on the Fowler-Nordheim/Direct-Tunneling models. Our experiments and calculations reveal that an ultra-thin oxide layer can be formed on the pristine surface of graphene. We quantitatively analyze the consequences of this layer on the properties of the electrodes, and observed a change in the conduction mode at the interface （from Ohmic to Schottky）, an effect that should be considered in the design of future graphene-based devices. Future mass production of carbon-based devices should include similar reliability studies, and the methodologies presented here （including the accelerated tests, characterization and modeling） may help other scientists to move from lab prototypes towards industrial device production.     

Study of the Adsorption Space of Modified Clinoptilolites

Carbon dioxide （CO2） adsorption is an important adsorbent characterization method and a significant industrial process. In separation and recovery technology, the adsorption of the CO2 is important to reduce the concentration of this gas considered as one of the greenhouse gases. Natural zeolites, particularly clinoptilolite, are widely applied as adsorbents. In this regard, in the present research, the structure, composition and morphology of modified with hexafluorosilicate （HFSi） and orthophosphoric acid （H3PO4） clinoptilolites were investigated by characterizations and measurements made with, X-ray diffraction （XRD）, thermogravimetric analysis （TGA）, scanning electron microscopy-energy dispersive X-ray analysis （SEM-EDAX） and gravimetric adsorption. Additionally, the surface Chemistry of the modified clinoptilolites was analyzed by applying diffuse reflectance fourier transform infrared spectrometry （DRIFTS）. Further, the interaction of CO2 within the adsorption space of these modified clinoptilolites and a synthetic ZSM-5 zeolite was studied with the help of adsorption measurements. After all, an appropriate theoretical methodology for the analysis of the XRD and adsorption data was applied. The calculated cell parameters of the tested are similar to those reported for a typical clinoptilolite of： a = 17.662 A, b = 17.911A, c = 7.407 ~ and fl = 116.40 The resolution of the TGA derivative profiles indicated the presence of two steps for water release, one of them represents the loss of majority of the water present in the micropores. This was evidenced as a broad peak centered at about 50℃ for the CSW-HFSi-0.1, but at 100 ℃ for the samples CSW-HFSi-0.4. The SEM micrographs corresponding to the modified clinoptilolites, was evidenced that the CSW zeolite shows secondary particles exhibiting diameters from 3 to 40 μm, formed by primary clinoptilolite crystallites showing a crystallite size, φ = 40 nm. The EDAX elemental analysis it can be demonstrated that the exchange process replaced about 85% of the charge compensating ions. The DRIFT spectra of the modified clinoptilolites, specifically, CSW-HFSi-0.1, show a narrow band at about： 3,740 cm-1 corresponding to terminal silanol groups （Si-OH） and a band 3,600-3,650 cm1 resulting from extra-framework AI-OH. With the precision of the measured micropore volumes related to the excellent fitting of the adsorption data by the D-R isotherm equation, it can be affirm that carbon adsorption took only place in the micropore region. The isosteric heat of adsorption calculated for the modified clinoptilolites was greater than those values reported of ZSM-5 zeolite, particle packing silica, dealuminated Y zeolite （DAY） Cd, Zn and Ni-nitroprussides and Cu-nitroprusside and a Ni-MOF. With the obtained result it can be concluded that the modified clinoptilolites with HFSi showed a quality as adsorbent comparable to commercial synthetic zeolites.     

Dyeing bacterial cellulose pellicles for energetic heteroatom doped carbon nanofiber aerogels

The energy crisis and environmental pollution are serious challenges that humanity will face for the long-term. Despite tremendous efforts, the development of environmentally friendly methods to fabricate new energy materials is still challenging. Here we report, for the first time, a new strategy to fabricate various doped carbon nanofiber （CNF） aerogels by pyrolysis of bacterial cellulose （BC） pellicles which had adsorbed or were dyed with different toxic organic dyes. The proposed strategy makes it possible to remove the toxic dyes from waste-water and then synthesize doped CNF aerogels using the dyed BC pellicles as precursors. Compared with other reported processes for preparing heteroatom doped carbon （HDC） nanomaterials, the present synthetic method has some significant advantages, such as being green, general, low-cost and easily scalable. Moreover, the as-prepared doped CNF aerogels exhibit great potential as electrocatalysts for the oxygen reduction reaction （ORR） and as electrode materials for supercapacitors.     

A Tool for Interrogation of Macromolecular Structure

Our program BABELPDB allows browsing and interrogating the native and derived structural features of biomacromolecules using data obtained from the Protein Data Bank （PDB）. Major features of BABELPDB are： （1） convert from PDB to other formats, （2） add or remove H-atoms, （3） strip the crystallization water molecules and （4） separate the ct-carbons （Cα）. The co-ordinates obtained with BABELPDB permit characterizing the presence of H-bonds. The algorithm for detecting H-bonds is implemented in our program TOPO for the theoretical simulation of the molecular shape, An example is given to illustrate the capabilities of the software： the calculation of the fractal dimension of the lysozyme molecule with （1.908） and without （1.920） H-atoms. The figures compare well with reference calculations performed with our version of program GEPOL and results from Pfeifer et al. For proteins, Cα-skeleton extracted with BABELPDB allows drawing the ribbon image, which determines their secondary structure.     

Numerical Study of Solid Iron Carburization in a Carbon Monoxide Atmosphere

The diffusion step during the high temperature carburization of a spherical iron particle in a carbon monoxide atmosphere is mathematically modeled and numerically simulated in this work. The continuity equation is numerically solved using a forward finite-differences scheme, and a temperature range of 1,486-1,664 K is considered. An integration time during which the solid iron particle is not yet melted is assumed. The programming code was verified using experimental results previously reported by other authors. Radial carbon concentration is determined for several temperatures, and the average carbon concentration in the particle is obtained by numerical integration.     

Light and Electron Microscopy Studies of the Visible Diffusion Zone of Mild Steel Pack Cyanided in Processed Cassava Leaves

This study investigates the microstructure of the processed cassava leaves. Standard parts machined from low visible diffusion zone formed in low carbon steel pack cyanided using carbon steel were pack cyanided by high temperature in-situ diffusion of nascent carbon and nitrogen into austenite. Formation of a visible diffusion zone was confirmed after observation with a Reichert-Jung Polyval optical microscope coupled with Zeiss AxioCam ICc 1 camera. High magnification Scanning Electron Microscope （SEM） imaging of the visible diffusion zone was done with a CamScan Series 2 scanning electron microscope. The zone was found variable in depth as measured from a representative position. The structure of all samples consists of ferrite and pearlite as determined by optical and SEM examination. Resulting products were thus both tough and hard suitable for service environments requiring high resistance to both wear and impact failure.     

Modulating the Surface State of SiC to Control Carrier Transport in Graphene/SiC

Silicon carbide (SiC) with epitaxial graphene (EG/SiC) shows a great potential in the applications of electronic and photoelectric devices. The performance of devices is primarily dependent on the interfacial heterojunction between graphene and SiC. Here, the band structure of the EG/SiC heterojunction is experimentally investigated by Kelvin probe force microscopy. The dependence of the barrier height at the EG/SiC heterojunction to the initial surface state of SiC is revealed. Both the barrier height and band bending tendency of the heterojunction can be modulated by controlling the surface state of SiC, leading to the tuned carrier transport behavior at the EG/SiC interface. The barrier height at the EG/SiC(000‐1) interface is almost ten times that of the EG/SiC(0001) interface. As a result, the amount of carrier transport at the EG/SiC(000‐1) interface is about ten times that of the EG/SiC(0001) interface. These results offer insights into the carrier transport behavior at the EG/SiC heterojunction by controlling the initial surface state of SiC, and this strategy can be extended in all devices with graphene as the top layer.     

Highly stretchable pseudocapacitors based on buckled reticulate hybrid electrodes

In order to develop an excellent pseudocapacitor with both high specific capacitance and outstanding stretchability to match with other devices applicable in future wearable and bio-implantable systems, we focus our studies on three vital aspects： Stretchability of hybrid film electrodes, the interface between different components, and the integrated performance in stretchability and electrochemistry of supercapacitors based on single-walled carbon nanotube/ polyaniline （SWCNT/PANI） composite films on pre-elongated elastomers. Owing to the moderate porosity, the buckled hybrid film avoids the cracking which occurs in conventional stretchable hybrid electrodes, and both a high specific capacitance of 435 F.g-1 and a high strain tolerance of 140% have been achieved. The good SWCNT/PANI interfacial coupling and the reinforced solid electrolyte penetration structure enable the integrated pseudocapacitors to have stretch- resistant interfaces between different units and maintain a high performance under a stretching of 120% elongation, even after 1,000 cyclic elongations.     

Amine Functionalized Metal–Organic Framework Coordinated with Transition Metal Ions: d–d Transition Enhanced Optical Absorption and Role of Transition Metal Sites on Solar Light Driven H2 Production

Design and development of efficient photocatalysts for H₂ production from water and sunlight have gained significant attention as the solar assisted approach is considered to be a promising approach for the generation of clean fuel. However, the poor charge carrier separation and light harvesting ability of existing photocatalysts limits the efficiency of photoconversion of water. In this work, the synthesis of transition metal ions (M²⁺ = Co²⁺, Cu²⁺, and Ni²⁺) coordinated with Ti‐metal organic frameworks (Ti‐MOFs) through a simple post‐synthetic coordination method for efficient solar light‐driven H₂ production is reported. Notably, coordination of M²⁺ ions with Ti‐MOF significantly improves the optical absorption by d–d transitions and the multimetal sites facilitate the fast charge carrier separation, thereby enhancing the solar light‐driven H₂ production activity. Very interestingly, the rate of solar light‐driven H₂ production is varied with respect to different metal ions coordination due to the position of d–d bands absorption in the solar spectrum, and the complexing tendency of M²⁺ ions with sacrificial electron donors. A maximum solar H₂ production rate of 1583.55 µmol h^?1 g^?1 is achieved with a Cu²⁺ coordinated Ti‐MOF, which is ≈13 fold higher than that of the pristine Ti‐MOF.     

载气种类对单壁碳纳米管管径的影响研究

单壁碳纳米管的管径对其性能、特别是储氢性能有极其重要的影响,但至今未见制备过程中系统控制单壁碳纳米管管径的报道.本文分别以氦气、氮气和氩气为载气,采用催化裂解法制备了不同直径范围的单壁碳纳米管.HRTEM和Raman光谱分析表明,以氦气、氩气为载气制得的碳管直径分布范围相对较窄,平均直径分别约为1.6和5.0nm.以氮气为载气时碳管直径分布相对较宽,约为2.0～4.5nm.氮气与碳反应生成氮化碳可能是导致单壁碳纳米管直径分布相对较宽的主要原因.分别以氦气、氮气和氩气为载气制得的单壁碳纳米管,在273K,15MPa时质量储氢分数依次为4.21%、6.30%和8.05%.     

Axial loading verification method for small bones using carrier fringes in speckle pattern interferometry

A computerized system for real-time displacement visualization using carrier fringes in an electronic speckle in-plane sensitive interferometer allows force calibration for micro-displacement analysis of rat bones and verification of axial loading conditions. Once the force has been calibrated and the load is applied along the bone axis, the difference-of-phase method is used to obtain the phase map, which after phase unwrapping, allows the evaluation of the displacements produced by the bone deformation. The proposed method avoids common loading mistakes using first carrier fringes to assure that the loads are within the measuring capabilities of the in-plane interferometer and the Carré phase-stepping method to compensate for linear phase step miscalibration. The experimental results obtained with the calibration of loading forces and axial loading verification show the advantages of the system proposed here over a system which uses a cantilever configuration to make a similar bone deformation analysis.     

硅表面钝化及对异质结太阳电池特性的影响

研究了不同的晶体硅表面钝化方法,测试分析了硅片的少数载流子寿命以及对晶体硅/非晶硅异质结(HIT)太阳电池性能的影响。发现适当时间的HF溶液处理、氢等离子体处理和表面覆盖约3nm的本征非晶硅层能有效提高硅片的少子寿命,从而提高HIT太阳电池的开路电压。对电池制备工艺综合优化后,得到了基于n型晶体硅的光电转换效率为16.75%(Voc=0.596V,Jsc=41.605mA/cm2,FF=0.676,AM1.5,25℃)的HIT太阳电池。     

TiO2 nanotube branched tree on a carbon nanofiber nanostructure as an anode for high energy and power lithium ion batteries

The inherently low electrical conductivity of TiO2-based electrodes as well as the high electrical resistance between an electrode and a current collector represents a major obstacle to their use as an anode for lithium ion batteries. In this study, we report on high-density TiO2 nanotubes （NTs） branched onto a carbon nanofiber （CNF） ＂tree＂ that provide a low resistance current path between the current collector and the TiO2 NTs. Compared to a TiO2 NT array grown directly on the current collector, the branched TiO2 NTs tree, coupled with the CNF electrode, exhibited -10 times higher areal energy density and excellent rate capability （discharge capacity of -150 mA.h.g-1 at a current density of 1,000 mA·g-1）. Based on the detailed experimental results and associated theoretical analysis, we demonstrate that the introduction of CNFs with direct electric contact with the current collector enables a significant increase in areal capacity （mA·h·cm-2） as well as excellent rate capability.     

r.f.PCVD法制备c-BN膜的研究

采用 Ｆ Ｔ Ｉ Ｒ、 Ｔ Ｅ Ｍ、 Ｓ Ｅ Ｍ 等技术, 对在渗硼层表面经ｒ.ｆ. Ｐ Ｃ Ｖ Ｄ 沉积的 Ｂ Ｎ 膜进行了研究试验证明, 与采用 Ｎ_２ 气和 Ｈ_２ 气相比, 以 Ａｒ ＋ １０ｖｏｌ％ Ｈ_２ 作为载气, 所获得的膜层ｃ-Ｂ Ｎ 含量最高, 膜厚最大, 可达４.６μｍ , 且膜基结合良好而以 Ｎ_２ 气或 Ｈ_２ 气为载气时, 前者会导致膜基结合力大大下降, 后者会引起沉积速度明显降低结果表明, 对于 Ｐ Ｃ Ｖ Ｄ 过程, 控制ｃ- Ｂ Ｎ 形成的主要因素是离子轰击能量的转移, 而不是氢的选择溅射过程试验获得的膜层由ａ- Ｂ Ｎ 和ｃ- Ｂ Ｎ 组成, ｃ- Ｂ Ｎ的尺寸为２０ ～４０ｎｍ     

固定微生物用聚合物多孔载体的研究

用悬浮共聚随后碱解的方法制得了部分水解聚（丙烯酸甲酯－醋酸乙烯酯－甲基丙烯酸甲酯多孔载体（载体Ａ）。研究了聚合物组成、致孔剂、交联剂和ＮａＯＨ用量与载体Ａ孔结构的关系，用电镜、Ｘ射线衍射和电子衍射测定了载体的结构。结果表明，载体Ａ孔结构受致孔剂、交联剂和ＮａＯＨ用量及聚合物种类、组成影响较大。载体Ａ适宜于微生物固定化，固定化载体表面和孔内均聚集了大量菌群，微生物集量大，产甲烷量优于其它聚合物、活性     

Synthesis and TEM structural characterization of C60-flattened carbon nanotube nanopeapods

A fully flattened carbon nanotube （FNT）, a graphene nanoribbon （GNR） analogue, provides a hollow space at edges for endohedral doping. Due to the unique shape of the hollow space of FNTs, novel types of low-dimensional arrangements of atoms and molecules can be obtained through endohedral doping into FNTs, which provides a new type of nanopeapods. FNT-based nanopeapods have been synthesized through endohedral doping of C60, and their structural characterization with transmission electron microscopy （TEM） performed. The doping of C60 into the inner hollow space of FNTs has been carried out via the gas-phase filling method, where open-ended FNTs are sealed in a glass ampoule and heated at 723-773 K for two days. TEM observations show that most of the encapsulated C60 molecules align as single molecular chains along the edges of FNTs and that some of the C60 forms two-dimensional close-packed structures inside FNTs.