Alumina-grafted SBA-15 as a high performance support for Pd-catalysed cinnamyl alcohol selective oxidation

Ultrathin alumina monolayers grafted onto an ordered mesoporous SBA-15 silica framework afford a composite catalyst support with unique structural properties and surface chemistry. Palladium nanoparticles deposited onto Al-SBA-15 via wet impregnation exhibit the high dispersion and surface oxidation characteristic of pure aluminas, in conjunction with the high active site densities characteristic of thermally stable, high-area mesoporous silicas. This combination confers significant rate enhancements in the aerobic selective oxidation (selox) of cinnamyl alcohol over Pd/Al-SBA-15 compared to mesoporous alumina or silica supports. Operando, liquid-phase XAS highlights the interplay between dissolved oxygen and the oxidation state of palladium nanoparticles dispersed over Al-SBA-15 towards on-stream reduction: ambient pressures of flowing oxygen are sufficient to hinder palladium oxide reduction to metal, enabling a high selox activity to be maintained, whereas rapid PdO reduction and concomitant catalyst deactivation occurs under static oxygen. Selectivity to the desired cinnamaldehyde product mirrors these trends in activity, with flowing oxygen minimising CO cleavage of the cinnamyl alcohol reactant to trans-β-methylstyrene, and of cinnamaldehyde decarbonylation to styrene. © 2013 Elsevier B.V.

In situ X-ray studies of crotyl alcohol selective oxidation over Au/Pd(1 1 1) surface alloys

The selective oxidation of crotyl alcohol to crotonaldehyde over ultrathin Au overlayers on Pd(1 1 1) and Au/Pd(1 1 1) surface alloys has been investigated by time-resolved X-ray photoelectron spectroscopy (XPS) and mass spectrometry. Pure gold is catalytically inert towards crotyl alcohol which undergoes reversible adsorption. In contrast, thermal processing of a 3.9 monolayer (ML) gold overlayer allows access to a range of AuPd surface alloy compositions, which are extremely selective towards crotonaldehyde production, and greatly reduce the extent of hydrocarbon decomposition and eventual carbon laydown compared with base Pd(1 1 1). XPS and CO titrations suggest that palladium-rich surface alloys offer the optimal balance between alcohol oxidative dehydrogenation activity while minimising competitive decomposition pathways, and that Pd monomers are not the active surface ensemble for such selox chemistry over AuPd alloys. Crown Copyright © 2008.

High-pressure XPS of crotyl alcohol selective oxidation over metallic and oxidized Pd(111)

Here, we report on the first application of high-pressure XPS (HP-XPS) to the surface catalyzed selective oxidation of a hydrocarbon over palladium, wherein the reactivity of metal and oxide surfaces in directing the oxidative dehydrogenation of crotyl alcohol (CrOH) to crotonaldehyde (CrHCO) is evaluated. Crotonaldehyde formation is disfavored over Pd(111) under all reaction conditions, with only crotyl alcohol decomposition observed. In contrast, 2D Pd5O4 and 3D PdO overlayers are able to selectively oxidize crotyl alcohol (1 mTorr) to crotonaldehyde in the presence of co-fed oxygen (140 mTorr) at temperatures as low as 40 °C. However, 2D Pd5O4 ultrathin films are unstable toward reduction by the alcohol at ambient temperature, whereas the 3D PdO oxide is able to sustain catalytic crotonaldehyde production even up to 150 °C. Co-fed oxygen is essential to stabilize palladium surface oxides toward in situ reduction by crotyl alcohol, with stability increasing with oxide film dimensionality.

XPS and XMCD study of Fe3O4/GaAs interface

Ultrathin Fe oxide films of various thicknesses prepared by post-growth oxidation on GaAs(100) surface have been investigated with X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS), and X-ray magnetic circular dichroism (XMCD). The XPS confirms that the surfaces of the oxide are Fe3O4 rather than Fe2O3. XAS and XMCD measurements indicate the presence of insulating Fe divalent oxide phases (FeO) beneath the surface Fe3O4 layer with the sample thickness above 4 nm. This FeO might act as a barrier for the spin injection into the GaAs.

Epitaxial growth and magnetic properties of half-metallic Fe3O4 on GaAs(100)

The growth and magnetic properties of epitaxial magnetite Fe3O4 on GaAs(100) have been studied by reflection high-energy electron diffraction, x-ray photoelectron spectroscopy, magneto-optical Kerr effect, and x-ray magnetic circular dichroism. The epitaxial Fe3O4 films were synthesized by in situ post growth annealing of ultrathin epitaxial Fe films at 500K in an oxygen partial pressure of 5×10−5mbar. The XMCD measurements show characteristic contributions from different sites of the ferrimagnetic magnetite unit cell, namely, Fetd3+, Feoh2+, and Feoh3+. The epitaxial relationship was found to be Fe3O4(100)⟨011⟩∕∕GaAs(100)⟨010⟩ with the unit cell of Fe3O4 rotated by 45° to match that of GaAs(100) substrate. The films show a uniaxial magnetic anisotropy in a thickness range of about 2.0–6.0nm with the easy axes along the [011] direction of the GaAs(100) substrate.

Propene combustion over a model Pt/Al2O3/NiAl{110} catalyst

The genesis of a catalytically active model Pt/Al2O3/NiAl{110} oxidation catalyst is described. An ultrathin, crystalline γ-Al2O3 film was prepared via direct oxidation of a NiAl{110} single-crystal substrate. The room-temperature deposition of Pt clusters over the γ-Al2O3 film was characterised by LEED, AES and CO titration and follows a Stranski–Krastanov growth mode. Surface sulfation was attempted via SO2/O2 adsorption and thermal processing over bare and Pt promoted Al2O3/NiAl{110}. Platinum greatly enhances the saturation SOx coverage over that of bare alumina. Over clean Pt/γ-Al2O3 surfaces some adsorbed propene desorbs molecularly [similar]250 K while the remainder decomposes liberating hydrogen. Coadsorbed oxygen or sulfate promote propene combustion, with adsorbed sulfoxy species the most efficient oxidant. The chemistry of these alumina-supported Pt clusters shows a general evolution from small polycrystalline clusters to larger clusters with properties akin to low-index, Pt single-crystal surfaces.

Carbon nanotube reinforced aluminum based nanocomposite fabricated by thermal spray forming

The present research concentrates on the fabrication of bulk aluminum matrix nanocomposite structures with carbon nanotube reinforcement. The objective of the work was to fabricate and characterize multi-walled carbon nanotube (MWCNT) reinforced hypereutectic Al-Si (23 wt% Si, 2 wt% Ni, 1 wt% Cu, rest Al) nanocomposite bulk structure with nanocrystalline matrix through thermal spray forming techniques viz. plasma spray forming (PSF) and high velocity oxy-fuel (HVOF) spray forming. This is the first research study, which has shown that thermal spray forming can be successfully used to synthesize carbon nanotube reinforced nanocomposites. Microstructural characterization based on quantitative microscopy, scanning and transmission electron microscopy (SEM and TEM), energy dispersive spectroscopy (EDS), X-ray diffraction (XRD), Raman spectroscopy and X ray photoelectron spectroscopy (XPS) confirms (i) retention and macro/sub-macro level homogenous distribution of multiwalled carbon nanotubes in the Al-Si matrix and (ii) evolution of nanostructured grains in the matrix. Formation of ultrathin β-SiC layer on MWCNT surface, due to chemical reaction of Si atoms diffusing from Al-Si alloy and C atoms from the outer walls of MWCNTs has been confirmed theoretically and experimentally. The presence of SiC layer at the interface improves the wettability and the interfacial adhesion between the MWCNT reinforcement and the Al-Si matrix. Sintering of the as-sprayed nanocomposites was carried out in an inert environment for further densification. As-sprayed PSF nanocomposite showed lower microhardness compared to HVOF, due to the higher porosity content and lower residual stress. The hardness of the nanocomposites increased with sintering time due to effective pore removal. Uniaxial tensile test on CNT-bulk nanocomposite was carried out, which is the first ever study of such nature. The tensile test results showed inconsistency in the data attributed to inhomogeneous microstructure and limitation of the test samples geometry. The elastic moduli of nanocomposites were computed using different micromechanics models and compared with experimentally measured values. The elastic moduli of nanocomposites measured by nanoindentation technique, increased gradually with sintering attributed to porosity removal. The experimentally measured values conformed better with theoretically predicted values, particularly in the case of Hashin-Shtrikman bound method.

Carbon nanotube based systems for high energy efficient applications

In the current age of fast-depleting conventional energy sources, top priority is given to exploring non-conventional energy sources, designing highly efficient energy storage systems and converting existing machines/instruments/devices into energy-efficient ones. ‘Energy efficiency’ is one of the important challenges for today’s scientific and research community, worldwide. In line with this demand, the current research was focused on developing two highly energy-efficient devices – field emitters and Li-ion batteries, using beneficial properties of carbon nanotubes (CNT). Interface-engineered, directly grown CNTs were used as cathode in field emitters, while similar structure was applied as anode in Li-ion batteries. Interface engineering was found to offer minimum resistance to electron flow and strong bonding with the substrate. Both field emitters and Li-ion battery anodes were benefitted from these advantages, demonstrating high energy efficiency. Field emitter, developed during this research, could be characterized by low turn-on field, high emission current, very high field enhancement factor and extremely good stability during long-run. Further, application of 3-dimensional design to these field emitters resulted in achieving one of the highest emission current densities reported so far. The 3-D field emitter registered 27 times increase in current density, as compared to their 2-D counterparts. These achievements were further followed by adding new functionalities, transparency and flexibility, to field emitters, keeping in view of current demand for flexible displays. A CNT-graphene hybrid structure showed appreciable emission, along with very good transparency and flexibility. Li-ion battery anodes, prepared using the interface-engineered CNTs, have offered 140% increment in capacity, as compared to conventional graphite anodes. Further, it has shown very good rate capability and an exceptional ‘zero capacity degradation’ during long cycle operation. Enhanced safety and charge transfer mechanism of this novel anode structure could be explained from structural characterization. In an attempt to progress further, CNTs were coated with ultrathin alumina by atomic layer deposition technique. These alumina-coated CNT anodes offered much higher capacity and an exceptional rate capability, with very low capacity degradation in higher current densities. These highly energy efficient CNT based anodes are expected to enhance capacities of future Li-ion batteries.

Análise das principais variáveis na flotação industrial do complexo de mineração de Tapira - MG

Faced with an agribusiness expansion scenario and the increase in fertilizer consumption due to the exponential growth of the population, it is necessary to make better use of existing reserves, by obtaining products of better quality and in adequate quantities to meet demand national. In Tapira Mining Complex, Vale Fertilizantes, the phosphate concentrate is produced with content of 35.0% P2O5 from ore with content of about 8.0% P2O5, which are intended to supply Complex Industrial Uberaba and Araxá Minero Chemical Complex for the production of fertilizers. The industrial flotation step responsible for the recovery of P2O5 and hence the viability of the business is divided into the crumbly, grainy and ultrathin circuits, and, friable and granular concentrate comprise the conventional concentrated. Today only 14.7% of the mass which feeds the mill product becomes, the remainder being considered losses in the process, and the larger mass losses are located in the waste of flotation, representing 42.3%. From 2012 to 2014, the daily global mass recovery processing plants varied from 12.4 to 15.9% while the daily metallurgical recovery of P2O5 from 48.7 to 82.4%. By the degree of variability, it appears that the plant operated under different conditions. Seen this, this study aimed to analyze the influence of operational and process variables in P2O5 mass and metallurgical recoveries of industrial flotation circuits of grainy, crumbly and ultrathin. And besides was made an analysis of the effect of ore variables, as degrees, hardnesse and the ore front 02 percentage, in global recoveries of processing plant and the effect of dosages of reagents in the recoveries obtained from the bench flotation using the experimental design methodology. All work was performed using the historical database of Vale Fertilizantes of Tapira-MG, where all independent variables were dimensionless as the experimental range used. To make the statistical analysis it used the response surface technique and the values of the independent variables that maximize recoveries were found by canonical analysis. In the study of industrial flotation circuit crispy were obtained from 41.3% mass recovery and 91.3% metallurgical recovery P2O5, good values for the circuit, and the highest recoveries occur for solids concentration of the new flotation power between 45 and 50%, which values are assigned to the residence time of the pulp in cells and industrial flotation columns. The greater the number of ore heaps resumed on the higher the mass recovery, but in this scenario flotation becomes unstable because there is enormous weight variation in the feed. Higher recoveries are obtained for mass depressant dosage exceeding 120 g / t for synthetic collector dosage of 11.6%. In the study of industrial flotation circuit of the granulate were obtained 28.3% to 79.4% mass recovery and metallurgical recovery of P2O5 being considered good values for the circuit. Higher recoveries are obtained when the front ore 02 percentage is above 90%, because the ore of this front have more clear apatite. Likewise recoveries increase when the level of pulp rougher step is highest due to the high mass of circulating step receives loads. In the analysis of industrial flotation circuit of the ultrafine were obtained 23.95% of mass recovery, and the same is maximized to depressant dosage and the top collector 420 and 300 g / t, respectively. The analysis of the influence of variables ore, it was observed that higher recoveries are obtained for ores with P2O5 content above 8.0%, Fe2O3 content in the order of 28% forward and 02 of ore percentage of 83%. Hard ore percentage has strong influence on recoveries due to mass division in the circuit that is linked to this variable. However, the hard ore percentage that maximizes recoveries was very close to the design capacity of the processing plant, which is 20%. Finally, the study of the bench flotation, has noted that in friable and granular circuits the highest recoveries are achieved for a collector dosage exceeding 250 g / t and the simultaneous increase of collector dosage and synthetic collector percentage contributes to the increase recovery in the flotation, but this scenario is suitable to produce a concentrate poorer in terms of P2O5 content, showing that higher recovery is not always the ideal scenario. Thus, the results show the values of variables that provide higher recoveries in the flotation and hence lower losses in the waste.

Nanostructured Metal Oxide Coatings for Electrochemical Energy Conversion and Storage Electrodes

The realization of an energy future based on safe, clean, sustainable, and economically viable technologies is one of the grand challenges facing modern society. Electrochemical energy technologies underpin the potential success of this effort to divert energy sources away from fossil fuels, whether one considers alternative energy conversion strategies through photoelectrochemical (PEC) production of chemical fuels or fuel cells run with sustainable hydrogen, or energy storage strategies, such as in batteries and supercapacitors. This dissertation builds on recent advances in nanomaterials design, synthesis, and characterization to develop novel electrodes that can electrochemically convert and store energy.

Chapter 2 of this dissertation focuses on refining the properties of TiO2-based PEC water-splitting photoanodes used for the direct electrochemical conversion of solar energy into hydrogen fuel. The approach utilized atomic layer deposition (ALD); a growth process uniquely suited for the conformal and uniform deposition of thin films with angstrom-level thickness precision. ALD’s thickness control enabled a better understanding of how the effects of nitrogen doping via NH3 annealing treatments, used to reduce TiO2’s bandgap, can have a strong dependence on TiO2’s thickness and crystalline quality. In addition, it was found that some of the negative effects on the PEC performance typically associated with N-doped TiO2 could be mitigated if the NH3-annealing was directly preceded by an air-annealing step, especially for ultrathin (i.e., < 10 nm) TiO2 films. ALD was also used to conformally coat an ultraporous conductive fluorine-doped tin oxide nanoparticle (nanoFTO) scaffold with an ultrathin layer of TiO2. The integration of these ultrathin films and the oxide nanoparticles resulted in a heteronanostructure design with excellent PEC water oxidation photocurrents (0.7 mA/cm2 at 0 V vs. Ag/AgCl) and charge transfer efficiency.

In Chapter 3, two innovative nanoarchitectures were engineered in order to enhance the pseudocapacitive energy storage of next generation supercapacitor electrodes. The morphology and quantity of MnO2 electrodeposits was controlled by adjusting the density of graphene foliates on a novel graphenated carbon nanotube (g-CNT) scaffold. This control enabled the nanocomposite supercapacitor electrode to reach a capacitance of 640 F/g, under MnO2 specific mass loading conditions (2.3 mg/cm2) that are higher than previously reported. In the second engineered nanoarchitecture, the electrochemical energy storage properties of a transparent electrode based on a network of solution-processed Cu/Ni cores/shell nanowires (NWs) were activated by electrochemically converting the Ni metal shell into Ni(OH)2. Furthermore, an adjustment of the molar percentage of Ni plated onto the Cu NWs was found to result in a tradeoff between capacitance, transmittance, and stability of the resulting nickel hydroxide-based electrode. The nominal area capacitance and power performance results obtained for this Cu/Ni(OH)2 transparent electrode demonstrates that it has significant potential as a hybrid supercapacitor electrode for integration into cutting edge flexible and transparent electronic devices.

Temperature measurement of cold atoms using transient absorption of a resonant probe through an optical nanofibre

Optical nanofibres are ultrathin optical fibres with a waist diameter typically less than the wavelength of light being guided through them. Cold atoms can couple to the evanescent field of the nanofibre-guided modes and such systems are emerging as promising technologies for the development of atom-photon hybrid quantum devices. Atoms within the evanescent field region of an optical nanofibre can be probed by sending near or on-resonant light through the fibre; however, the probe light can detrimentally affect the properties of the atoms. In this paper, we report on the modification of the local temperature of laser-cooled 87Rb atoms in a magneto-optical trap centred around an optical nanofibre when near-resonant probe light propagates through it. A transient absorption technique has been used to measure the temperature of the affected atoms and temperature variations from 160 μk to 850 μk, for a probe power ranging from 0 to 50 nW, have been observed. This effect could have implications in relation to using optical nanofibres for probing and manipulating cold or ultracold atoms.

Intra-pulse transition between ion acceleration mechanisms in intense laser-foil interactions

Multiple ion acceleration mechanisms can occur when an ultrathin foil is irradiated with an intense laser pulse, with the dominant mechanism changing over the course of the interaction. Measurement of the spatial-intensity distribution of the beam of energetic protons is used to investigate the transition from radiation pressure acceleration to transparency-driven processes. It is shown numerically that radiation pressure drives an increased expansion of the target ions within the spatial extent of the laser focal spot, which induces a radial deflection of relatively low energy sheath-accelerated protons to form an annular distribution. Through variation of the target foil thickness, the opening angle of the ring is shown to be correlated to the point in time transparency occurs during the interaction and is maximized when it occurs at the peak of the laser intensity profile. Corresponding experimental measurements of the ring size variation with target thickness exhibit the same trends and provide insight into the intra-pulse laser-plasma evolution.

Electrical and optical studies on carbon nanotube arrays

Single-walled carbon nanotubes (SWNTs) have been studied as a prominent class of high performance electronic materials for next generation electronics. Their geometry dependent electronic structure, ballistic transport and low power dissipation due to quasi one dimensional transport, and their capability of carrying high current densities are some of the main reasons for the optimistic expectations on SWNTs. However, device applications of individual SWNTs have been hindered by uncontrolled variations in characteristics and lack of scalable methods to integrate SWNTs into electronic devices. One relatively new direction in SWNT electronics, which avoids these issues, is using arrays of SWNTs, where the ensemble average may provide uniformity from device to device, and this new breed of electronic material can be integrated into electronic devices in a scalable fashion. This dissertation describes (1) methods for characterization of SWNT arrays, (2) how the electrical transport in these two-dimensional arrays depend on length scales and spatial anisotropy, (3) the interaction of aligned SWNTs with the underlying substrate, and (4) methods for scalable integration of SWNT arrays into electronic devices. The electrical characterization of SWNT arrays have been realized by polymer electrolyte-gated SWNT thin film transistors (TFTs). Polymer electrolyte-gating addresses many technical difficulties inherent to electrical characterization by gating through oxide-dielectrics. Having shown polymer electrolyte-gating can be successfully applied on SWNT arrays, we have studied the length scaling dependence of electrical transport in SWNT arrays. Ultrathin films formed by sub-monolayer surface coverage of SWNT arrays are very interesting systems in terms of the physics of two-dimensional electronic transport. We have observed that they behave qualitatively different than the classical conducting films, which obey the Ohm’s law. The resistance of an ultrathin film of SWNT arrays is indeed non-linear with the length of the film, across which the transport occurs. More interestingly, a transition between conducting and insulating states is observed at a critical surface coverage, which is called percolation limit. The surface coverage of conducting SWNTs can be manipulated by turning on and off the semiconductors in the SWNT array, leading to the operation principle of SWNT TFTs. The percolation limit depends also on the length and the spatial orientation of SWNTs. We have also observed that the percolation limit increases abruptly for aligned arrays of SWNTs, which are grown on single crystal quartz substrates. In this dissertation, we also compare our experimental results with a two-dimensional stick network model, which gives a good qualitative picture of the electrical transport in SWNT arrays in terms of surface coverage, length scaling, and spatial orientation, and briefly discuss the validity of this model. However, the electronic properties of SWNT arrays are not only determined by geometrical arguments. The contact resistances at the nanotube-nanotube and nanotube-electrode (bulk metal) interfaces, and interactions with the local chemical groups and the underlying substrates are among other issues related to the electronic transport in SWNT arrays. Different aspects of these factors have been studied in detail by many groups. In fact, I have also included a brief discussion about electron injection onto semiconducting SWNTs by polymer dopants. On the other hand, we have compared the substrate-SWNT interactions for isotropic (in two dimensions) arrays of SWNTs grown on Si/SiO2 substrates and horizontally (on substrate) aligned arrays of SWNTs grown on single crystal quartz substrates. The anisotropic interactions associated with the quartz lattice between quartz and SWNTs that allow near perfect horizontal alignment on substrate along a particular crystallographic direction is examined by Raman spectroscopy, and shown to lead to uniaxial compressive strain in as-grown SWNTs on single crystal quartz. This is the first experimental demonstration of the hard-to-achieve uniaxial compression of SWNTs. Temperature dependence of Raman G-band spectra along the length of individual nanotubes reveals that the compressive strain is non-uniform and can be larger than 1% locally at room temperature. Effects of device fabrication steps on the non-uniform strain are also examined and implications on electrical performance are discussed. Based on our findings, there are discussions about device performances and designs included in this dissertation. The channel length dependences of device mobilities and on/off ratios are included for SWNT TFTs. Time response of polymer-electrolyte gated SWNT TFTs has been measured to be ~300 Hz, and a proof-of-concept logic inverter has been fabricated by using polymer electrolyte gated SWNT TFTs for macroelectronic applications. Finally, I dedicated a chapter on scalable device designs based on aligned arrays of SWNTs, including a design for SWNT memory devices.

MOLECULAR MASS MANIPULATION ENABLED BY GRAPHENE BASED NANOSTRUCTURES

The surge of interest in graphene, as epitomized by the Nobel Prize in Physics in 2010, is attributed to its extraordinary properties. Graphene is ultrathin, mechanically tough, and has amendable surface chemistry. These features make graphene and graphene based nanostructure an ideal candidate for the use of molecular mass manipulation. The controllable and programmable molecular mass manipulation is crucial in enabling future graphene based applications, however is challenging to achieve. This dissertation studies several aspects in molecular mass manipulation including mass transportation, patterning and storage. For molecular mass transportation, two methods based on carbon nanoscroll are demonstrated to be effective. They are torsional buckling instability assisted transportation and surface energy induced radial shrinkage. To achieve a more controllable transportation, a fundamental law of direction transport of molecular mass by straining basal graphene is studied. For molecular mass patterning, we reveal a barrier effect of line defects in graphene, which can enable molecular confining and patterning in a domain of desirable geometry. Such a strategy makes controllable patterning feasible for various types of molecules. For molecular mass storage, we propose a novel partially hydrogenated bilayer graphene structure which has large capacity for mass uptake. Also the mass release can be achieved by simply stretching the structure. Therefore the mass uptake and release is reversible. This kind of structure is crucial in enabling hydrogen fuel based technology. Lastly, spontaneous nanofluidic channel formation enabled by patterned hydrogenation is studied. This novel strategy enables programmable channel formation with pre-defined complex geometry.

MANIPULATION OF IONS, ELECTRONS, AND PHOTONS IN 2D MATERIALS BY ION INTERCALATION

2D materials have attracted tremendous attention due to their unique physical and chemical properties since the discovery of graphene. Despite these intrinsic properties, various modification methods have been applied to 2D materials that yield even more exciting results. Among all modification methods, the intercalation of 2D materials provides the highest possible doping and/or phase change to the pristine 2D materials. This doping effect highly modifies 2D materials, with extraordinary electrical transport as well as optical, thermal, magnetic, and catalytic properties, which are advantageous for optoelectronics, superconductors, thermoelectronics, catalysis and energy storage applications. To study the property changes of 2D materials, we designed and built a planar nanobattery that allows electrochemical ion intercalation in 2D materials. More importantly, this planar nanobattery enables characterization of electrical, optical and structural properties of 2D materials in situ and real time upon ion intercalation. With this device, we successfully intercalated Li-ions into few layer graphene (FLG) and ultrathin graphite, heavily dopes the graphene to 0.6 x 10^15 /cm2, which simultaneously increased its conductivity and transmittance in the visible range. The intercalated LiC6 single crystallite achieved extraordinary optoelectronic properties, in which an eight-layered Li intercalated FLG achieved transmittance of 91.7% (at 550 nm) and sheet resistance of 3 ohm/sq. We extend the research to obtain scalable, printable graphene based transparent conductors with ion intercalation. Surfactant free, printed reduced graphene oxide transparent conductor thin film with Na-ion intercalation is obtained with transmittance of 79% and sheet resistance of 300 ohm/sq (at 550 nm). The figure of merit is calculated as the best pure rGO based transparent conductors. We further improved the tunability of the reduced graphene oxide film by using two layers of CNT films to sandwich it. The tunable range of rGO film is demonstrated from 0.9 um to 10 um in wavelength. Other ions such as K-ion is also studied of its intercalation chemistry and optical properties in graphitic materials. We also used the in situ characterization tools to understand the fundamental properties and improve the performance of battery electrode materials. We investigated the Na-ion interaction with rGO by in situ Transmission electron microscopy (TEM). For the first time, we observed reversible Na metal cluster (with diameter larger than 10 nm) deposition on rGO surface, which we evidenced with atom-resolved HRTEM image of Na metal and electron diffraction pattern. This discovery leads to a porous reduced graphene oxide sodium ion battery anode with record high reversible specific capacity around 450 mAh/g at 25mA/g, a high rate performance of 200 mAh/g at 250 mA/g, and stable cycling performance up to 750 cycles. In addition, direct observation of irreversible formation of Na2O on rGO unveils the origin of commonly observed low 1st Columbic Efficiency of rGO containing electrodes. Another example for in situ characterization for battery electrode is using the planar nanobattery for 2D MoS2 crystallite. Planar nanobattery allows the intrinsic electrical conductivity measurement with single crystalline 2D battery electrode upon ion intercalation and deintercalation process, which is lacking in conventional battery characterization techniques. We discovered that with a “rapid-charging” process at the first cycle, the lithiated MoS2 undergoes a drastic resistance decrease, which in a regular lithiation process, the resistance always increases after lithiation at its final stage. This discovery leads to a 2- fold increase in specific capacity with with rapid first lithiated MoS2 composite electrode material, compare with the regular first lithiated MoS2 composite electrode material, at current density of 250 mA/g.