WO2011072213A2 - Production de graphène et de catalyseurs nanoparticulaires supportés sur le graphène à l'aide d'un rayonnement laser - Google Patents

Production de graphène et de catalyseurs nanoparticulaires supportés sur le graphène à l'aide d'un rayonnement laser Download PDF

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WO2011072213A2
WO2011072213A2 PCT/US2010/059870 US2010059870W WO2011072213A2 WO 2011072213 A2 WO2011072213 A2 WO 2011072213A2 US 2010059870 W US2010059870 W US 2010059870W WO 2011072213 A2 WO2011072213 A2 WO 2011072213A2
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graphene
nanocomposite
metal
water
semiconductor
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PCT/US2010/059870
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English (en)
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WO2011072213A3 (fr
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M. Samy El-Shall
Victor Abdelsayed
Saud I. Al-Resayes
Zeid Abdullah M. Alothman
Sherif Moussa
Mona B. Mohamed
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Virginia Commonwealth University
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Priority to US13/514,671 priority Critical patent/US9768355B2/en
Publication of WO2011072213A2 publication Critical patent/WO2011072213A2/fr
Publication of WO2011072213A3 publication Critical patent/WO2011072213A3/fr

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Definitions

  • the invention generally relates to methods and apparatuses to produce graphene and nanoparticle catalysts supported on graphene without the use of reducing agents.
  • the invention provides methods and apparatuses which use ultraviolet (UV), visible (VIS) and/or infrared (IR) light to reduce (deoxygenate) graphite oxide (GO) to graphene, or to reduce a mixture of GO plus one or more metals ions to produce nanoparticle catalysts supported on graphene.
  • the invention further provides methods and systems to generate and utilize heat that is produced by irradiating GO, graphene and their metal and semiconductor nanocomposites with UV, VIS, and/or IR radiation, e.g. using sunlight, lasers, etc.
  • An embodiment of the invention provides methods of making graphene sheets and metallic catalysts supported on graphene sheets by exposing graphite oxide (GO) or GO plus one or more metal ions to UV, VIS, and/or IR radiation.
  • the methods of the invention do not require the use of other reducing agents to covert GO to graphene and thus contamination of the graphene by such agents and the generation of noxious by-products is eliminated.
  • the technology provided herein is thus "green technology” i.e. the technology is environmentally friendly.
  • exposing GO, graphene, and metal and semiconductor nanocomposites of GO and graphene to UV, VIS, and/or IR radiant energy results in the highly efficient production of heat (photothermal energy conversion), and methods and apparatuses for the production of heat in this manner are provided.
  • the materials used to generate heat in this manner can be regenerated and reused.
  • the GO provided in the providing step is in solution, and the solution may be an aqueous solution. Li other embodiments, the solution comprises one or more organic solvents.
  • the GO provided in the providing step is solid graphite oxide.
  • the method is carried out in the absence of chemical reducing agents.
  • the GO provided in the providing step is mixed with at least one metal or metal alloy and the exposing step produces metal or metal alloy nanoparticles supported on the graphene.
  • At least one of said at least one metals may be selected from the group consisting of Au, Ag, Pd. Co, Pd, Co, Au, Ag, Cu, Pt, Ni, Fe, Mn, Cr, V, Ti, Sc, Ce, Pr, Nd, Sm t Gd, Horn Er, Yb, Al, Ga, Sn, Pb, In, Mg, Ca, Sr, Na, K, Rb, and Cs.
  • the GO provided in the providing step is mixed with at least one semiconductor material, and the exposing step produces semiconductor nanoparticles supported on the graphene.
  • the at least one semiconductor material may be selected from the group consisting of silicon, titanium oxide and zinc oxide.
  • the providing step provides GO that is exfoliated.
  • the invention also provides a method of producing heat via photothermal energy conversion.
  • the method comprises the step of exposing at least one photothermally active material to a source of one or more of ultraviolet (UV), visible (VIS), or infrared (IR) radiant energy, wherein the photothermally active material is selected from the group consisting of: graphite oxide (GO), partially reduced GO, graphene, a metal nanocomposite of GO, a metal nanocomposite of partially reduced GO, a metal nanocomposite of graphene, a semiconductor nanocomposite of GO, a semiconductor nanocomposite of partially reduced GO, and a semiconductor nanocomposite of graphene.
  • the at least one photothermally active material is dispersed in a liquid medium.
  • the source of one or more of ultraviolet (UV), visible (VIS), or infrared (IR) light energy is sunlight; in other embodiments, the source of one or more of ultraviolet (UV), visible (VIS), or infrared (IR) light energy is a laser.
  • the invention also provides an apparatus for producing heat via photothermal energy conversion.
  • the apparatus comprises: 1) a container for containing at least one
  • the container permitting exposure of the at least one photothermally active material to a source of one or more of ultraviolet (UV), visible (VIS), or infrared (IR) light energy
  • the photothermally active material being selected from the group consisting of: graphite oxide (GO), partially reduced GO, graphene, a metal nanocomposite of GO, a metal nanocomposite of partially reduced GO, a metal nanocomposite of graphene, a semiconductor nanocomposite of GO, a semiconductor nanocomposite of partially reduced GO, and a semicomductor nanocomposite of graphene); 2) a container for containing a heatable medium; and 3) one or more conduits for transporting heated medium to location where heat is to be released from said heated medium.
  • the heatable medium is water.
  • the container for containing at least one photothermally active material and the container for containing a heatable medium are the same container.
  • the invention also provides an apparatus for desalinating sea water.
  • the apparatus comprises 1 ⁇ a container for containing at least one photothermally active material, the container permitting exposure of the at least one photothermally active material to a source of one or more of ultraviolet (UV), visible (VIS), or infrared (IR) light energy, and the photothermally active material being selected from the group consisting of: graphite oxide (GO), partially reduced GO, graphene, a metal nanocomposite of GO, a metal
  • nanocomposite of partially reduced GO a metal nanocomposite of graphene, a
  • the container for containing at least one photothermally active material and the container for containing sea water are the same container.
  • the invention also provides a method for destroying unwanted cells or tissue in a subject in need thereof, comprising the steps of 1) placing at least one photothermally active material at or near said unwanted cells or tissue; and 2) exposing the at least one photothermally active material to a source of one or more of ultraviolet (UV), visible (VIS), or infrared (IR) radiant energy, the photothermally active material being selected from the group consisting of: graphite oxide (GO), partially reduced GO, graphene, a metal nanocomposite of GO, a metal nanocomposite of partially reduced GO, a metal nanocomposite of graphene, a semiconductor nanocomposite of GO, a semiconductor nanocomposite of partially reduced GO, and a semicomductor nanocomposite of graphene; Heat produced in the exposing step destroys said unwanted cells or tissue in said subject.
  • the unwanted cells or tissue are hyperproliferating cells or tissue.
  • the invention also provides a photovoltaic cell, comprising a transparent conducting layer, a photoabs orbing layer comprising at least one semiconductor nanocomposite of graphene; and a back electrode.
  • the transparent conducting layer comprises a graphene monolayer on a glass or polymer substrate; and in another embodiment, the back electrode comprises graphene.
  • the graphene is made by the methods of the invention.
  • the invention provides a light-emitting-diode (LED), comprising a substrate, and a semiconductor nanocomposite of graphene associated with the substrate.
  • the semiconductor nanocomposite of graphene is doped with impurities to create a p-n junction on the substrate.
  • the graphene is made by the methods of the invention,
  • FIG. 1A-C A, X-ray diffraction (XRD) of GO as a function of the 532 nm laser irradiation time (5W, 30 Hz) at 0, 5, and 10 min irradiation times; B, XRD of GO, LCG after laser irradiation at 532 and 355 nm; C, XRD of GO following the 1064 nra laser irradiation for 1 and 2 min using 100 mJ/pulse, 30 Hz.
  • XRD X-ray diffraction
  • a and B UV-vis (ultraviolet- visible) spectra of GO and LCG dispersed in ethanoi;
  • B UV-vis spectra showing the change of GO solution in water as a function of laser irradiation time (532 nm, 5 W, 30 Hz).
  • FIG. 3A-D A, Fourier transform-Infrared (FT-IR) spectra of graphite oxide (GO) and laser converted graphene (LCG); B, XPS CI s spectra of GO and LCG; C, Raman spectra of GO and graphene formed after laser irradiation of GO.
  • FT-IR Fourier transform-Infrared
  • FIG. A and B Temperature changes during laser irradiation of graphite oxide solutions with the fundamental (1064 nm), 2 nd harmonic (532 nm), and 3rd harmonic (355 nm) of the neodyniium-doped yttrium aluminium garnet (Nd/YAG) laser (5W, 30 Hz).
  • the * denotes bleaching the solution after 6 min with the 355 nm irradiation (5W, 30 Hz).
  • Dotted curves show the temperature changes of irradiating the same volume of pure water with the corresponding laser frequency (5W, 30 Hz);
  • B Temperature changes during laser irradiation of graphite oxide solutions with the 2nd harmonic of the Nd YAG laser (532 nm, 5W, 30 Hz) after repeated irradiation cycles.
  • the dashed curve shows the temperature change of irradiating the same volume of pure water with the 532 nm (5W, 30 Hz).
  • the results of cycles 2-7 were largely superimposable after about 4 minutes of radiation and are shown as one line.
  • Figure 5 XRD spectra of graphene oxide (GO) and laser-converted graphene (LCG) prepared by 532 nm laser irradiation (4W, 30 Hz) of GO for 10 minutes in different solvents as indicated.
  • FIG. 6A and B Absorption spectra of 25 ⁇ , HAuC + GO in 50% ethanol -water, 2% PEG-water and pure water recorded after two minutes laser irradiation (532 nm, 4 W, 30 Hz). Dotted lines represent data of bank solutions containing the same amount of HAuCU but no GO under identical laser irradiation conditions.
  • B Absorption spectra of the same solutions in (a) irradiated with lower laser power (532 nm, 1 W, 30 Hz) showing no formation of gold nanoparticles in the pure water solution (black).
  • FIG. 7A-D A, XRD data of GO before and after the 532 nm laser irradiation (4 W, 30 Hz) for 10 minutes in different solvents as indicated.
  • B XRD data of Au nanoparticles incorporated within partially reduced GO.
  • C XRD data obtained after the 532 nm laser irradiation (4 W, 30 Hz) of GO in water containing different amounts of HAuCU as indicated.
  • D Absorption spectra of GO solutions in water containing different amounts of HAuCU as indicated after the 532 nm laser irradiation.
  • FIG. 8A and B A, XPS (CI S) spectra of GO and partially reduced GO containing Au nanoparticles prepared after 10 minutes laser irradiation (532 nm, 4 W, 30 Hz) of HAuCU - GO solutions in different solvents as indicated.
  • B XPS (Au 4f) spectra of Au nanoparticles incorporated in partially reduced GO prepared in different solvents as indicated.
  • FIG. 9A-C A, Absorption spectra of AgN03 - GO solutions in 50% ethanol-water, 2% PEG-water and pure water recorded after five minutes laser irradiation (532 nm, 4 W, 30 Hz). Dotted lines represent data of bank solutions containing the same amount of AgNOi but no GO after 10 minutes laser irradiation (532 nm, 4 W, 30 Hz).
  • B XRD data of GO before and after the 532 nm laser irradiation (4 W, 30 Hz) for five minutes in different solvents as indicated.
  • Figure 1 1A and B.
  • A Repeated laser irradiation (532 nm, 30 Hz, 2 W average power) cycles of 3 niL HAuC + GO aqueous solution containing 10 HAuCL; and 0.6 mg GO.
  • B Absorption spectra of the HAuCU + GO solution recorded after different irradiation cycles using the 532 nm laser irradiation with an average laser power of 2 W.
  • FIG. 13A-C A, XRD of Pd nanoparticles supported on graphene; B, UV-0V Is of Ag nanoparticles supported on graphene; c, XRD of Au nanoparticles supported on graphene.
  • Pd, Ag and Au nanoparticles supported on graphene were prepared by the 532nm laser irradiation in solution.
  • FIG 16A and B A, Temperature changes during laser irradiation (532 nm, 4 and 5 W, 30 Hz) of graphite oxide (GO) solutions (3 ml solution, 2mg GO/10 ml H 2 0) containing 1 mg Si nanoparticles; B, Temperature changes during laser irradiation (532 nm, 5 W, 30 Hz) of graphite oxide (GO) solutions (3 ml solution, 2mg GO/10 ml 3 ⁇ 40) containing 1 mg Si nanoparticles.
  • GO graphite oxide
  • FIG 17A-C Laser synthesis of bimetallic PdCo nanoparticles supported on graphene.
  • A XRD data of reduced grahene oxide film containing PdCo nanoparticles showing the absence of the graphene oxide diffraction peak ;
  • B XRD data of reduced grahene oxide film containing PdCo nanoparticles showing the diffraction peak due to PdCo bimetallic nanoparticles;
  • C TEM of bimetallic PdCo nanoparticles supported on graphene. bimetallic PdCo nanoparticles supported on graphene.
  • Figure 18A and B EDS and TEM of laser synthesis of bimetallic PdCo nanoparticles supported on graphene.
  • A Atomic percent composition of the PdCo bimetallic nanoparticles supported on graphene showing a composition of 70 % (at) Pd and 30% (at) Co.
  • B Atomic percent composition of the PdCo bimetallic nanoparticles supported on graphene showing a composition of 90 % (at) Pd and 10% (at) Co.
  • FIG. 20 Fabrication of photovoltaic (PV) and optionally light-emitting diode (LED) devices using dual purpose graphene substrates.
  • PV photovoltaic
  • LED light-emitting diode
  • FIG. 21 Schematic of a simple solar still.
  • FIG. 22 Schematic depiction of apparatus and system for production of heat by the methods of the invention.
  • FIG. 23 Schematic depiction of apparatus and system for generation of electricity by the methods of the invention.
  • Figure 24 Figure 23. Schematic depiction of apparatus and system for desalination by the methods of the invention.
  • FIG. 25 Schematic depiction of light-emitting-diode (LED) of the invention.
  • the invention provides advances in 1) the manufacture of graphene (using either GO in solution or solid GO); 2) the manufacture of metal catalysts supported on graphene; and 3) the generation of heat using reusable GO, graphene and metal or semiconductor nanocomposites thereof.
  • UV light we mean electromagnetic radiation with wavelength in the range of from about 10 to 400nm.
  • visible (VIS) light we mean electromagnetic radiation in the range of from about 390 nm to 750 nm.
  • ultraviolet light we mean electromagnetic radiation in the range of from about 0.7 to about 300 micrometers ( ⁇ ).
  • light energy or as “UV-VIS-IR energy” or “UV-VIS-IR light”
  • UV-VIS-IR light we mean electromagnetic radiation with wavelength in the range of from about 10 to 400nm.
  • UV-VIS-IR energy ultraviolet-VIS-IR energy
  • graphene we mean sp 2 -bonded carbon atoms that are densely packed in a one- atom-thick planar sheet.
  • Graphene atoms form a honeycomb or “chicken-wire” atomic scale crystal lattice made of carbon atoms and their bonds.
  • the crystalline or “flake” form of graphite consists of many graphene sheets stacked together.
  • Graphite oxide (formerly called graphitic oxide or graphitic acid) as used herein, refers to a compound of carbon, oxygen, and hydrogen in variable ratios, obtained by treating graphite with strong oxidizers.
  • the maximally oxidized bulk product is a yellow solid with C:0 ratio between 2.1 and 2.9, that retains the layer structure of graphite but with a much larger and irregular spacing.
  • the structure and properties of graphite oxide are variable and depend on the particular synthesis method and degree of oxidation. It typically preserves the layer structure of the parent graphite, but the layers are buckled and the interlayer spacing is about two times larger ( ⁇ 7 A) than that of graphite. Strictly speaking "oxide" is an incorrect but historically established name.
  • exfoliated graphite oxide we mean GO in which the layers have been separated.
  • graphene is produced by irradiating, with "light” or “radiant” energy, GO in suspension or dispersed in a liquid medium without the use of any chemical reducing agent. Irradiation is carried out in a manner that results in reduction and hence deoxygenation of the GO, and the production of the characteristic sp 2 -bonded carbon atoms densely packed in a one-atom-thick planar sheet.
  • Liquid media that can be used to disperse GO in a manner suitable for irradiation include but are not limited to: aqueous-based media such as water; aqueous solutions of water and alcohols such as ethanol (e.g. from about 10 to about 90 % ETOH, or from about 20 to about 80%, or from about 30 to about 70%, or from about 40 to about 60%, and usually about 50% ETOH); solutions of polyethylene glycol (PEG) in water (e.g. from about 1% to about 10%, e.g. about 1 , 2, 3, 4, 5, 6, 7, 8, 9 or 10% PEG in water); other alcohols such as methanol, isopropanol, etc., or other polar liquids such as acetonitrile,
  • PEG polyethylene glycol
  • the concentration of GO in the medium that is irradiated is generally in the range of from about 0.1 mg/mL (or even less) to about 10 mg/mL(or greater), and is usually in the range of from about 1 mg/mL to about 5 mg/mL.
  • Types of light energy that may be used in the production of graphene from GO include but are not limited to various sources of UV, VIS and/or IR radiation such as lasers, radiation from tungsten-halogen lamps, sunlight, mercury lamps, hydrogen lamps, etc. Any source that provides a suitable wavelength of light may be used in the practice of the invention
  • the wavelength that is used is generally in the range of from about 100 to about 800 nm, or from about 300 to about 1 lOOnm, and may be, for example, about 193 nm, or about 266 nm, or about 248 nm, or about 308 nm, or about 355 nm, or about 532 nm, or about 980 nm, or about 1064 nm.
  • the power of the laser radiation is generally in the range of from about IWatt (W) to about 10W, and is generally in the range of from about 2W to about 9W, or even in the range of from about 3W to about 8W, i.e.
  • the frequency i.e. number of cycles per second, "hertz” or "Hz"
  • the frequency is generally in the range of from about 10 to about 50 Hz, or from about 20 to about 40 Hz, and may be about 30Hz.
  • a YAG laser is employed at 355 nm, 5W and 30 Hz.
  • the power employed is generally in the range of from about 100 to 1000W, and may be from about 200 to about 900W, or from about 300 to about 800W, or from about 400 to about 700W, or from about 500 to about 600W, with a power of about 500W being frequently used.
  • the length of exposure of GO to the light energy will vary depending on the type and strength of radiation that is used, the concentration of GO in the suspension, and the solution volume. Generally, these variables are adjusted so that the time of radiation is in the range of from about 1 to about 10 minutes, i.e. about 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 minutes. Further, several cycles of irradiation may be used, e.g. from about 1 to about 10 or more cycles (i.e. about 1 , 2, 3, 4, 5, 6, 7, 8, 9, or 10 cycles) with each cycle including an exposure of the GO to the source of radiation of at least about one minute or more, as described above.
  • the GO Prior to exposing the GO to light energy, the GO may be exfoliated in order to separate the layers. This is generally accomplished by dispersing GO in water using ultrasonic or stirring until a clear well-dispersed solution is obtained with a golden yellow color.
  • the starting temperature at which the conversion of GO to graphene is carried out is generally ambient (i.e. room) temperature, i.e. about 20 to 25°C (68 to 77°F), although this need not always be the case. In some embodiments, the temperature may be higher (e.g. up to about 37°C) or lower (e.g. as low as about 1-2°C) while still successfully producing graphene. It is also possible to start with frozen GO solution (below 0 °C, e.g. -50°C or - 10°C, etc.) and convert the frozen solution to liquid by the photothermal effect of GO. Those of skill in the art will recognize that an increase in starting temperature may accelerate the reaction whereas a decrease in initial temperature may slow the reaction rate, either of which may be desirable for particular applications.
  • irradiation is carried out in a manner that results in the complete conversion of GO to graphene. However, this is not always the case.
  • one or more of the amount, duration, intensity and wavelength(s) of irradiation is adjusted or tuned so as to cause only partial deoxygenation of the GO, but not complete conversion to graphene.
  • the result may be the partial deoxygenation of the GO, or the substantially complete dexoygenation of GO, producing graphene.
  • the deoxygenation of GO to graphene need not be an "all or nothing" event.
  • substantially complete usually at least about 75%, 80%, 85%, 90%, 95%, 99%, or even up to about 100% of the GO is converted to graphene.
  • the graphene is produced using lasers, and what is produced is thus termed “laser converted graphene” or “LCG”.
  • laser converted graphene or “LCG”.
  • individual (single) LCG sheets are produced by laser reduction of exfoliated GO in water, and the reaction is carried out under ambient conditions (e.g. at room temperature, which is about 20-25°C).
  • the progress of the reaction may be monitored by any suitable method, examples of which include but are not limited to UV-VIS spectral data, FTIR, Raman spectroscopy, etc.
  • the source of radiation is withdrawn or removed and the graphene sheets are removed from the reaction mixture.
  • the solution may be centrifuged and the graphene separated after centrifuging, or the solution may be filtered to separate the graphene sheets, etc.
  • the graphene may be rinsed (e.g. with water or another solvent, e.g. an alcohol), dried and stored for further use. Using solid GO
  • the GO that is utilized to produce graphene is solid GO.
  • metal powder or nanoparticles are mixed with GO to form a mixture that is, e.g. pressed into a pellet (cake, block, layer, sheet, etc.) using high pressure.
  • the mixed pellet is then used for the laser desorption process as described above, and metal-graphene nanocomposites are formed.
  • GO solid target is converted into graphene by the Laser Vaporization Controlled Condensation (LVCC) method as described in US patents 5, 580,655; 5,695,617; 6,136,156, 6,368,406 and 7,413,725, the complete contents of which are incorporated herein by reference.
  • LVCC Laser Vaporization Controlled Condensation
  • the graphene sheets produced by both the "in solution” and “solid GO” methods may be used in any of a variety of applications and as components of a variety of apparatuses, e.g. they may be used in nanoelectronics, supercapacitors, batteries, photovoltaics, LEDs, and related devices.
  • the properties of graphene such as the high thermal, chemical, and mechanical stability as well as a high surface area, also represent desirable characteristics for its use as a 2-dimensional catalyst support for metallic and bimetallic nanoparticles.
  • the invention also provides methods for producing graphene sheets which support one or more metal atoms, e.g. for use in catalyzing a variety of chemical reactions and transformation, particularly at high temperature.
  • the main advantage of using the photochemical and photothermal reduction methods described herein to prepare metal nanoparticles supported on graphene is to avoid the use of toxic chemical reducing agents and thus provide a green approach for the synthesis and processing of metal-graphene nanocomposites.
  • the absence of traces of reducing or capping agents from the surface of the supported nanocatalysts is advantageous.
  • the present methods provide better control of the reduction processes without the need of high temperatures, and the possibility of the facile simultaneous reduction of two or more different metal ions on the graphene surface which could produce graphene nanocomposites with desirable catalytic, magnetic and optical properties.
  • metal-graphene nanocomposites may be carried out using either GO dispersed in a liquid medium or solid GO. Generally, the overall procedure is the same as that which is described above for the production of graphene. However, in this embodiment, what is irradiated is a mixture of GO plus at least one metal of interest.
  • soluble metal salts are used.
  • metal powder or nanoparticles are mixed with GO to form a mixture that is, e.g. pressed into a pellet using high pressure pellet production.
  • the mixed pellet is then used for the laser desorption process as described above for the LVCC method.
  • metal ions upon exposure to light energy as described herein, simultaneous reduction of the GO and metal ions takes place and metal-graphene nanocomposites are formed.
  • metals examples include but are not limited to Pd, Co, Au, Ag, Cu, Pt, Ni, Fe, Mn, Cr, V, Ti, Sc, etc and rare earth metals such as Ce, Pr, Nd, Sm, Gd, Horn Er, Yb, etc., and other metals such as Al, Ga, Sn, Pb, In, Mg, Ca, Sr, Na, , Rb, Cs, etc.
  • semiconductors can be used such as Si, Ge, CdSe, CdS, CdTe, ZnO, ZnS, ZnSe, etc.
  • the metals are provided as salts, i.e.
  • the resulting catalyst is bi-metallic (or tri- metallic, etc., depending on how many metals are present).
  • metals include but are not limited to: Pd plus Co; Au plus Ag, Pd plus Pt, Cu plus Pd, Pt plus Fe, etc.
  • the metals in the mixture that is irradiated are generally in the form of e.g. metal salts, and the concentration of the metal ions is generally in the range of from about 1 % to about 20-30 %, depending on, for example, the desired density of metal on the graphene sheet that is formed.
  • Metal catalysts supported on graphene sheets made according to the methods described herein may be used for any of a variety of purposes, including but not limited to catalysis, e.g. for use in Fischer-Tropsch Synthesis, hydrogen production reactions, CO oxidation, etc., as well as for sensors, hydrogen storage, energy conversion, and for other applications.
  • catalysis e.g. for use in Fischer-Tropsch Synthesis, hydrogen production reactions, CO oxidation, etc.
  • sensors e.g. for sensors, hydrogen storage, energy conversion, and for other applications.
  • semiconductor materials mixed with and irradiated with the GO and graphene sheets with associated semiconductor particles are formed.
  • examples of such substances include but are not limited to silicon, titanium and zinc oxides, CdSe, ZnS, CdS, etc.
  • the conditions for carrying out such reactions are generally the same as those for the simultaneous reduction of GO and metal ions as described above.
  • Si silicon
  • the concentration of Si in the mixture that is irradiated is generally from about 1% to about 20%, and the Si is generally in the form of Silicon powder or Si nanoparticles. Similar concentrations are used for the other semiconductor materials. Further, in some embodiment, silicon, titanium and zinc oxides, CdSe, ZnS, CdS, etc.
  • the conditions for carrying out such reactions are generally the same as those for the simultaneous reduction of GO and metal ions as described above.
  • the concentration of Si in the mixture that is irradiated is generally from about 1% to about 20%, and the Si is generally in the form of Silicon powder or Si nanoparticles. Similar
  • semiconductor materials may be reduced together with GO and one or more metals of interest as described above.
  • the invention provides a method for the very high efficiency conversion of visible, infrared and ultraviolet radiation into thermal energy, i.e. heat.
  • graphite oxide and graphene as well as their metal and semiconductor nanocomposites are exposed to light energy, and, as a result, heat is produced via a photothermal coupling reaction.
  • the invention provides methods and apparatuses for generating heat by this method.
  • the materials that are used in this embodiment of the invention include but are not limited to GO, graphene, and metal and semiconductor nanocomposites of GO and graphene.
  • Exemplary metal and semiconductor nanocomposites of GO and graphene include but are not limited to those formed with gold, silver, palladium, copper, platinum, silicon, titanium dioxide, zinc oxide, etc. These materials may be referred to herein as "GO, graphene and nanocomposites thereof or as "photothermal ly active materials", etc.
  • This embodiment of the invention has applications in a wide variety of scenarios, including but not limited to phototherapy in the medical field, for the production of heat in general, e.g. for domestic purposes, and for desalination of water. Each of these exemplary uses is discussed below.
  • the method involves: 1 ) identification of a patient or subject in need of phototherapy (e.g. a subject with unwanted cells or tissues such as hyperproliferating cells of tissues (e.g. cancerous tumors, etc.); 2) identification of one or more locations within or on the body of the patient where the application of heat would be beneficial (e.g. in the environs of a tumor); 3) placement of GO, graphene and/or one or more nanocomposites thereof at the identified location(s) where it is desired to produce heat (e.g.
  • irradiation of the GO, graphene and/or one or more nanocomposites with a suitable wavelength of electromagnetic radiation causes the generation of intense heat at the targeted area, and the targeted, unwanted cells or tissues at or in the vicinity of the targeted area are harmed or destroyed (killed).
  • irradiation is carried out only once whereas in other embodiments, irradiation is carried out repeatedly at spaced-apart intervals, i.e. the targeted area is subjected to repeated cycles of radiation.
  • the amount of GO, graphene and/or one or more nanocomposites at the irradiated (targeted) site(s) may be varied or adjusted so as to influence the amount of heat that is generated, thus lending a high level of flexibility to the method.
  • the amount of heat that is generated at any given time or site can be modulated in a flexible manner, e.g. increased or reduced, as required or desired, by varying one or both of 1) the amount of GO, graphene and/or one or more nanocomposites at the irradiated site; and 2) the frequency, duration, intensity, and particular wavelengths of radiation that are used.
  • a laser is used as the radiation source.
  • a laser it is possible to narrowly focus the radiation, pinpoint the targeted area, and avoid irradiating surrounding tissue.
  • Those of skill in the art will recognize that the use of lasers for phototherapy or similar purposes in known.
  • the phototherapy can be carried out much more rapidly and efficiently, and even areas that are otherwise difficult to access may be targeted.
  • Exemplary uses for this aspect of the technology include but are not limited to applications in phototherapy (e.g. for the treatment of cancer; treatment of macular degeneration; etc.); as well as for the destruction or removal of: unwanted fatty deposits (e.g. in arteries) or fatty tissue (e.g. for cosmetic surgery); unwanted pigments, hair follicles, diseased or dead tissue, hyperproliferating cells or tissue, etc.
  • the heat generating properties of the invention are used for applications in which the heat that is generated from the reaction is captured or conserved and then used for heating on a large scale, e.g. for domestic or commercial heating.
  • one or more of the materials described herein are incorporated into an apparatus in a manner that permits or facilitates exposure of the material to a source of light energy.
  • the source of light energy is sunlight, although this is not always the case.
  • the material that is exposed to light energy is generally in the form of a suspension of the material in a medium that absorbs or captures the heat (e.g.
  • the medium is moved or circulated to an environment that is to be heated via transfer of the heat from the medium to the environment.
  • the graphene material may be in the form of a sheet which is submerged in or coated with e.g. a liquid medium.
  • the graphene materials can be used repeatedly and/or regenerated for repeated uses without degradation or loss of efficiency.
  • This embodiment of the invention may be implemented in such apparatuses as e.g. hot water or steam heating systems (e.g. boilers), and the like.
  • Figure 22 shows a schematic depiction of an exemplary embodiment of this type.
  • container 100 contains heatable medium 1 10 (e.g. water, other liquid medium, air, etc.) and photothermally active material 120 (GO, partially reduced GO, graphene and/or one or more nanocomposites thereof).
  • Incident light 130 e.g. sunlight
  • Surrounding heatable medium 1 10 is heated and transported via conduit 140 to a location where the heat is released from heated medium 160, e.g. to destination such as dwelling 150, where heated medium 160 circulates and releases heat.
  • the heat (and/or optionally light) that is produced is used directly, e.g. to heat homes or dwellings, e.g. for humans or other life forms that do not thrive in or are generally adverse to the cold.
  • dwellings may be conventional (e.g. houses, dormitories, buildings for livestock or other animals, etc.) or for heating greenhouses or orchards (e.g. to prevent the loss of crops such as citrus crops during a freeze), for desalination (discussed below), etc.
  • Heating units employing the technology of the invention may be "built-in" to a structure, or may be portable (mobile). Other less conventional applications may occur to those of skill in the art, e.g.
  • the photothermal cells or arrays may be activated by exposure to an alternative light source, e.g. laser, tungsten-halogen lamp, etc.
  • the heat that is generated as described herein may be used, e.g. to heat substances (e.g. liquids) such as water for any use (e.g. in homes, recreational facilities, business, etc.) or to create steam for heating, or for the generation of electricity (e.g. via a steam turbine connected to an electrical power generator), etc.
  • heat substances e.g. liquids
  • FIG 23 shows container 200 which contains medium 210 (e.g. water) and photothermally active material 220 (GO, partially reduced GO, graphene and/or one or more nanocomposites thereof), incident light 230 (e.g.
  • the methods and apparatuses have application in manufacturing, where the heat may be used to drive chemical reactions for the synthesis of various products (e.g. by heating the reaction components or the medium in which the reaction is carried out, by creating steam, etc.
  • the materials used to generate heat in this manner can be regenerated after several cycles of exposure to light energy, and then reused with high efficiency. Regeneration is accomplished e.g. by washing, filtration or centrifuging if necessary and/or by re-oxidizing the graphene or graphene nanocomposite, etc.
  • This method of heat generation can be applied for other purposes as well, e.g. those where the targeted generation of heat at a distance is desired or advantageous.
  • photothermal reactive material placed in an explosive device can be irradiated from a distance (e.g. with a laser), causing detonation of the device from a distance.
  • a distance e.g. with a laser
  • Examples of this application include but are not limited to uses by the military during warfare, in excavations, or during construction and mining where the removal of earth or rock, etc, is required, etc.
  • the materials and methods of the invention may be used in a variety of scenarios where it is desirable to produce heat above and beyond that which is supplied by exposure to sunlight.
  • the photothermally active materials as described herein may be used in any of a variety of forms, e.g. as particles, sheets, discs, etc, or as coatings or paints, or other wise attached to or incorporated into an item.
  • the materials described herein may be used to replace e.g. carbon black in various applications such as those described in US patents 6,508,247; 6,827,772; 7,255,134; and 7,820,865, the complete contents of each of which are herein incorporated by reference.
  • graphene polymer composites may be used to coat or otherwise be incorporated into materials used for building or heating swimming pools, aquaria, algae ponds, etc. (e.g. pipes, floating, removable, or stationary panels; liners; cement; concrete; tiles; etc.).
  • the materials may be advantageously incorporated into building materials (e.g. roofing, siding, materials for banking a building during winter, etc.).
  • the materials may have applications for use in fabric or clothing (e.g. cold weather footwear, jackets, sweaters, hats, etc. or in items intended for emergency e.g. blankets); in materials for use in accelerating the removal or melting of snow and ice, e.g.
  • tarps or sheets of materials that can be placed on e.g. a sidewalk, or placed on or incorporated into a vehicle, especially a vehicle that is primarily used during cold conditions; or used to protect trees or crops during a freeze; or for use in camping material, e.g. tents, sleeping bags, etc.; or in cooking materials (e.g. pots) or in stoves or ovens, particularly in areas where sources of fuel are scarce; or even for novelty items to cause an increase in heat that is surprisingly out of proportion to incident sunlight.
  • the materials of the invention may be used in any circumstance where sunlight is available and where it is desired to efficiently provide photothermal heating.
  • suitable wavelengths of radiant energy may also be supplied by other sources (lamps, flashlights, laser sources, etc. as described herein).
  • suitable sources lamps, flashlights, laser sources, etc. as described herein.
  • efficient photothermally induced heating can be provided in any environment even in the absence of sunlight.
  • the interiors of buildings walls, floors, ceilings, etc.
  • covers for foods may be made from or coated with photothermally active materials and heated when exposed to one or more suitable wavelengths of radiation.
  • the photothermally active materials as described herein may be used in any of a variety of forms, e.g. as particles, sheets, discs, etc, or as coatings or paints, or other wise attached to or incorporated into an item, so long as they are positioned or located so as to provide heat in a suitable manner.
  • particles of the materials may be mixed with water (e.g. in a swimming pool), and optionally, agitated to distribute the particles; or materials which make up the pool may be coated with photothermally active materials, etc.
  • the latter approach may have advantages in that particulate material may be more difficult to remove if required, e.g. to clean the system.
  • the heat-generating capability of the technology is used in the process of desalination, i.e. for the removal of salts and other minerals from water that contains unacceptably high levels of these substances.
  • the technology is used for the desalination of sea water in order to produce desalinated water that is suitable for consumption (e.g. by humans, livestock, etc.) and/or for irrigation.
  • the technology is especially well adapted to geographical locations which have ample sunshine but where there is a scarcity of sources of fresh water.
  • the photothermally active materials as described herein may be used in any of a variety of forms, e.g.
  • particles of the materials may be mixed with sea water, and optionally, agitated to distribute the particles; or a container in which sea water is present may be coated with the photothermally active materials, etc.
  • the latter approach may have advantages in that particulate material may be more difficult to remove if required, e.g. to clean the system.
  • the heat produced by the methods described herein is used to heat water which contains unwanted materials (e.g. salts, minerals, chemicals, etc., for example, sea water, brackish water, water discharged from manufacturing facilities, water contaminated with feces or microbes, etc.) sufficiently to cause evaporation of water vapor, leaving behind the salts, minerals and/or contaminants.
  • the water vapor is captured and condensed to produce "fresh" water.
  • the methods of the invention are used to heat the water to at least from about 70 to about 80 °C, and then a second energy source is used to supply further heating. This embodiment still provides significant energy savings by decreasing the amount of heat required from the second energy source.
  • water vapor produced by this method is used as a source of humidity e.g. to produce humidified air, instead of or in addition to producing water.
  • the method also provides apparatuses capable of carrying out these reactions.
  • Such an apparatus comprises at least: means (e.g. a container) for containing at least one photothermally active material of the invention (GO, graphene and/or metal or semiconductor nanocomposites thereof) and water which contains salt and/or unwanted minerals or chemicals; means for irradiating the combined material and water (if artificial sources of light energy are used) or means for allowing exposure of the water to natural sunlight (e.g.
  • the salt and/or mineral laden water may not come into direct contact with the photothermally active material, but may be heated indirectly by transfer of heat from another liquid that is heated by the photothermal energy conversion.
  • FIG. 24 An exemplary desalination apparatus is depicted in Figure 24.
  • container 300 contains e.g. seawater 310 and photothermally active material 320.
  • Incident light energy (e.g. sunlight) 330 falls on photothermally active material 320, which produces heat, thereby heating seawater 310.
  • Water vapor (represented by arrow 380) is created and transported by optional conduit 340 to condenser 350, which condenses the water vapor.
  • Receptacle 360 receives (catches, contains, etc.) condensed fresh water 370.
  • some elements of the apparatus are optional or may be combined, e.g.
  • condenser 350 may be located within or part of conduit 340, or condenser 350 may be located in or part of receptacle 360, etc.
  • Various other conduits, valves, pipes etc. may be employed in the apparatus, and any or all of these components may also be coated with or have incorporated therein the photothermally active materia! described herein, e.g. a GO or graphene-polymer composition may be used to coat or manufacture pipes.
  • the materials of the invention are employed in solar humidification-dehuniidification (HDH) methods for thermal water desalination.
  • HDH is based on evaporation of sea water or brackish water and consecutive condensation of the generated humid air, mostly at ambient pressure, thereby mimicking the natural water cycle, but over a much shorter time frame.
  • the simplest configuration is implemented as a solar still, evaporating the sea water inside a glass or other suitable polymer covered container, and condensing the water vapor on the lower side of the cover, from which it is captured. More sophisticated designs separate the solar heat gain section from the evaporation- condensation chamber.
  • An exemplary optimized design may comprise separated evaporation and condensation sections.
  • MEH multiple-effect humidification
  • the graphene and graphene nanocom osites produced by the methods of the invention also have applications for the production of electricity and light, and the invention also provides methods and apparatuses for the production of electricity and/or light.
  • FIG. 20 A schematic of an exemplary photovoltaic cell of the invention is depicted in Figure 20. This figure shows transparent conducting layer 10, photoabsorber 20 and back electrode 30, one or more of which incorporates one or more graphene or graphene-metal or graphene-semiconductor composites produced as described herein.
  • Transparent conducting layer 10 is generally a glass or polymer substrate into or onto which the materials of the invention (e.g. a graphene monolayer or graphene-metal monolayer made by the methods described herein) may be loaded or positioned.
  • Graphene monolayer fabricated as described herein are both transparent and conductive, and may replace indium tin oxide (ITO)-coatings which can be extremely problematic, suffering from price volatility, sustained high cost, and limited worldwide availability.
  • Photoabsorber 20 further comprises, for example, a graphene-semiconductor nanocomposite made as described herein.
  • Back electrode 30 generally comprises graphene (typically a graphene monolayer produced as described herein) and/or metallic ink.
  • such cells or arrays of such cells are arranged in suitable locations such as on rooftops or areas exposed to sunlight without interference (e.g. open lands).
  • suitable locations such as on rooftops or areas exposed to sunlight without interference (e.g. open lands).
  • many other configurations may also be employed, including portable versions of the cells or arrays.
  • the invention provides LEDs comprising a substrate (e.g. a chip), and a semiconductor nanocomposite of graphene associated with the substrate.
  • the LEDs are made by the methods and processes described herein fore the generation of graphene from GO.
  • the semiconductor nanocomposite of graphene is doped with impurities to create one or more p- n junctions (positive-negative junctions) on the substrate.
  • p-side anode
  • n-side cathode
  • Charge-carriers i.e.
  • An exemplary LED 300 is depicted in Figure 25, which shows substrate 410 with associated graphene layer 420 (e.g. a semiconductor nanocomposite of graphene) having associated semiconductor nanoparticles 430, and doped with impurities 3440.
  • substrate 410 with associated graphene layer 420 e.g. a semiconductor nanocomposite of graphene
  • associated semiconductor nanoparticles 430 e.g. a semiconductor nanocomposite of graphene
  • a single device may be fabricated which advantageously produces both heat and light.
  • This example describes the development of a facile laser reduction method for the synthesis of laser converted graphene (LCG).
  • the method provides a solution processable synthesis of individual graphene sheets in water under ambient conditions without the use of any chemical reducing agent.
  • the XRD pattern of the exfoliated GO is characterized by a peak at 2 ⁇ 10.9 with a larger d-spacing of 8.14 A (compared with the typical value of 3.34 A in graphite) resulting from the insertion of hydroxy! and epoxy groups between the carbon sheets and the carboxyl groups along the terminal and lateral sides of the sheets as a result of the oxidation process of graphite.
  • the irradiation time required for the deoxygenation of GO using the 532 or the 355 nm lasers varies from a few to several minutes depending on the laser power, the concentration of GO, and the volume of the solution.
  • Experiments using the fundamental of the YAG laser (1064 nm, 30Hz, 5W) resulted in a rapid partial
  • NLO nonlinear optical
  • OL optical limiting
  • Figure 3 A compares the FT-IR spectra of GO and the LCG.
  • the XPS data of the LCG clearly indicate that most of the oxygen-containing groups in GO are removed after the 532 nm laser irradiation of GO in water (Figure 3B).
  • the Raman spectra of the prepared GO and LCG are shown in Figure 3C.
  • the spectrum of the exfoliated GO shows a broadened and blue-shifted G-band (1594 cm “1 ) and the D-band with small intensity at 1354 cm-1 (as compared with graphite).
  • the spectrum of the LCG shows a strong G-band around 1572 cm “1 , almost at the same frequency as that of graphite with a small shoulder, identified as the DO-band around 1612 cm “1 , and a weak D- band around 1345 cm " ' .
  • the D-band and the DO-shoulder have been attributed to structural disorder at defect sites and finite size effects, respectively.
  • TEM images of the LCG sheets show wrinkled and partially folded sheets with a lateral dimension of up to a few micrometers in length.
  • AFM images with cross- section analysis show that most of the flakes consist of a single graphene sheet.
  • the vertical heights of the sheet at different lateral locations were determined to be 0.99, 1.03, and 1.02 nm. This is consistent with the reported AFM results on graphene, where the single layer graphene is ⁇ 1 nm.
  • the shorter excitation wavelength of 355 nm is strongly absorbed and good for heating the GO surface, but the GO solution bleaches out at higher laser power and longer irradiation times (>5 W, 30 Hz, and >6 min). This indicates that the 532 nm irradiation is more efficient for obtaining rapid photothermal energy conversion by GO in water. It is important to note that in the case of the IR irradiation, the increase in the temperature of the GO solution is mainly due the absorption of the IR photons by water.
  • the advantage of the 532 nm (or the 355 nm) irradiation is that it efficiently converts GO to the more thermally and chemically stable graphene with integrated electronic conjugation. Because of the stability of graphene and its stronger NLO and OL properties as compared with GO, 5 repeated irradiation cycles can be performed with no loss of photothermal conversion efficiency (not shown).We were able to repeat the heating (laser on) and cooling (laser off) cycles reproducibly over seven cycles with almost the same temperature profiles (not shown). The temperature of the solution returns to room temperature after the laser is turned off at almost the same rate as heating occurs during laser irradiation.
  • the photothermal energy conversion of the LCG (second irradiation cycle of GO) appears to be similar to that of CCG prepared by the hydrazine hydrate reduction of GO.
  • These results demonstrate the very high stability of the LCG as a potential photothermal converter for a variety of applications that require fast and efficient temperature rise.
  • the first application of graphene composites in photothermal therapy has been reported very recently. 1 1
  • the laser reduction of GO in water, the accompanied significant temperature rise of water, and the repeated cycles of laser heating of the LCG have not been demonstrated prior to this work. It is reasonable to speculate that the demonstration of efficient photothermal energy conversion by GO and graphene would trigger several other applications in addition to photothermal therapy.
  • the observed temperature rise reflects the steady-state net heat transfer from the LCG to water following the deoxygenation of GO by photothermal energy conversion.
  • the suggested mechanism involves the absorption of the photon energy at 532 or 355 nm by GO resulting in the formation of a heated electron gas that subsequently cools rapidly (picosecond time scale) by exchanging energy with the GO lattice. 8,9
  • nanosecond pulse lasers are suitable for thermal confinement of absorbed energy. 8 ' 9
  • the computed temperatures from pulse laser heating can be on the order of several thousand degrees. 9
  • the laser energy will be dissipated to the surroundings, and a steady state will be reached.
  • GO was prepared by the oxidation of high purity graphite powder (99.9999%, 200 mesh, Alfa Aesar) according to the method of Hummers and Offeman. 10 After repeated washing of the resulting yellowish-brown cake with hot water, the powder was dried at room temperature under vacuum overnight. Dried GO (2 mg) was sonicated in 10 mL of deionized water until a homogeneous yellow dispersion was obtained.
  • the temperature of the solution was monitored during the laser irradiation using a thermocouple immersed in the solution.
  • the LCG sheets were separated and dried overnight under vacuum before the XRD, Raman, IR, and XPS measurements.
  • X'Pert Philips Materials Research diffractometer using Cu KRl radiation.
  • the XPS analysis was performed on a Thermo Fisher Scientific ESCALAB 250 using a monochromatic Al KR.
  • Absorption spectra were recorded using a Hewlett- Packard HP-8453 diode array spectrophotometer.
  • FT-IR spectra a KBr (IR grade) disk containing either GO or LCG was prepared and scanned from 4000 to 500 cm "1 using the Nicolet 6700 FT-IR system under transmission mode.
  • the Raman spectra were measured using an excitation wavelength of 457.9 nm provided by a Spectra-Physics model 2025 argon ion laser.
  • the laser beam was focused to a 0.10 mm diameter spot on the sample with a laser power of lmW.
  • the samples were pressed into a depression at the end of a 3 mm diameter stainless steel rod held at a 30° angle in the path of the laser beam.
  • the detector was a Princeton Instruments 1340 400 liquid nitrogen CCD detector attached to a Spexmodel 1870 0.5m single spectrograph with interchangeable 1200 and 600 lines/mm holographic gratings (Jobin-Yvon).
  • the Raman scattered light was collected by a Canon 50mmf/0.95 camera lens.
  • the holographic gratings provided high discrimination, Schott and Corning glass cutoff filters were used to provide additional filtering of reflected laser light, when necessary.
  • GO was prepared by the oxidation of high purity graphite powder (99.9999%, 200 mesh, Alfa Aesar) according to the method of Hummers and Offeman. 8 After repeated washing of the resulting yellowish-brown cake with hot water, the powder was dried at room temperature under vacuum overnight. 2 mg of the dried GO was sonicated in 10 mL of deionized water (or 50% ethanol-water or 2% PEG-water mixture) until a homogeneous yellow dispersion was obtained.
  • deionized water or 50% ethanol-water or 2% PEG-water mixture
  • the tungsten-halogen lamp used was 500 W.
  • the distance between center of the sample and light source was 35 cm and no filters were used.
  • the temperature of the solution was monitored during irradiation using a thermocouple immersed in the solution.
  • the LCG sheets and the metal-LCG nanocomposites were separated and dried overnight under vacuum before the XRD or the XPS measurements.
  • TEM images were obtained using a Joel JEM-1230 electron microscope operated at 120 kV equipped with a Gatan UltraScan 4000SP 4K x 4K CCD camera. Absorption spectra were recorded using a Hewlett-Packard HP-8453 diode array spectrophotometer. The X-ray diffraction patterns were measured with an X'Pert Philips Materials Research Diffractometer using Cu Kal radiation. The X-ray photoelectron spectroscopy (XPS) analysis was performed on a Thermo Fisher Scientific ESCALAB 250 using a monochromatic Al KR.
  • XPS X-ray photoelectron spectroscopy
  • XRD data of the LCG obtained after the 532 nm (4 W, 30 Hz) irradiation of GO for 10 min in different solvents was obtained.
  • the yellow golden color of the GO solution changes to black with complete disappearance of the XRD 10.9° peak ( Figure 5), thus indicating the reduction of GO and the restoration of the sp 2 carbon sites in the LCG.
  • the irradiation time required for the reduction of GO varies from a few to several minutes depending on the nature of the solvent, the laser power, the concentration of GO and the volume of the solution. For example, under identical conditions of GO concentration (0.2 mg/mL), solution volume (3 mL) and laser power (4 W, 30 Hz), the reduction of GO is completed after 5, 8, and 10 min in 50% ethanol-water, 2% PEG- water and pure water, respectively.
  • two photon absorption is expected to contribute significantly to the absorption of the laser energy by GO due to excited state nonlinearties which enhance the two-photon absorption of GO at 532 nm in the nanosecond regime.
  • UV-Vis spectra of GO following the 532 nm laser irradiation in 50% ethanol-water and 2 % PEG-water mixtures, and in pure water showed that, in all cases, the characteristic shoulder of GO at 305 nm disappears after laser irradiation, and the absorption peak of GO at 230 nm redshifts to about 270 nm due to the ⁇ * transitions of extended aromatic C-C bonds as the electronic conjugation within graphene is restored in the LCG.
  • the XPS data of the LCG in 50% ethanol-water, 2 % PEG-water, and pure water clearly indicate that most of the oxygen-containing groups in GO are removed after the laser irradiation.
  • the TEM images of the reduced GO showed wrinkled and partially folded sheets with a lateral dimension of up to a few microns in length. No obvious differences were observed in the TEM images of the LCG in different solvent environments.
  • the reduction of GO in the presence of ethanol or PEG is much faster than in pure water under identical solution volume, concentration and laser power conditions.
  • 532 nm irradiation with 1 W laser power (30 Hz) converts GO in pure water into graphene in about 40 min (7.2 x 10 3 laser pulses), while in the presence of 50% ethanol or 2% PEG, the same concentration of GO can be reduced in about 22, or 32 min, respectively.
  • the ethanol and PEG solutions exhibit higher reduction efficiencies than pure water. Without being bound by theory, this is attributed to the role of ethanol or PEG in scavenging the holes generated by the laser irradiation of GO.
  • Figure 6A compares the absorption spectra of GO solutions containing the same amount of HAuC in 50% ethanol-water and 2% PEG-water mixtures and in pure water before and after the 532 nm irradiation (4 W, 30 Hz) for 2 min.
  • the reduction of the gold ions and formation of Au nanoparticles is clearly evident by the observation of the Surface Plasmon Resonance (SPR) band of Au nanoparticles (527-531 nm) as shown. It is clear that laser excitation of GO is involved in the reduction of the Au ions since irradiation of the HAuCU solutions in the absence of GO under identical conditions does not result in the formation of Au nanoparticles (Figure 5).
  • SPR Surface Plasmon Resonance
  • the SPR band shifts from 531 nm after 2 min irradiation to 548 nm after 6 min irradiation of GO in the 50% ethanol-water mixture (not shown).
  • the SPR band shifts from 535 nm to 558 nm after 2 min and 10 min irradiation times, respectively of GO in the 2% PEG-water mixture (not shown).
  • the redshift in the SPR band is attributed to the formation of large aggregated Au nanoparticles as confirmed by the TEM images showing the presence of particles in the size range of 30-70 nm after 10 min irradiation (not shown).
  • These large particles are formed via an Ostwald ripening process where the initially formed small particles with higher surface energies are consumed in the growth of the large particles with lower surface energies at longer irradiation times.
  • Selective formation of small Au nanoparticles can be achieved by decreasing the concentration of HAuC and using shorter irradiation times where the Ostwald ripening process can be minimized.
  • the increase in the SPR band intensity of the Au nanoparticles for the 50 % ethanol and the 2 %PEG solutions as compared to pure water is attributed to increasing the concentration of the Au nanoparticles in the presence of ethanol or PEG consistent with the increased reduction efficiencies of these solutions over pure water.
  • the reduction of the Au ions is not observed in pure water as indicated by the absence of the SPR band of Au nanoparticles as shown in Figure 6B. This suggests that the laser reduction mechanism is different in water than in the presence of alcohol or PEG.
  • TEM images were obtained of the Au nanoparticles dispersed on the surface of the LCG graphene sheets formed by the 2 min laser irradiation of the GO solutions containing the same amount of HAuCl 4 in 50% ethanol- water and 2% PEG-water mixtures and in pure water. From the images, it was clear that the concentration of the Au nanoparticles formed in the GO-water solution is significantly lower than the concentration formed in the presence of ethanol or PEG. Again, this is likely a consequence of the favorable reducing environment created by ethanol or PEG as compared to water.
  • irradiation of GO in water in the presence of HAuCU shows that a small GO peak remains in the XRD suggesting that only a partial reduction of GO takes place.
  • the XRD pattern of Au is clearly observed in the resulting Au-LCG nanocomposites formed by laser irradiation of the GO solutions containing the same amount of HAuCU as shown in Figure 7B.
  • the partial reduction of GO in the presence of the Au ions is attributed to the formation of Au nanoparticles which efficiently absorb the 532 nm photons due to the SPR (-530 nm) thus decreasing the probability of two-photon absorption by GO.
  • This will result in decreasing both the number of the photogenerated electrons needed for the reduction of GO as well as the photothermal energy conversion resulting from the nonradiative recombination of the electron-hole pairs.
  • the temperature rise reflects the steady state net heat transfer to the solution following the nonradiative recombination of the e-h pairs in GO. It is clear that laser irradiation of the metal ions' solutions in the absence of GO does not show any significant temperature rise under identical conditions as shown in Figure 10. Therefore, it can be concluded that the temperature rise of the GO solutions containing metal ions following the 532 nm irradiation is mainly due to the photothermal energy conversion by GO and the LCG. Also, the SPR bands of Au and Ag are not observed in the UV-Vis spectra of the laser irradiated HAuC14 and AgNOj solutions in the absence of GO.
  • the reduction of the metal ions appears to be coupled to the absorption of the 532 nm photons by GO and the subsequent photogenerated electron or photothermal reduction processes depending on the nature of the solvent.
  • a decrease in the temperature rise of the GO solution containing metal ions is observed as compared to the GO solution without the metal ions as shown in Figure 10. Similar trends have been observed for the Au and Ag ions in the GO solutions of 2% PEG- water and pure water (not shown). It is reasonable to assume that the decrease in the temperature rise of the irradiated solution in the presence of GO-metal ions mixture is qualitatively related to the contribution of the photothermal effects to the reduction mechanism of the metal ions and GO.
  • the energy required for reduction of the metal ions is provided by the photothermal energy conversion of GO and therefore the net amount of heat transferred to the solution is decreased.
  • the photothermal effects appear to be similar in 50% ethanol-water, 2% PEG-water and in pure water, the enhancement of the reduction of GO and metal ions in ethanol and PEG is most likely due to hole scavenging properties of these solvents which leave the photogenerated electrons available for the reduction of the metal ions and GO.
  • Figure 11 A shows the temperature profiles of repeated irradiation cycles of the HAuCU-GO solution using a 2 W average laser power. After each cycle, the solution was cooled down before starting the next irradiation cycle. In the 7 th cycle, irradiation starts when the temperature of the solution was 36 °C and it became 47 °C after irradiation for 10 min. Then the solution was cooled down to room temperature and the S th cycle started for 10 min where the temperature reached only 41 °C, and the solution color changes to dark blue. This suggests that the drop in temperature is associated with the formation of large aggregated Au nanoparticles.
  • the reduction of the Au ions is much more efficient and faster in the presence of ethanol consistent with the 532 nm laser irradiation results. Therefore, the main features of the photocatalytic reduction of GO and metal ions observed using pulse laser irradiation are reproduced by using the tungsten-halogen lamp. This demonstrates the possibility of using solar energy for the photoreduction of metal ions-GO mixtures and the formation of metal-graphene nanocomposites.
  • the reduction mechanism of the metal ions probably involves the participation of electrons from the LCG or the partially reduced GO.
  • GO as a semiconductor absorbs either two photons of 532 nm or one photon of 355 nm resulting in the creation of an e " -h+ pair.
  • the holes are scavenged to produce protons and reducing organic radicals.
  • the electrons are used for the reduction of the metal ions, and since the alcohol radicals ( C2H4OH) are strong reducing agents they undergo oxidation to CH3CHO and therefore reduce GO.
  • the present approach leads to the formation of metal nanocrystals dispersed on the reduced or partially reduced GO surfaces without the use of chemical reducing or capping agents which tend to significantly reduce the catalytic activity and poison the nanoparticle catalysts.
  • the observed photothermal effects leading to a significant increase in the temperature of the solution suggests that metal-graphene nanocomposites could be promising materials for the efficient conversion of solar energy into usable heat for a variety of thermal, thermochemical and thermomechanical applications.
  • EXAMPLE 3 Photothermal Energy Conversion by Metal and Semiconductor Nanoparticle Composites of Graphite Oxide and Graphene in Water Using Lasers and Tungsten-Halogen Lamps
  • This Example describes a method for the conversion of sunlight and other visible, infrared and ultraviolet radiation into thermal energy which can be used for heating water for domestic use as well as for the evaporation of sea water for efficient desalination.
  • the invention uses graphite oxide and graphene as well as their metal and semiconductor nanocomposites such gold nanoparticles-graphene oxide nanocomposites, gold
  • nanoparticles-graphene nanocomposites, and silicon-graphite oxide, and silicon-graphene nanocomposites are silver, palladium, copper, and platinum.
  • Other semiconductor nanoparticles used with graphite oxide and graphene are titanium dioxide and zinc oxide.
  • Figure 15 shows the temperature increase in solutions of (a) pure water; (b), 1 ml Au particles + 9 ml water; (c) 10 ml of water with 1 mg of suspended GO; (d), 10 ml of water with 1 mg of suspended GO + 10 ⁇ of HAuC /HCl; (e) mixture contains 1 ml of gold spheres and 9 ml of GO mixture, in response to irradiation of the solutions with energy from a tungsten-halogen lamp (500 W).
  • a tungsten-halogen lamp 500 W
  • Figures 16A and B show the efficient coupling of photothermal energy conversion via laser irradiation of GO solutions containing silicon nanoparticles.
  • Bimetallic PdCo nanoparticles supported on graphene are prepared by the laser irradiation process in solutions and the resulting PdCO nanoparticles exhibit higher catalytic activity for CO oxidation as compared to Pd/graphene and Co/graphene catalysts made from Pd nanoparticles or Co nanoparticles supported on graphene, as shown in the data presented in Figures 17A-C, 18A and B and 1 .
  • Solar thermal technology has been used for centuries to provide water heating and/or steam for many purposes. The most common uses are: domestic water heating; and commercial applications in order to provide larger quantities of hot water for use in hotels, hospitals, and restaurants. Additional uses include solar crop drying technologies, basic solar stills to purify water in remote regions where contaminated water cannot be avoided, solar- driven desalination and solar thermal processed steam for industrial purposes. In the latter example, processed steam can be used for different industrial applications based on its ultimate temperature.
  • a solar steam boiler can produce steam at temperatures up to 150 °C and can thus replace the low pressure steam boilers currently used in the textile, chemical, and food industries.
  • a solar steam boiler comprises at least two or more containers for the solar heating of a medium such as air.
  • An exterior side of an exemplary boiler structure that is exposed to incident solar radiation is usually either coated with a blackened heat absorbing material or is covered with absorber plates as "fins". These absorber plates are normally made of metals such as copper or aluminum and are usually painted with selective coatings that absorb and retain heat better than ordinary black paint.
  • Metallic nanoparticles exhibit a very strong UV-VIS absorption band not present in the corresponding bulk spectrum. This absorption is due to the collective excitation of conduction electrons when particle sizes are smaller than the mean free path of carriers in these materials, an effect known as a localized surface plasmon resonance (LSPR).
  • LSPR localized surface plasmon resonance
  • one or more layers of metal nanoparticles are adsorbed onto thermally conductive graphene sheets and incorporated into the design of the solar stills and/or other apparatuses of the invention.
  • the graphene-metal nanocomposites absorb sunlight with very high efficiency.
  • graphene sheets coated with metal nanoparticles increase the boiler's overall efficiency and ultimately produce steam at temperatures over 260 °C.
  • Incorporation of the graphene sheets may be accomplished by any of several methods, e.g. by attaching them to the photoabsorbing surface of the apparatus e.g.
  • a suitable adhesive e.g. a photoabsorbing surface, the "fins” of a still, etc.
  • a suitable surface e.g. a photoabsorbing surface, the "fins” of a still, etc.
  • incorporating the graphene sheets into a photoabsorbing material when it is manufactured by adding particulate material directly to the water that is to be heated, etc.
  • the general principle of solar desalination is based on the fact that glass and other like materials transmit incident short-wave solar radiation.
  • this visible radiation is directed so as to pass through a glass cover and into a container of sea water, and the incident radiation heats the sea water.
  • Wavelengths re-radiated from the surface of the heated water have infrared frequencies, and very little of the infrared energy is transmitted back through the glass. As a consequence, this infrared energy is trapped and heats the sea water even further.
  • This style of desalination system is generally suitable for small production rates, the still's output rate per unit area being relatively small. For example, a prior art well-designed unit having a thermal efficiency of about 50% can produce -4.5 L/m 2 /day.
  • the equipment is both simple to construct and operate with little or no electrical needs. This lends itself to use in remote areas. However, for large capacity plants very large tracts of land are needed in order to make the process worthwhile since capital, land and civil engineering costs are inevitably high.
  • FIG. 21 A schematic of an exemplary solar still is depicted in Figure 21.
  • Nanomaterials that can be used in water purification and desalination processes include metal and metal oxide nanoparticles as well as graphene and carbon nanotubes.
  • a methodology which combines solar desalination and nanotechnology has been developed in our laboratory. This approach is based on producing low cost graphene/gold/silver nanoparticle composites for water desalination.
  • the resulting structures absorb light strongly and convert excess energy into heat in an efficient manner.
  • These new composite materials are added to sea water to dramatically enhance the rate of water evaporation upon exposure to sunlight. For example, using the technology provided herein, production rates of ⁇ 10 or more (e.g. 20-100) L/m 2 /day are attained.
  • the materials may be added to the sea water as particles, or the container that contains the sea water may he coated with the materials, or panels or sheets of the materials may be placed in juxtaposition to the sea water and in a manner that exposes the materials to incident sunlight, or in any other manner that provides efficient exposure of the materials to the sunlight, and transmission of the heat that is generated into the seawater. Sufficient heat is produced to cause evaporation of the sea water, and production of water vapor, which then is condensed to fresh water.

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Abstract

L'invention porte sur des procédés et des appareils pour produire du graphène et des catalyseurs nanoparticulaires supportés sur du graphène sans l'utilisation d'agents réducteurs, et avec la production simultanée de chaleur. Les procédés et appareils emploient une énergie radiante pour réduire (désoxygéner) de l'oxyde de graphite (GO) en graphène, ou pour réduire un mélange de GO plus un ou plusieurs métaux pour produire des catalyseurs nanoparticulaires supportés sur le graphène. L'invention porte également sur des procédés et systèmes pour générer et utiliser la chaleur qui est produite par irradiation du GO, du graphène et de leurs nanocomposites métalliques et semi-conducteurs par un rayonnement visible, infrarouge et/ou ultraviolet, par exemple à l'aide de la lumière du soleil, de lasers, etc.
PCT/US2010/059870 2009-12-10 2010-12-10 Production de graphène et de catalyseurs nanoparticulaires supportés sur le graphène à l'aide d'un rayonnement laser WO2011072213A2 (fr)

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