US20130048506A1 - Porous Metal Dendrites as Gas Diffusion Electrodes for High Efficiency Aqueous Reduction of CO2 to Hydrocarbons - Google Patents

Porous Metal Dendrites as Gas Diffusion Electrodes for High Efficiency Aqueous Reduction of CO2 to Hydrocarbons Download PDF

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US20130048506A1
US20130048506A1 US13/659,354 US201213659354A US2013048506A1 US 20130048506 A1 US20130048506 A1 US 20130048506A1 US 201213659354 A US201213659354 A US 201213659354A US 2013048506 A1 US2013048506 A1 US 2013048506A1
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copper
electrode
electrolytic cell
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Ed Chen
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Columbia University in the City of New York
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/50—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon dioxide with hydrogen
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • C25B11/031—Porous electrodes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20—C2-C4 olefins
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production

Definitions

  • One aspect of the presently disclosed subject matter provides an electrolytic cell system to convert carbon dioxide to a hydrocarbon (e.g., ethylene) that includes a first electrode including a substrate having a metal porous dendritic structure applied thereon; a second electrode, and an electrical input adapted for coupling to a source of electricity, for applying a voltage across the first electrode and the second electrode.
  • a hydrocarbon e.g., ethylene
  • the metal porous dentritic structure is a metal selected from platinum, gold, silver, zinc, cobalt, nickel, tin, palladium and copper.
  • the metal porous dendritic structure is a copper dendritic structure.
  • the substrate is selected from copper, copper foil, glassy carbon and titanium. The first electrode and/or the second electrode can be at least partially saturated with carbon dioxide.
  • the presently disclosed electrolytic cell system can further include an electrolyte source capable of being introduced into a region in between the first electrode and the second electrode of the electrolytic cell system.
  • the electrolyte is selected from a bicarbonate salt (e.g., potassium hydrogen carbonate), sodium chloride, carbonic acid, hydrogen, potassium and methanol.
  • the electrolytic cell system can include a membrane to dissolve carbon dioxide in the electrolyte.
  • the electrolytic cell system includes a conduit to pass carbon dioxide directly to the surface of the first electrode.
  • the presently disclosed electrolytic cell system can further include a source of a metal porphryrin salt capable of being introduced into a region in between the first electrode and the second electrode of the electrolytic cell system.
  • the metal porphyrin salt can be a metal chlorophyllin salt, such as copper chlorophyllin.
  • an electrode for an electrolytic cell system comprising a substrate with a metal porous dendritic structure applied thereon.
  • the metal can be selected from platinum, gold, silver, zinc, cobalt, nickel, tin, palladium and copper.
  • Another aspect of the presently disclosed subject matter provides a method of converting carbon dioxide to a hydrocarbon (e.g., ethylene) that includes providing an electrolytic cell that includes a first electrode including a substrate having a metal porous dendritic structure applied thereon; a second electrode, and an electrical input adapted for coupling to a source of electricity, for applying a voltage across the first electrode and the second electrode; introducing a source of carbon dioxide to the electrolytic cell; and applying the voltage across the first electrode and the second electrode.
  • a hydrocarbon e.g., ethylene
  • the metal of the pourous dendritic structure can be selected from platinum, gold, silver, zinc, cobalt, nickel, tin, palladium and copper.
  • the copper dendritic structure can be prepared, for example, by a process that includes adding copper chlorophyllin to the electrolytic cell and electrodepositing the copper chlorophyllin on the first electrode.
  • the carbon dioxide is obtained from an air stream, a combustion exhaust stream, or a pre-existing carbon dioxide source.
  • Another aspect of the presently disclosed subject matter provides a method for preparing an electrode for use in an electrolytic cell that includes providing an electrolytic cell; applying a solution of a metal porphyrin salt to the electrolytic cell; and applying electricity to plate the metal porphyrin salt on the substrate.
  • the metal porphyrin salt can be a metal chlorophyllin salt (e.g., copper chlorophyllin).
  • the metal porphyrin salt is pulse plated or reverse pulse plated on the substrate.
  • the metal porphyrin salt is applied to the substrate using high current density to create hydrogen bubble templates on the surface of the substrate.
  • FIG. 1 depicts a cyclic voltametry (CV) of copper and platinum electrodes immersed in a 0.1 M sodium bicarbonate solution saturated with carbon dioxide.
  • the A) red line graph is a CV of a piece of copper foil 0.2 grams in mass
  • B) the blue line is a CV of porous copper dendritic electrode with a mass of 5 mg. Current densities for the porous copper is much higher, despite the differences in mass.
  • the “red” line (A) are the two lines that have the highest i/A at about ⁇ 1.5 volts and the “blue lines” (B) are the two lines that have the lowest i/A at about ⁇ 1.5 volts.
  • FIG. 2 is a photograph of copper deposits grown at 150 mA/cm 2 with PVA.
  • FIG. 3 is a photograph of copper deposits grown at 150 mA/cm 2 with no additive.
  • FIG. 4 is a photograph of copper grown with a PEG additive on glassy carbon.
  • FIG. 5 is a cyclic voltametry (CV) a high acid copper solution 10 g/L Cu, and 32 g/L of sulfuric acid (left diagram) and CV of high acid copper solution 10 g/L Cu and 32 g/L sulfuric acid with 1% chlorophyllin additive.
  • CV cyclic voltametry
  • FIG. 6 is a photograph of chlorophllyn residue on porous structure during reverse pulse application, magnified 400 times.
  • the chlorophllyn membrane is attracted to the anode, and is selectively pulled off of the growing fractal front while remaining in the recessed regions, containing loss of surface area while increasing growth of surface area.
  • FIG. 7 is a photograph of copper particles formed with chlorophyllin additive and 10 alternating pulses of ⁇ 0.32 A/cm 2 and 0.1 A/cm 2 . Copper structures can be resolved down to 50 nm, and take on a non-spherical form which display higher surface areas.
  • FIG. 8 is a photograph of copper particles formed with chlorophyllin additive and 10 alternating pulses of ⁇ 0.32 A/cm 2 and 0.1 A/cm 2 . Copper structures can be resolved down to 50 nm, and take on a non-spherical form which provide higher surface areas.
  • FIG. 9 is a photograph of a dendritic fractal cluster produced under a pulsating regime of 500 pulses with a current density of 0.69 A/cm 2 .
  • FIG. 10 is a photograph of a dendritic structure after a pulsating regime of 1000 pulses with a current density of 0.69 A/cm 2 .
  • FIG. 11 is a photograph showing the beginnings of the dendritic copper foam beginning to form.
  • FIG. 12 is a photograph of copper PDS for visual characterization magnified 30 times.
  • FIG. 13 is a photograph of copper PDS magnified 300 times and 5000 times.
  • FIG. 14 is a photograph of a dendrite structure magnified 20,000 times.
  • the presently disclosed subject matter provides a method of converting CO 2 to methanol, methane and other hydrocarbons in an electrolytic cell.
  • the method includes introducing an electrolyte saturated with CO 2 to an electrolytic cell that includes a substrate with a metal plated thereon, and applying electricity to the electrolytic cell to electrochemically reduce the CO 2 .
  • the metal can be selected from, for example, Pt, Au, Ag, Zn, Co, Pb, Ni, Pd and Cu.
  • the substrate is plated with a metal porous dendritic structure, such as a copper porous dendritic structure.
  • Substrates can include, but are not limited to, glassy carbon and titanium.
  • Electrolytes can include, but are not limited to, sodium chloride, sodium carbonate, sodium bicarbonate and potassium hydrogen carbonate.
  • the presently disclosed subject matter also provides an electrolytic cell system that includes an electrolyte saturated with carbon dioxide, a cathode that includes a substrate with a metal plating, and a source of electricity capable of being applied to the electrolytic cell.
  • the metal can be selected from, for example, Pt, Au, Ag, Zn, Co, Ni and Cu.
  • the substrate is plated with a metal porous dendritic structure, such as a a copper porous dendritic structure.
  • Substrates can include, but are not limited to, glassy carbon and titanium.
  • a metal porous dendritic structure is obtained using a metal porphyrin salt.
  • porphyrin refers to a cyclic structure composed of four pyrrole rings together with four nitrogen atoms and two replaceable hydrogens for which various metal atoms can readily be substituted. Porphyrins may be substituted or unsubstituted. An example of a porphyrin is chlorophyllin. Porphyrins, many of which are naturally-occurring, can be obtained from commercial sources. Alternatively, porphyrins can be synthesized. See, e.g., P. Rothemund (1936): “A New Porphyrin Synthesis. The Synthesis of Porphin,” J. Am. Chem.
  • an electrode is prepared by pulse and reverse pulse plating a substrate with a copper porous dendritic structure using a copper chlorophyllin salt as one of the copper sources.
  • This electrode can be used in the methods and systems described herein.
  • Metal Porous Dendritic Structures can be a high performance material in the catalysis of carbon dioxide as well as air capture and electrolytic reduction of CO 2 due to the high surface areas as well as the absorptive catalytic capacity of Copper PDS.
  • copper PDS can solve one of the major difficulties in the electrolytic reduction of CO 2 , as presented in the literature—constructing a electrode which maximizes adsorption of gaseous CO 2 in the reduction reaction with H 2 on the cathode surface. This can allow a commercially feasible process linking electrolytic reduction with air capture, and, in certain embodiments, create a standard temperature and pressure (STP) Fischer Tropsch (FT) device.
  • STP standard temperature and pressure
  • FT Fischer Tropsch
  • Electrodes can be created using a plating mechanism which has been described. See, e.g., Nikolic N D, K I Popov, Lj. J. Pavlovic, M G Pavlovic. “The Effect of Hydrogen Codeposition on the Morphology of Copper Electrodeposits. I. The Concept of Effective Overpotential:” Journal of Electroanalytical Chemistry, 558 (2006) 88-98, which is hereby incorporated by reference.
  • a bath of copper sulfate and sulfuric acid solution (10 g/L Cu, 32 g/L H 2 SO 4 ) can be prepared.
  • An Autolab 4800 Potentiostat can be used with a glassy carbon and copper PDS cathode and a platinum wire anode.
  • Copper Chlorophyllin salt (C 34 H 31 CuN 4 O 6.3 Na Sigma Commercial Grade) can be added to the solution at 1% by weight. Because chlorophyllin is characterized by anodic attraction, the reverse pulse regime creates regions of chlorophyllin membranes covering the dendritic structures, creating additional diffusion-limited growth of dendrites of a smaller scale.
  • Pulse and reverse pulse electrodeposition can be used to form microporous, copper PDS (SEM photos included).
  • a current density of pulsating regimes of ⁇ 0.015 and 0.01 can be used, which translates into a current density of ⁇ 0.32 A/m 2 and 0.21 A/m 2 of 15 ms and 5 ms respectively.
  • This regime can be repeated numerous times (e.g., 10,000 times), which creates a small pore on the glassy carbon.
  • a microporous correl structure results.
  • the presently disclosed subject matter provides electrodes grown in this manner, as well as electroless plating of other nobel metals such as, but not limited to, Pt, Au, Ag, as well as other metals such as Zn, Co, Ni to the copper template to electrochemically reduce CO 2 to hydrocarbons (e.g., ethylene) using electricity in an electrolytic cell which can use sodium bicarbonate or potassium bicarbonate as the electrolyte, or methanol.
  • CO 2 can be dissolved into electrolyte using a membrane, such as a liquicell membrane.
  • potentials can vary from, for example, ⁇ 0.5 V to ⁇ 3 V vs. SHE.
  • Emobidments of the presently disclosed subject matter provides rapid electrochemical reduction of CO 2 to hydrocarbons at current efficiencies of more than, for example, 100 times more than copper foil per gram.
  • Unique products can also be produced on the electrode including C 2 to C 6 hydrocarbons, formate, ethylene, propane, and methanol.
  • ethylene is the primary hydrocarbon produced by the electrolytic cell system.
  • BET surface areas were measured between 20 to 41 m 2 /gram. Use of these electrodes can profitably produce valuable hydrocarbons from carbon dioxide, producing near carbon neutral fuels, while also taking advantage of future and existing carbon credits for offsetting emissions.
  • the presently disclosed subject matter provides for the electrolytic reduction of carbon dioxide. Further embodiments provide a process linking electrolytic reduction with air capture, creating a standard temperature and pressure (STP) Fischer Tropsch (FT) device. The mechanics of dendrite formation and review of the theoretical literature on fractal catalyst simulations is also provided.
  • STP standard temperature and pressure
  • FT Fischer Tropsch
  • Porous dendritic metal foams can be used in electrocatalytic applications, particularly the conversion of CO 2 directly to useful hydrocarbons, such as ethylene. Furthermore, because these catalysts are both produced and applied in an electrochemical environment, any lost catalyst area can be rapidly regenerated in situ. These possible applications extend to porous copper, platinum, and gold structures on reactions such as the electrocatalytic reduction of CO 2 to C 2 -C 6 hydrocarbons, methanol, CO, hydrogen, formate, and other organic compounds, with hydrocarbons being produced at large molar percentages and current densities.
  • the high surface area, coupled with the microporous structure creates outsized absorptivity, while the continuous structure of the foam allows for high electrical conductivity.
  • the experiment is conducted in three portions.
  • the first experiment involved growing porous fractals which maintained their stability and cohesion to the surface of the substrate.
  • the second phase of the experiments were conducted to determine the surface area of the dendritic pores, compared to spherical copper powder, and dendritic copper powder.
  • the third phase of the experiment involved testing the efficiency of the copper PDS electrode for electrocatalytic effects on the reduction of CO 2 to higher hydrocarbons.
  • One purpose of the growth phase of the experiments are to grow fractal surfaces which can be tested for catalytic activity.
  • titanium and glassy carbon produced dendritic structures on their surfaces in this particular example. This is due to the low nucleation densities achieved on the surface of these two substrates. Low nucleation densities result in high current densities, which also have correspondingly high electric potentials.
  • glassy carbon is used as substrate for experiments because of the low nucleation densities achieved due to the low conductivity of the glassy carbon, as well as the repeatibility of the surface of glassy carbon. Low nucleation densities on the surface of titanium are due to inconstitent oxidation patterns.
  • glassy carbon is a substrate of choice in the literature when studying copper crystal growth.
  • a bath of copper sulfate and sulfuric acid solution (10 g/L Cu, 32 g/L H 2 SO 4 ) is prepared.
  • An Autolab 4800 Potentiostat is used with a glassy carbon with copper PDS cathode and a platinum wire anode.
  • Copper chlorophyllin salt (C 34 H 31 CuN 4 O 6.3 Na Sigma Commercial Grade) is added to the solution at 1% by weight.
  • chlorophyllin is characterized by anodic attraction
  • the reverse pulse regime creates regions of chlorophyllin membranes covering the dendritic structures, creating additional diffusion-limited growth of dendrites of a smaller scale by limiting the exposure of cathodic surface area and concentrating a high current density on the tips of new dendrites while preventing structures previously grown from smoothing out with more copper particles.
  • the surface of dendrites after an anode phase of a pulse is shown below to demonstrate the chlorophyllin anodic attraction.
  • Other additives used in experiments were PVA, PEG, and PVP. Results of nucleation for each can be displayed.
  • Pulse and reverse pulse electrodeposition are used to form microporous, copper PDS.
  • a current of pulsating regimes of ⁇ 0.015 A and 0.01 A are used, which translated into a current density of ⁇ 0.32 A/m 2 . and 0.21 A/m 2 of 15 ms and 5 ms respectively. This regime is repeated 10,000 times, which creates a small pore on the glassy carbon substrate.
  • a microporous carrel structure results.
  • the conceptual advantages of pulse and reverse pulse plating for standard electroplating applications is discussed in a review by Chandrasekar and Pushpavanam (2007). It creates dissolution, and the potential of new nucleations.
  • Other metals such as zinc and iron, which are known to produce dendrites, can also be used as templates for copper and other metal electrodes through electroless plating.
  • BET surface area measurements were conducted.
  • the theory of BET surface area measurements can be found in Brunauer, S., P. H. Emmett and E. Teller, J. Am. Chem. Soc., 1938, 60, 309. doi:10.1021/ja01269a023, which is hereby incorporated by reference.
  • the substrate is removed carefully from the electrolyte. If too many pulses are used, pores can lose their structural integrity. Too few pulses, and the pores can be too readily oxidized upon contact with air.
  • Pores are rinsed with deionized water to remove residues of sulfuric acid, then acetone is used to remove deionized water and prevent redissolution of copper PDS.
  • the pore is degassed for a period of six hours at 100° C. in a Quantchrome Nova 3000 Surface Area Analyzer under a nitrogen atmosphere to prevent oxidation.
  • the PDS can lose its structure, or can be oxidized into a hard brown crust.
  • residues can react with copper and can turn the powder into a blue residue.
  • Additional dendritic powder which are dendritic copper grown at high current densities without a pulsing regime, are collected and analyzed as free copper which did not remain on substrate. Furthermore, commercially available spherical copper powder is also analyzed. After sample is degassed, pores are then measured for BET surface area by scraping dendritic pores from glassy carbon substrate into a sealed vacuum tube which is evacuated to set pressures, and partial vapor pressures measured with a transducer at each pressure point.
  • the resulting foam was collected in free form from a tube chamber within the electrolytic cell. This setup is necessary to maintain the high current densities necessary to produce the foam, while also allowing for the flow of copper ions into the cell.
  • the resulting product is washed with deionized water and placed in an argon atmosphere to prevent oxidation of copper powder.
  • a copper correl structure is also grown on a glassy carbon substrate. The BET surface area of the intact coral structure is measured. Cyclic voltametry is performed on the copper electrode on the oxidation of CO 2 to methanol to compare the activity of the fractal catalyst with the activity of a flat geometry deposit.
  • a 0.1 M Na 2 CO 3 is prepared with deionized water, and saturated with carbon dioxide by bubbling gas through solution for one hour.
  • a piece of commercially available, thin copper foil (Alfa Aesar Cu foil Puratronic, 99.9999% (metal basis), 0.25 mm thick) is used as an electrode in the reduction process.
  • a MetroOhm Autolab 4800 potentiostat is used, and a platinum wire counterelectrode is used as well.
  • Gas phase products are analyzed using gas chromotography. A volume of 100 ml is extracted from the cell after running the cell for 10 minutes to purge all air from the system. The production of hydrogen and CO is not detected by the GC. Its weight is determined to be 0.2 grams, which is approximately 40 times the weight of the copper dendritic electrode, which had a weight of 0.00503 grams. However, it's apparent surface area is the same when projected to a two dimensional plane.
  • a copper gas diffusion electrode is fabricated which addresses one of the major needs for improvement—making room temperature and pressure, aqueous electrochemical reduction of carbon dioxide to higher hydrocarbons feasible; this electrode is at least two orders of magnitude more active per gram than an equivalent copper foil.
  • a CV Cyclic Voltametry
  • a method was found to grow surfaces which are significantly more complex, as measured by BET surface area, than those produced in the literature using techniques which have not yet been reported, namely the addition of chlorophyllin.
  • the interface of the copper surface also can be used as a template for other catalysts, providing the potential for creating unique electrocatalytic alloys.
  • Copper PDS electrodes demonstrated electrochemical reduction of CO 2 to hydrocarbons with a peak occurring at a slightly lower potential. Because this process occurs due to adsorption on electrode surfaces, it is possible the gaseous diffusion electrodes would produce higher yields than a simple foil electrode. Copper PDS has very significant surface area and a very low volumetric density. In addition, copper PDS displays many irregularities on its surface, a condition that has been found to be conducive to catalytic reactions, perhaps due to local concentrations in electric field potentials at boundary discontinuities. It is interesting to note that when these structures were placed into the saturated solution of sodium bicarbonate, bubbles nucleated at a far higher rate on the structures, than elsewhere in the solution or other electrodes.
  • the CV showed another interesting effect for copper PDS gaseous diffusion electrodes.
  • the oxidation peaks for the copper gas diffusion electrode differed from the peaks of the foil electrode.
  • the gas diffusion electrodes showed two peaks, while the foil electrode only showed a single peak.
  • the dual peaks implies that two reverse reactions are occurring, each of a slightly different reaction energy, as shown in FIG. 1 .
  • Copper chlorophyllin is used because of the chelated copper at the center of the molecule, as well as its characteristic anodic attraction during pulsing cycles. SEM photographs are taken of the structures after a short number of pulses, as well as longer pulses. From these photographs, it can be seen that the addition of chlorophyllin resulted in the further branching of the nucleating copper particles. Photographs are given from spherical nucleation of copper obtained without additives, to the nucleation of copper with more structure on smaller scales with chlorophyllin as an additive. Nucleation without additives can be controlled to 100 nm. However, using a chlorophyllin additive, structures can be resolved to 50 nm and particles take on a popcorn-like structure.
  • a CV of plating solution with chlorophyllin and without chlorophyllin shows that chlorophyllin increases the resistivity of the solution significantly. Because of the small concentrations of chlorophyllin added to achieve this effect, it is likely that the resistance effect occurs at the electrode surface rather than due to lowering the conductivity of the electrolyte itself.
  • FIG. 5 the figure on the left shows a high acid copper solution without the addition of chlorophyllin.
  • the second graph on the right of FIG. 5 shows the same high acid copper solution with chlorophyllin.
  • the top line refers to copper plating and the bottom line refers to copper dissolution.
  • copper chlorophyllin is found to have a considerable effect upon the structure of the copper crystals. Chlorophyllin undergoes anodic attraction during alternating pulses, creating a situation in which the chlorophyllin coats the developing dendritic fractal structure, creating regions of even higher thermodynamic instability allowing additional growth of dendrites on the already complex surface.
  • FIG. 6 shows an anodic pulse, and the resulting chlorophyllin film coating the copper electrode.
  • the chlorophyllin can produce this effect because it is selectively pulled from the fractal structure in a way that exposes surfaces to rough, protruding points which promote additional dendritic growth.
  • FIG. 7 and FIG. 8 show a highly structured dendritic copper particle resolved to 500 nm. These particles have much higher complexities than other particles reported in the literature, and most likely form due to the interaction of the process with copper chlorophyllin.
  • FIG. 9 and FIG. 10 show the result of dendritic agglomeration after 500 pulses and 1000 pulses.
  • FIG. 11 shows the incipient formation of copper PDS after 2000 pulses.
  • FIG. 12 shows the final copper PDS grown on glass carbon. The diameter of the pore is about 2 mm and it protrudes about 1 mm off the surface of the glass carbon.
  • FIG. 13 shows closeups of the fully formed copper PDS, which take the form of buds, leaves, stalks and stems. The space between pore openings are filled with dendritic copper, structured down to only a few nanometers, as shown in FIG. 14 .
  • the outside surface of PDS can be further controlled based on, for example, a program of finishing pulses.
  • the average pore size of the foam in this example is 10 to 50 microns, which is consistent with those reported in the literature.
  • pore sizes can be reduced through the reduction in bubble size of template hydrogen gas. While not being bound by any particular theory, it is believed that the tips of dendrites could be resolved to 50 nanometers, and display a highly textured surface which is also self-similar across multiple scales.
  • the absorptive resins are to be used in an electrolytic cell, optionally functionalized onto the copper, to produce a direct means electrolytic reduction of CO 2 to ethylene, methane and/or other hydrocarbons on the surface of the resin support.
  • High surface area copper can provide rapid decomposition and neutralization of toxins such as hydrazine, trichloroethylene, nitrobenzene, and phenols, as well as the potential for applications in other fields, such as the electrolytic reduction of carbon dioxide to methane, methanol, and other hydrocarbons, and rapid, high current energy generation in fuel cells. Solely for pupose of convenience, this section will discuss the electrolytic reduction of CO 2 on copper electrodes.
  • a rough calculation of the cost of methane can be calculated.
  • a high current efficiency of 60% hydrocarbons, with the balance being hydrogen, formate, and CO can be achieved using a simple copper foil.
  • Under complete conversion of CO 2 to methane one would obtain 44 grams CO 2 per 16 grams of methane.
  • the price of 1 mmBTU of natural gas is $4.304 (www.nymex.com).
  • Aqueous electroreduction of CO 2 to ethylene, methane and other hydrocarbons could be a significant strategy for upgrading the value of CO 2 to enhance the economic feasibility of air capture and other CCS (carbon capture and storage) technologies.
  • CCS carbon capture and storage
  • This is particularly true with ionic resin exchange membranes which capture CO 2 as the technology requires the immersion of the CO 2 saturated membranes into water to facilitate the desorption of CO 2 .
  • the resulting solution can be saturated with CO 2 and fed into an electrolytic cell for the conversion of the gas into hydrocarbons. This could be facilitated with copper dendritic gas diffusion electrodes, which would allow for a high efficiency conversion with the minimal use of copper, a catalyst that is already cheap and plentiful.
  • Fisher-Tropsch (FT) synthesis can also be conducted from the higher hydrocarbons produced from the initial copper electrodes.
  • Fisher Trospch synthesis can also be conducted electrolytically at room temperature. The limiting factor again is the solubility of the gas in the electrolyte, as well as the ability of electrodes to adhere gaseous reactant species.
  • any metal with a more positive electromotive potential can undergo electroless plating, in which metal ions which have a higher EMF will spontaneously exchange ions with the metal of a lower EMF.
  • platinum, silver, palladium and gold can be plated electrolessly to form dendritic pores of a similar structure.
  • zinc leaves are grown instead of copper leaves, a larger array of potential porous dendritic electrodes could be produced from a wide variety of metals, since zinc has a relatively low EMF.
  • an electroless process could be used to replace zinc with chromium, iron, nickel or cobalt, all of which can play significant roles in Fischer Tropsch synthesis.
  • a further application of the presently disclosed subject matter is the use of carbon nanotubes as electrodes for the further refining of hydrocarbons into FT synthetic fuels. Since the experiments performed are conducted on glassy carbon, a relatively low surface area substrate with a low conductivity and activity (Rozwadowskp 1979), improvements in current efficiencies for reduction of carbon dioxide can be obtained if glassy carbon substrates are replaced with a carbon nanotube substrate as a heterogeneous catalyst support due to the increased absorptive, conductance, and electrochemical activity of nanotubes (Planeix 1994).
  • nanostructured electrodes have already been found for electrolytic applications (Wang 2004) for such applications as sensors (Pietrobon et al 2009, Welch et al 2006), fuel cells (Lien et at 2005), and fuel conversion (Tong 2007) and reforming of methane (Pawelec 2006).
  • Direct plating of metal catalyst particles has found some success, though chemical means have been the dominant method of electrode preparation (Yao et al 2004, Yang et al 2009).
  • Nanotubes are already a promising route for high pressure and temperature FT synthesis (Prinsloo et al 2002, Serp et al 2003), including the direct impregnation of high activity catalysts such as cobalt (Choi et al 2002) onto carbon nanotube structures, which has been shown to increase yields of lighter hydrocarbons and lower the peak temperatures of the reaction (Tavasoli et al 2008, Lu 2007) as well as selectivities of specific hydrocarbons (Lordi et al 2001).
  • high activity catalysts such as cobalt (Choi et al 2002) onto carbon nanotube structures
  • Electrodeposition has found application for creating nanostructures with unique properties. Electrodeposition provides a high degree of control and repeatability for production of nanoparticles, including shape control as well as size control, depending upon the applied currents and potentials, as well as nucleation characteristics of electrode materials. See Liu, H. F. Favier, K Ng, M P Zach, and R M Penner: “Size Selective Electrodeposition of Meso-scale Metal Particles: a general method.” Electrochimica Acta 47 (2001) 671-677; Radisic, Aleksandar Philippe M. Vereecken, James B. Hannon, Peter C. Searson, and Frances M. Ross: “Quantifying Electrochemical Nucleation and Growth of Nanoscale Clusters Using Real-Time Kinetic Data, Nanoletters (2006) Vol, 6 No 2. 238-242.
  • Electrodeposition has been used to produce nanowires directly on carbon nanotubes. Electrodeposition goes a long way towards solving the problem most nanoparticles face: the lack of stability that other methods such as chemical reduction as well as the method of microwave irradiation which are more difficult to structure into a stable, repeatable configurations. Particles can be deposited directly onto a supporting structure such as nanotubes.
  • Catalytic metals relevant to FT synthesis can be deposited unto carbon nanotubes and other carbon substrates such as glassy carbon as supports include platinum and platinum-ruthenium, gold and silver. See, e.g., Auer E, Freund A, Pietsch J, Tacke T: Carbons as Supports for Industrial Precious Metal Catalysts. Appl Catal A. 1998; 173: 259-71.
  • Sonoelectrochemistry has also been used to produce fractal and dendritic nanostructures.
  • Sonochemistry must first be discussed, and involves using an ultrasonic horn to agitate liquid systems. Sonochemical effects occur because of acoustic cavitation which form as the peaks and troughs of an ultrasonic wave pass rapidly through the liquid medium creating regions of rarification and attenuation, See Adewuyi, Yusuf G: “Sonochemistry: Environmental Science and Engineering Applications.” Ind Eng. Chem. Res.
  • Taeghwan Hyeon, and Mingming Fang “Nanostructured Materials Generated by High-Intensity Ultrasound: Sonochemical Synthesis and Catalytic Studies.” Chem. Material. 1996 8, 2172-2179. (Suslick et al 1986).
  • Sonoelectrochemistry couples the power ultrasound to electrochemistry.
  • Kinetics and cavitation are the two main avenues through which sonoelectrochemistry produce its unique results on the nanoscale.
  • Microjets are generated at the electrode surface by the cavitation events with speeds of up to 100 msec.
  • the setup should include an ultrasonic immersion horn probe in which the horn tip can be placed inside the electrochemical cell, producing a sonoelectrochemical cell.
  • the other components would be a graphite counter electrode, Ar inlet degassing unit, Pyrex reservoir to maintain thermal conditions, a Titanium tipped sonic horn, an SCE reference electrode, and Pt 102 resistance thermocouple.
  • Additives such as PVA have been used in the sonochemical process to prevent the agglomeration of particles as they are deposited.
  • Hass et al (2008) used a sonoelectrochemical method to synthesize copper dendrite nanostructures. See Haas, Iris, Sangaraju Shanmugam, and Aharon Vietnamese, “Synthesis of Copper Dendrite Nanostructures by a Sonoelectrochemical Method.” Chem. Eur. J. 2008, 14, 4696-4703. Because sonochemistry relies on ultrasonic pulses that produce small bubbles which collapse very quickly (Compton 1997), this can explain why dendritic structures form.
  • Lead Oxide nanostructures are created using ultrasonic pulses on a glassy carbon electrode (Garcia et al 1998). It is likely that these dendritic structures form as a powder, which are later linked together on the carbon matrix by the intereaction between the polymer chains which hold the particles together and prevent them from agglomerating, as well as the interaction between the PVA and the carbon matrix. PVA functions by forming a polymer matrix which creates this effect, while the —OH group allows for electric interaction between particles, which would be prevented from occurring by the surfactant PVP. They concluded that neither the electrode, nor the pulseform or pretreatment made any difference in the dendritic structures formed, and instead these formed only after on the carbon-copper matrix used in TEM studies. Haas reported that the BET surface area of the dendritic structure is less than 2 m 2 /gram.
  • dendritic fractal structures which had dimensions between 1.74 and 1.76, and had details of up to 50 nm in resolution, these dendrites are dependent upon the interaction between the colloid solution and the interface on which it is prepared to be scanned rather than from any inherent activity from the sonoelectrochemical cell.
  • the major contribution of the sonoelectrochemical cell is to create nanoparticles from reduction of copper, and then the stabilization of these nanoparticles by the PVA.
  • the dendritic structures only formed on a copper carbon grid, which is used as preparation material for TEM study. Perhaps, by creating a electrical matrix on the surface of carbon nanotubes, it can be possible to load nanotubes with dendrites.
  • Dendrites are also the most efficient way to distribute surface area in a three dimensional structure while maintaining a coherent, single structure. Other dispersion methods optimize the total catalytic surface area, without maintaining a coherent shape that also preserves the charge transport properties of the metal. While interest in the formation of non-noble nanoparticles and structures have been growing due to the relatively high stability of copper nanoparticles, the presently disclosed subject matter relates to uses of porous copper dendritic structures.
  • One advance in copper dendritic structures has come where the porous dendritic structures grown under high current densities can be used as a template to electrolessly exchange copper ions with platinum ions, creating a dendritic structure that is fully platinum. These structures have been shown to increase the current density of the electrocatalytic reduction of O 2 over 2.5 times.
  • This mechanism can be used to produce dendrites at low overpotentials in low ion concentrations.
  • Different crystal growth regimes can be established depending on the over potential.
  • the growth rate of crystals depends upon the overpotential applied to the electrochemical system.
  • Mass transport is the most important factor in dendritic crystal growth. Mass transport-limited growth occurs when the rate of crystal growth is greater than the availability of ions in the immediate mass transport boundary layer. Imperfections in the crystal faces create a nonlinear effect in these conditions, as the apexes of the imperfections grow at a higher rate than the receded faces, further increasing the differences between the apexes and valleys of the crystal faces. At high overpotentials in relatively low concentrations of metal ions, a diffusion boundary layer forms around the electrode, which leads the deposition into a mass transport limited regime. High overpotentials also increase the number of crystal branches as well as the total surface area per volume.
  • Dendrites form a tree-like structure with a backbone as well as leaves.
  • the physical connection between the crystals of the leaves as well as the backbone crystal allow nanocrystals to act as a single crystal, conducting phonons and electrons as a single structure (Choi 2008).
  • the continuous structure of metallic dendritic structures can provide the first clue as to novel catalyst actions as will be further sketched out in this thesis.
  • Porous dendritic structures occur because of mass transport limited branching growth.
  • the hydrogen bubbles evolved during electrodeposition of copper at high potentials results in the formation of diffusion limited regions near the cathode. These diffusion limited regions produce branching structures while the bubbles create a template for the development of porous dendritic structures.
  • Copper PDS have been synthesized from copper, as well as other metals such as tin, to form metallic foam with high surface area and high adsorptive characteristics.
  • Many experts in catalysis dismiss the notion of dendritic surfaces as being economically viable for applications due to the assumed short lifetimes of their surfaces.
  • fractal distributions of catalytic metals have been proposed, only a few multi-scale structures which display self similarity have been synthesized. Furthermore, these structures are usually too delicate to find practical use.
  • copper PDS have a higher stability than other fractal distributed catalysts grown at the submicron scale, as these dendritic structures are structured on both a microscale and macroscale and form a continuous structure, rather than a powder.
  • porous dendritic structures are controlled fractal surfaces, rather than random fractal surfaces.
  • Meankin's (1986) simulation of catalyst selectivity in random fractals finds small effects due to the unique geometries of random fractals.
  • controlled fractal surfaces can have very specific effects on different types of chemical reactions catalyzed by the base metals beyond those found by Meakin.
  • the porous dendritic structures described in this paper might have a geometry which deflects gas particles into paths which maximize the number of impacts with the catalyst surface.
  • the mechanisms simulated are based on the inner recesses of the fractals to have a higher ability to absorb a particle of a specific size, and thus create new products.
  • the fundamental mechanism of action would be similar: that though the distribution of catalysis events is equal on all surfaces, the distribution of diffusion absorption events varies greatly as some surfaces are harbored from certain objects (Meakin 1986), perhaps because of their geometry.
  • metals are delocalized electron shells which have the capacity to absorb kinetic energy from surrounding molecules, while also imparting electronic energy to reacting species. If one were to assume that metals, which are high conductors of heat, do not possess kinetic energy when in solid state, then each molecule that strikes the surface of the delocalized shell of an electron will impart some fraction of its energy, 1/f, to metal surface plus a constant, c, amount of energy which is the attractive surface energy of the metal. The reacting species will subsequently slow down. Species which have a low enough kinetic energy below the surface binding energy of the metal will stick to the surface of the metal. When two demobilized reactant molecules come in contact on the surface of the metal, the vibrational energy their reaction creates can be high enough for them to leave the surface of the metal.
  • fractal geometry would be significantly better than another standard Euclidian geometry.
  • Surface area is not the primary determinant of catalyst activity, in itself. Rather, surface area is only important in increasing the number of collisions with reactant molecules.
  • an optimized 2 dimensional coating of catalyst particles will still be of a lower efficiency than a porous fractal geometry because fractal geometries maximize the collisions per molecule by directing the trajectory of molecules after the collision towards another metal surface in the vicinity, whose angle directs particles towards another internal wall of the porous dendritic cage.
  • Reactant molecules are trapped within the interfacial spaces and slow down dramatically faster because of multiple collisions. Because of the potential for multiple collisions, even molecules which are moving with initial kinetic energy which exceeds the surface binding energy of the metal, can be demobilized after multiple collisions with the surface of the metal.
  • the catalyst surface is a polycrystalline with higher heat and phonon conductivity than the surrounding region, and it is connected to an effectively infinite heat sink, the infrared radiation given off by the metallic catalyst surface would likely not exceed ambient temperatures, despite what is an effective hot spot trap within the fractal pore, since the metal can be said to absorb the kinetic energy throughout its delocalized electron shell, and only has average excitation equal to the average kinetic energy it absorbs.
  • the pore can become a hotspot because when first exposed to the ambient environment with a given temperature T, which has a corresponding Kinetic energy KE, carried primarily by the movement of molecules. As these molecules come into contact with the opening of the hole, it has a probability p for every unit of time t of getting trapped by the cage. Furthermore, there is a probability q that a particle will escape from the trap where q depends on the number of particles trapped by the cage t with q ⁇ p. At some point, p and q will equilibrate and the average number of particles per unit volume will be greater within the fractal trap than outside the fractal trap.
  • particles can constantly lose kinetic energy based on each collisions with the surface of the metal, as the metal carries away the energy from particles with higher kinetic energy.
  • S the average number of collisions for a molecule within some involution of the fractal surface
  • B the proportion of molecules which could be captured by a surface with binding energy B
  • E the proportion of molecules which have an energy E ⁇ B.
  • the proportion of particles which have an energy less than B for a flat surface would be the cumulative density function of a normal Gaussian distribution where x equal in this case to the normalized number (B ⁇ E)/E and the probability of binding would be
  • ⁇ ⁇ ( x ) 1 2 ⁇ ⁇ ⁇ ⁇ - ⁇ ( B - E ) ⁇ / ⁇ E ⁇ ⁇ - t 2 ⁇ / ⁇ 2 ⁇ ⁇ ⁇ t 5 )
  • the fractal structure since it is a continuous structure, will have an increase of kinetic energy transferred through it as phonons, though it does not violate the second law, since these phonons are attached to a glassy carbon surface, which is catalyzed at relatively low temperatures of approximately 200 degrees Celsius.
  • the probability of a particle exceeding the binding energy of the metal is:
  • ⁇ ⁇ ( x ) 1 2 ⁇ ⁇ ⁇ ⁇ - ⁇ ( B - E * ( 1 - f ) i ) ⁇ / ⁇ ( E * ( 1 - f ) i ) ⁇ ⁇ - t 2 ⁇ / ⁇ 2 ⁇ ⁇ ⁇ t 7 )
  • ⁇ ⁇ ( x ) 1 2 ⁇ ⁇ ⁇ ⁇ ( B - E ) ⁇ / ⁇ E ( B - E * ( 1 - f ) i ) ⁇ / ⁇ ( E * ( 1 - f ) i ) ⁇ ⁇ - t 2 ⁇ / ⁇ 2 ⁇ ⁇ ⁇ ⁇ t 8 )

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