91 results about "Hydrogen selectivity" patented technology

The invention discloses a catalyst for hydrogen production through tar steam reforming and a preparation method and application thereof. The catalyst comprises a cobalt-magnesium-aluminum composite spinel carrier and an active component loaded on the cobalt-magnesium-aluminum composite spinel carrier, the active component comprises nickel and at least one metal additive selected from iron, zirconium and ruthenium. The preparation method mainly comprises the following steps: preparing the carrier by adopting a coprecipitation method, loading the active component by adopting an impregnation method, and drying and reducing to obtain the final catalyst. The catalyst is used for tar component steam reforming hydrogen production reaction, especially for treating raw materials containing phenol and water vapor at 600-700 DEG C, tar conversion can be efficiently catalyzed, product gas rich in hydrogen can be generated, hydrogen selectivity is high, and almost no methane is generated. The catalyst has the advantages of high activity, good stability, strong carbon deposition resistance and the like, and is suitable for purification and high-value utilization of biomass pyrolysis tar.

The application discloses a cold plasma microbubble and biomass supercritical water gasification hydrogen production system and method, and belongs to the field of biomass hydrogen production. The system comprises a raw material processing unit, a cold plasma pre-activation unit, a high-pressure subcritical pretreatment unit, a supercritical gasification reaction unit, a gas-liquid separation unit, a hydrogen gas purification unit, a waste heat recovery unit and a circulating water treatment unit. After being pulped, the raw material is modified by the cold plasma pre-activation unit to improve the activity, and then enters the supercritical reactor with a built-in catalytic bed through the high-pressure subcritical pretreatment unit containing plasma microbubble generated active species to complete the gasification. After the product gas-liquid separation, the hydrogen-containing gas is purified to obtain high-purity hydrogen gas, the liquid phase water is purified and reused, the waste heat is recovered to supply system energy consumption, and the circulating water is treated to discharge crystalline salt to prevent salt analysis. The application realizes the deep cooperation of cold plasma and supercritical water gasification, improves the gasification efficiency and hydrogen production selectivity, reduces the energy consumption, tar and carbon deposition, guarantees the stable operation of the system, reduces the comprehensive cost, and is suitable for the industrialization of biomass hydrogen production.

The invention discloses a preparation method of a transition metal phosphide catalyst anchored by using a carbon-based material as a carrier and application of the transition metal phosphide catalyst in the field of formic acid hydrogen production, and belongs to the technical field of formic acid hydrogen production catalysis. Transition metal phosphide is anchored on a carbon-based material carrier in situ by adopting a chemical reduction method to obtain a precursor, and the precursor is roasted and pickled in a nitrogen atmosphere to obtain the novel carbon-based material loaded transition metal phosphide catalyst. The catalyst has the advantages of simple preparation method, high catalytic efficiency, cheap non-noble metal raw materials and the like, shows the formic acid conversion rate of 100% and the hydrogen selectivity of 99% or above in the catalytic gas-phase formic acid hydrogen production reaction, and also has good catalytic stability.

A method of hydrogen (H2) storage and withdrawal is described. The method includes injecting a fluid stream into a subsurface formation via an injection well to form a composition containing a gas-phase mixture, a first liquid-phase mixture, and a solid matrix, injecting a H2-containing gas stream into the subsurface formation via the injection well to form a first gas mixture containing H2 gas, heating and pressurizing the subsurface formation containing the first gas mixture via at least one heat well to achieve a storage condition and maintaining the storage condition to store the H2 in the subsurface formation, injecting a CH4-containing gas stream into the subsurface formation via the at least one injection well to form a second gas mixture, withdrawing the second gas mixture via at least one production well, and introducing the second gas mixture into a hydrogen purification device including hydrogen-selective membranes.

This application discloses a heterogeneous catalyst for the selective hydrogenation of nitrile rubber and its application. The heterogeneous catalyst, by weight percentage, consists of 1–10% noble metal particles and 90–99% support, wherein the support is alumina, cerium oxide, titanium dioxide, zirconium oxide, or neodymium oxide. The content of positively valence noble metal in the catalyst accounts for 20–80% of the total noble metal element content, and the noble metal is uniformly loaded on the support. The noble metal is Rh, Os, Ir, Pt, Ru, or Pd, and the particle size of the noble metal particles is 1–20 nm. The heterogeneous catalyst of this invention can carry out hydrogenation reactions at room temperature and pressure, and its hydrogenation selectivity is as high as 100%, with a hydrogenation activity >99%.

The present application provides a method and device for after-treatment of exhaust gas from a hydrogen fuel engine, the method comprising: when the original exhaust temperature of the hydrogen fuel engine is greater than a first temperature threshold, controlling the exhaust gas to enter a first pipeline for after-treatment, wherein the first pipeline is provided with a hydrogen-oxygen catalyst and an ammonia selective catalytic reduction device, and the hydrogen-oxygen catalyst is located upstream of the ammonia selective catalytic reduction device; when the original exhaust temperature of the hydrogen fuel engine is less than or equal to a second temperature threshold, controlling the exhaust gas to enter a second pipeline for after-treatment, wherein the second temperature threshold is less than or equal to the first temperature threshold, and the second pipeline is provided with a hydrogen selective catalytic reduction device. Through the present application, a reasonable selection of exhaust after-treatment methods is made based on the original exhaust temperature of the hydrogen fuel engine, thereby effectively suppressing nitrogen oxide and hydrogen emissions under all operating conditions.

To provide a catalyst capable of selectively generating methanol through hydrogenation of carbon dioxide, and an efficient method for producing methanol employing the catalyst.SOLUTION: A catalyst comprising a material in which a semiconductor oxide represented by Formula (1) and a semiconductor oxide represented by Formula (2) are joined. Formula (1): AJaOm. Formula (2): DOnXx.SELECTED DRAWING: None

The invention belongs to the technical field of catalysts, and particularly relates to a Ni-based alloy solid solution catalyst, a preparation method thereof and application of the Ni-based alloy solid solution catalyst in biomass pyrolysis hydrogen production. The invention provides a Ni-based alloy solid solution catalyst which is an alloy composed of Ni, M and Bi, and M comprises one or more of Ce, La, Zn, Na, K, Ba, Al, Mg, Fe, Co, Cu, Sr, In, Cd, Mo and W. The Ni-based alloy solid solution catalyst can promote C-H fracture and water-gas shift reaction, and also can enable deposited carbon to float on the surface of the catalyst, so that the deposited carbon is effectively removed, and the hydrogen production selectivity is greatly improved.

Hydrogen purification devices and components thereof are disclosed. In some embodiments, a device includes a permeation frame that can include a perimeter portion and a membrane support portion surrounded by the perimeter portion. The membrane support portion can include opposing first and second surfaces, each of the first and second surfaces having a plurality of grooves. The membrane support portion can contact and support at least one hydrogen-selective membrane. The membrane support portion can be integrally formed with the perimeter portion. The permeation frame can also include one or more output apertures in at least one of the perimeter portion and the membrane support portion. The permeation frame can also include at least one input aperture in the perimeter portion. The at least one input aperture can be distinct and spaced apart from the one or more output apertures.

The present invention relates to the field of hydrogen peroxide preparation, and discloses a method for improving the hydrogenation selectivity of anthraquinone in the preparation of hydrogen peroxide by a fluidized bed. In the method of the present invention, a three-component mixed gas of hydrogen, nitrogen, and ammonia is introduced into the anthraquinone hydrogenation reaction system of the fluidized bed hydrogenation reactor in a volume ratio of 60-95:10-40:0.01-1. After being fully mixed with the catalyst and the working solution, a hydrogenation reaction occurs, which can significantly reduce the formation of tetrahydroanthraquinone and anthraquinone degradation products during the anthraquinone hydrogenation process, and greatly improve the selectivity of anthraquinone hydrogenation. The method for improving the hydrogenation selectivity of anthraquinone in the present invention is suitable for the hydrogenation reactions of various anthraquinones.

The invention discloses a preparation method of a monoclinic phase Co / ZrO2 catalyst for hydrogen production through ethanol oxidation reforming. The preparation method comprises the following steps: S1, dissolving Zr (NO3) 4. 5H2O and CO (NH2) 2 in deionized water; s2, transferring the mixed solution in the step S1 into a high-pressure kettle with a polytetrafluoroethylene lining for reaction; s3, filtering and washing the obtained precipitate; s4, drying for a period of time at a certain temperature, and calcining to obtain a ZrO2 carrier; s5, putting the ZrO2 carrier into a Co (NO3) 2 aqueous solution, and carrying out ultrasonic dispersion; s6, after drying, activating treatment is conducted through H2 / Ar mixed gas, and the catalyst for the ESR reaction is obtained. Experimental results show that the monoclinic phase Co / ZrO2 catalyst is rough and porous in surface, uniform in distribution and irregular in particle shape, has higher ethanol conversion rate, hydrogen selectivity and catalytic tolerance, and shows higher C-C bond cracking capacity and catalytic ethanol reforming activity in hydrogen production by ethanol oxidation reforming.

The invention relates to the technical field of chemical industry, in particular to a method for preparing styrene by oxidative dehydrogenation of ethylbenzene, which comprises the following steps: under the condition of low temperature of 150-300 DEG C, ethylbenzene is contacted with an oxygen storage catalyst in an oxidation state, the catalyst catalyzes ethylbenzene dehydrogenation to generate styrene and hydrogen, and then the hydrogen is selectively oxidized into water by self lattice oxygen, directional movement of reaction balance is realized; the catalyst consuming lattice oxygen is regenerated through oxygen-containing gas flow to recover the oxidation state and is recycled. The oxygen storage catalyst is a composite metal oxide or carbide-oxide composite material with a specific structure, and has the functions of ethylbenzene activation, lattice oxygen storage and release and molecular oxygen activation. The invention also provides two reactor implementation schemes of fixed bed switching and fluidized bed circulation. The problems that traditional high-temperature dehydrogenation is high in energy consumption and limited in selectivity and existing oxidative dehydrogenation uses pure oxygen to cause safety and excessive oxidation are solved, and low-temperature, efficient and safe styrene production is achieved.

A portable device for generating hydrogen from ammonia includes a first reactor layer having an ammonia inlet a retentate port, and a chamber containing an ammonia decomposition catalyst. A first gas-collecting layer has a manifold with a hydrogen outlet. A first hydrogen-selective membrane is disposed between the first reactor layer and the first gas-collecting layer. In this way, hydrogen gas generated in the chamber of the first reactor layer will permeate through the hydrogen-selective membrane into the manifold of the first gas-collecting layer. A burner layer is adjacent to the first reactor layer and separated from the chamber by a first conduction plate. The burner layer includes an intake port and an exhaust port. The intake port is in fluid connection with the retentate port of the first reactor layer.

The invention discloses a fibrous rare-earth-based ceramic reforming hydrogen production catalyst as well as a preparation method and application thereof. The catalyst takes fibrous titanium dioxide ceramic as a carrier, a composite oxide of cerium oxide and nickel oxide as an active component and a composite oxide of copper oxide and molybdenum oxide as a cocatalyst. The catalyst for hydrogen production by reforming is environment-friendly, the H2 selectivity for hydrogen production by reforming methanol at low temperature is high, the preparation process is simple, and the catalyst has a wide market application prospect.

The invention discloses a B-site doped perovskite catalyst as well as a preparation method and application thereof. The catalyst comprises a perovskite matrix, the B site of the perovskite matrix is doped with nickel and transition metal, and the transition metal is selected from any one of iron, manganese, chromium and cobalt. The catalyst has the advantages of being environmentally friendly, economical and high in structural stability, when the catalyst is applied to the catalytic acetic acid steam reforming hydrogen production reaction, the acetic acid conversion rate exceeds 80%, the hydrogen selectivity exceeds 80%, the hydrogen yield exceeds 80% in the catalytic acetic acid steam reforming hydrogen production reaction, the catalyst is high in stability, the structure of the catalyst cannot collapse after the reaction, and the catalyst can be applied to the catalytic acetic acid steam reforming hydrogen production reaction. And the service life is up to 200h.

The invention discloses a preparation method of alkyl cyclohexanol, an adopted catalyst and a preparation method of the catalyst.The preparation method belongs to the technical field of synthesis of alkyl cyclohexanol, the catalyst is a nitrogen-doped biomass-based mesoporous carbon-loaded bimetallic catalyst.A high-performance carbon carrier is prepared at low cost through pyrolysis and nitrogen doping processes, and the high-performance carbon carrier is prepared at high temperature; according to the present invention, the supported bimetallic is adopted as the active material, such that the catalyst has the high specific surface area and the high catalytic activity so as to regulate the oxidation state and the catalytic activity of the metal and enhance the reducibility of the metal particles, and the catalyst is used for the alkyl cyclohexanol preparation so as to promote the reaction to the product direction, and effectively improve the hydrogenation selectivity and the product conversion rate.

The invention discloses a metal monolithic catalyst for fuel reforming of a Stirling engine and a preparation method of the metal monolithic catalyst. The method comprises the following steps: performing in-situ oxidation on a FeCrAl honeycomb metal matrix at 950 DEG C to form an Al2O3 nano whisker layer with the diameter of 2-5 microns and the length of 10-20 microns; coating gamma-Al2O3 support slurry on the porous support layer in a dip-coating manner to form a porous support layer; alternately dipping in a cerium nitrate solution and a zirconium nitrate solution, and roasting to construct a Ce0. 75Zr0. 25O2 porous functional layer; and a high-dispersion noble metal active layer is loaded according to the molar ratio of Pt to Rh being 1: 1. The obtained catalyst has high interface bonding strength, high specific surface area and excellent mass and heat transfer performance, can realize high diesel conversion rate and high hydrogen selectivity under the working condition of high-temperature and high-pressure reforming, and shows good carbon deposition resistance and stable operation capability.

This application discloses a fusion reactor ash gas treatment device, belonging to the field of fusion reactor technology. The fusion reactor ash gas treatment device includes: a shell forming a vacuum chamber; a gas supply unit for inputting ash gas into the vacuum chamber; an inductively coupled plasma generator for generating plasma from the ash gas input into the vacuum chamber; a hydrogen selective membrane disposed within the vacuum chamber, dividing the vacuum chamber into a first chamber and a second chamber; the inductively coupled plasma generator is at least partially located in the first chamber; deuterium ions and tritium ions pass through the hydrogen selective membrane into the second chamber and combine to form deuterium-tritium gas; a bias power supply electrically connected to the hydrogen selective membrane for applying a negative bias voltage; a first discharge section connected to the first chamber; and a second discharge section connected to the second chamber. This device achieves rapid treatment and recycling of the ash gas, is not only compact and easy to operate, but also reduces the amount of deuterium-tritium gas retained and energy consumption, improving operational reliability.

The invention discloses an amino-functionalized rodlike silicon dioxide loaded monometal Pd nano-catalyst and application thereof, after rodlike silicon dioxide is subjected to surface modification by 3-aminopropyltrimethoxysilane, a Pd precursor solution and amino-functionalized rodlike silicon dioxide are mixed, and loaded Pd nano-particles are subjected to reduction treatment by sodium borohydride. Compared with a traditional spherical silicon dioxide carrier, the unique morphology of the rod-like silicon dioxide carrier adopted by the catalyst provides a high specific surface area and a short mass transfer channel, the anchoring capacity of Pd nanoparticles is improved through amino functionalization, sintering is inhibited, and efficient and uniform loading and small size control of single metal Pd are achieved. The catalyst is used for room-temperature formic acid decomposition hydrogen production reaction, and shows 100% formic acid conversion rate, 100% hydrogen selectivity, good cycling stability and high initial TOF (Time of Flight) value.

The invention relates to the technical field of catalysts, and discloses a hydrogenation catalyst and a preparation method and application thereof.The catalyst comprises a carrier and an active metal component loaded on the carrier, and the carrier comprises a composite metal oxide and zirconium oxide; wherein the composite metal oxide is M < 1-x > Al < x > O (x + 2) / 2, x is 0.1-0.4, and M is selected from at least one of Mg, Ni, Zn, Cu and Fe; wherein the active metal component is a lanthanide element; wherein the amount of the active metal component in the catalyst is 0.01-5g in terms of metal elements and in terms of the total weight of the carrier being 100g. The hydrogenation catalyst comprises a carrier and an active metal component, the carrier simultaneously comprises a composite metal oxide and zirconium oxide, and the hydrogenation catalyst has high hydrogenation activity, hydrogenation selectivity and hydrogenation degree, is easy to remove in the use process, and can be recycled.

Hydrogen selective membranes and related methods are generally described. In some embodiments, a hydrogen selective membrane may exhibit high permeance and selectivity in comparison to conventional polymer membranes, at low material costs. The membrane may also be thermally and chemically stable at high operational temperatures. In some embodiments, the membrane may include a layer of inorganic material (e.g., palladium) and a layer of atomically thin material (e.g., graphene) arranged on a porous substrate. The inorganic material may be arranged in a film-like or an isolated island-type architecture. In other embodiments, the inorganic material may be arranged within the pores of the porous substrate in an isolated plug-type fashion.

The invention discloses a methane and methanol dual-fuel reforming hydrogen production catalyst as well as a preparation method and application thereof. According to the catalyst, a FeCrAl honeycomb body is oxidized at the temperature of 950 DEG C to form an Al2O3 nano crystal whisker layer, a gamma-Al2O3 bottom layer and a Ce0. 75Zr0. 25O2 functional layer are sequentially coated, and Pt-Rh or Pt-Cu bimetallic components are loaded by adopting an excessive impregnation method. The catalyst is of a cobweb-shaped porous structure, has high specific surface area and excellent sintering resistance and carbon deposition resistance, realizes the methanol conversion rate of more than or equal to 75%, the methane conversion rate of more than or equal to 70% and the hydrogen selectivity of more than or equal to 90% in a wide temperature zone of 200-700 DEG C, and has good stability and industrial application prospects.

This invention relates to the field of hydrogen storage materials technology, specifically to a Pd-Y(OH)3 / NH2-rGO formic acid dehydrogenation catalyst, its preparation method, and its applications. The Pd-Y(OH)3 / NH2-rGO formic acid dehydrogenation catalyst of this invention consists of a sheet-like NH2-rGO support and Pd-Y(OH)3 nanoclusters; the Pd-Y(OH)3 nanoclusters are supported on the surface of NH2-rGO, and Pd and Y(OH)3 form a heterostructure through strong electron interactions. By introducing a non-noble metal yttrium component and forming a stable composite structure with palladium, this invention improves the activity and selectivity of the Pd-Y(OH)3 / NH2-rGO formic acid dehydrogenation catalyst while maintaining high performance and high stability. This overcomes the common problems of low catalytic activity and insufficient hydrogen selectivity in existing formic acid dehydrogenation catalysts, achieving a good balance between catalytic efficiency and material cost.

The invention relates to a water electrolysis hydrogen production purification system and hydrogen production equipment. The system comprises an anion exchange membrane electrolytic tank unit and a hydrogen purification unit, the anion exchange membrane electrolytic tank unit is used for electrolyzing deionized water to generate hydrogen; the hydrogen purification unit is connected with a cathode outlet of the anion exchange membrane electrolytic tank unit and is used for deeply purifying the hydrogen; wherein the anion exchange membrane electrolytic tank unit comprises a membrane electrode and a cathode diffusion layer; the cathode side of the membrane electrode is in close contact with the cathode diffusion layer; and the cathode diffusion layer has an asymmetric gradient aperture and hydrogen selective separation function and is used for performing in-situ selective separation and primary purification on the hydrogen. The integration level of the hydrogen production purification system can be improved, and the operation and maintenance cost can be reduced.

The invention belongs to the technical field of catalysts, and particularly discloses a quantum dot modified Pt / SiC catalyst as well as a preparation method, an activation method and application thereof. Quantum dot modified SiC serves as a carrier of the catalyst, Pt is loaded on the surface of the carrier through a liquid phase reduction method, the quantum dot modified Pt / SiC catalyst is obtained, and through modification of CeO2 QDs, adsorption of C = O in cinnamyl aldehyde is enhanced. The invention also provides a method for improving the hydrogenation performance by using a hydrogen overflow activated catalyst, and the Pt / CeO2 QDs-SiC catalyst subjected to activation pretreatment further enhances the adsorption of C = O and improves the hydrogenation selectivity, so that the cinnamyl aldehyde can be efficiently and selectively hydrogenated to generate cinnamyl alcohol under milder conditions.

The invention discloses a fusion reactor discharged ash gas treatment device, and belongs to the technical field of fusion reactors. The fusion reactor discharged ash gas treatment device comprises a shell forming a vacuum chamber; the gas supply part is used for inputting ash discharge gas into the vacuum chamber; the inductively coupled plasma generating device is used for enabling the discharged ash gas input into the vacuum chamber to generate plasma; the hydrogen selective membrane is arranged in the vacuum chamber and divides the vacuum chamber into a first cavity and a second cavity, the inductively coupled plasma generating device is at least partially located in the first cavity, and deuterium ions and tritium ions enter the second cavity through the hydrogen selective membrane and are combined to form deuterium and tritium gas; the bias power supply is electrically connected with the hydrogen selection membrane and is used for applying bias voltage with negative potential; the first discharge part is communicated with the first cavity; and the second discharge part is communicated with the second cavity. The deuterium and tritium gas treatment device not only is compact in structure and simple and convenient to operate, but also can reduce the retention volume and energy consumption of deuterium and tritium gas, and improves the operation reliability.

The invention relates to the technical field of CO2 catalytic conversion, in particular to a preparation method and application of a nickel-based catalyst for selective production of CH4 / CO through photo-thermal catalysis of CO2 hydrogenation, a soluble nickel salt, a soluble lanthanum salt or an aqueous solution of hydrates of the soluble nickel salt and the soluble lanthanum salt is dropwise added into mesoporous silica, so that mesopores are fully impregnated with the solution, and the nickel-based catalyst is obtained; and removing liquid from the obtained solid-liquid mixture, drying and roasting to obtain the nickel-based catalyst. The preparation method is simple in preparation route, low in cost and suitable for large-scale popularization in industrial production. When the catalyst is applied to selective production of CH4 / CO through photo-thermal catalysis of CO2 hydrogenation, the selectivity of CH4 and CO can reach 95% or above under different photo-thermal conditions, the photo-thermal catalysis condition adjusting mode is simple, and good application prospects are achieved.

This invention discloses a selective hydrogenation catalyst for phenylacetylene in the presence of styrene and its preparation method. The catalyst is a Ni-Zn catalyst with a regular surface morphology and a nano-leaf-like structure; the leaf thickness is 5-20 nm, the leaf width and length are 300-3000 nm, and the specific surface area is 70-240 m². 2 / g, pore volume is 0.25~0.60cm³ 3 / g. The nanosheet morphology on the surface of this catalyst not only effectively prevents the aggregation of Ni metal particles during high-temperature calcination and improves the dispersion of the active component, weakening the strong interaction between Ni and alumina, but also the active site isolation effect allows Zn to act as a selective promoter to improve the selectivity of styrene. Thus, it exhibits high activity and high selectivity in the selective hydrogenation reaction of phenylacetylene. When used for the selective hydrogenation of C8 fraction to remove phenylacetylene, this catalyst has the advantage of not easily agglomerating after high-temperature reduction, and at the same time has excellent hydrogenation selectivity.

The application discloses a kind of brominated self-porous polymer ammonia hydrogen separation membrane and preparation method thereof, comprising the following steps: S1, TTSBI-M is reacted with TFTPN at high temperature, and synthesis contains benzyl methyl self-porous polymer PIM-M;S2, PIM-M is completely dissolved in chlorobenzene, then liquid bromine is added, and bromomethylated self-porous polymer PIM-Br is prepared by reaction;S3, PIM-Br is dissolved in organic solvent to obtain casting solution, the casting solution is uniformly coated on clean glass plate, and PIM-Br base film is obtained after solvent volatilization;S4, the base film is soaked in the solution of amine containing two or more tertiary amine groups to carry out synchronous crosslinking quaternary ammonium reaction, and modified membrane is obtained;S5, the modified membrane is soaked in metal chloride solution to carry out chelation reaction, then the membrane is taken out and washed with deionized water, and ammonia hydrogen separation membrane based on brominated self-porous polymer is obtained.The obtained separation membrane has high ammonia separation effect, and when separating ammonia-containing gas, ammonia permeability is as high as 7145.3 Barrer, and ammonia / hydrogen selectivity is as high as 668.5.

Provided is a cathode electrode in which the selectivity of hydrogen can be suppressed from being increased even when a catalyst layer is immersed in an electrolyte solution, and in which a catalytic reaction for producing an olefin such as ethylene and an alcohol such as ethanol by a reduction reaction of carbon dioxide can be stably and efficiently maintained over a long period of time. The present invention provides a cathode electrode for electrically reducing carbon dioxide, the cathode electrode having a first layer that is positioned on the surface layer of the cathode electrode and has a first thickness, and a second layer that is adjacent to the first layer in the thickness direction of the first layer and has a second thickness, the first layer containing copper, and the second layer containing copper. The first layer is subjected to surface modification by a cation exchange material substituted by metal ions, and the second layer is a cathode electrode of a mixed layer of copper and carbon.