CN113308708B - Metal titanium activation method, activated metal titanium and application - Google Patents

Metal titanium activation method, activated metal titanium and application Download PDF

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CN113308708B
CN113308708B CN202110403911.9A CN202110403911A CN113308708B CN 113308708 B CN113308708 B CN 113308708B CN 202110403911 A CN202110403911 A CN 202110403911A CN 113308708 B CN113308708 B CN 113308708B
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titanium
hydrogen
metallic titanium
plasma
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CN113308708A (en
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张天助
陈钧
叶小球
吴吉良
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    • 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
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/48—Ion implantation
    • 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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • 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
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • C25B11/061—Metal or alloy
    • C25B11/063—Valve metal, e.g. titanium
    • 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
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

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  • Chemical Kinetics & Catalysis (AREA)
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  • Electrochemistry (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

The invention discloses a method for activating metallic titanium, activated metallic titanium and application; belonging to the technical field of catalytic material preparation. The method for activating metallic titanium of the present invention utilizes a plasma method and applies a bias voltage on the surface of the metallic titanium to inject hydrogen or hydrogen isotopes into the metallic titanium crystal lattice. The activated metal titanium prepared by the method is applied to the preparation of hydrogen by catalyzing and electrolyzing water. The activated metal titanium is directly used as an electrode for catalyzing water electrolysis to produce hydrogen; or the activated metal titanium is used as a catalyst carrier for catalyzing and electrolyzing water to produce hydrogen. The invention has scientific design and ingenious conception, and creatively injects hydrogen or isotopes thereof into the alpha-Ti crystal lattice by using a plasma method, thereby effectively improving the performance of hydrogen production by titanium-catalyzed water electrolysis. Through experimental tests, the metallic titanium sample activated by the method can effectively improve the performance of water decomposition and hydrogen evolution by electrocatalysis, and can also obviously improve the reaction activity of a catalytic system when the metallic titanium sample is used as a catalyst carrier.

Description

Metal titanium activation method, activated metal titanium and application
Technical Field
The invention belongs to the technical field of catalytic material preparation, and particularly relates to a metal titanium activation method, activated metal titanium and application.
Background
The development of clean and sustainable alternatives to fossil fuels is a key issue in the field of energy research today. The catalyst plays a central role in the conversion synthesis process of high-value energy carriers such as hydrogen and the like. A good catalyst means higher conversion efficiency and lower energy consumption.
However, high-performance catalysts currently used in the field of electrocatalytic hydrogen production and the like are mainly noble metals such as Pt, pb, rh, and the like. The noble metal catalytic materials are relatively expensive, limiting their large-scale application. Therefore, the preparation of low-cost and high-performance catalytic materials is a key and difficult problem for the development of new energy upstream industries.
Disclosure of Invention
One of the objectives of the present invention is to provide an activation method for metallic titanium, which can greatly improve the performance of electrocatalytic decomposition of water and hydrogen evolution of metallic titanium, and has good stability.
The second object of the present invention is to provide an activated titanium metal produced by the activation method.
The invention also aims to provide application of the activated metallic titanium.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention relates to a method for activating metallic titanium, which utilizes a plasma method and applies bias voltage on the surface of the metallic titanium simultaneously to inject hydrogen or hydrogen isotopes into the metallic titanium crystal lattice.
The method is simple, controllable, environment-friendly and friendly, hydrogen or isotopes thereof are injected into the metallic titanium crystal lattice, the local electronic structure of the metallic titanium is effectively changed, the reaction energy barrier is reduced by changing the charge distribution of the surface of the atoms in the catalytic reaction, and the effect of improving the catalytic activity is achieved.
In some embodiments of the invention, the method for activating metallic titanium comprises the steps of:
step 1, fixing clean metal titanium in a plasma processing device, and enabling a processing surface of the metal titanium to be vertical to the direction of a plasma beam;
step 2, vacuumizing the plasma processing device;
step 3, introducing hydrogen or isotope gas thereof, turning on a plasma power supply, and then applying bias voltage to the surface of the metallic titanium to perform plasma injection treatment;
and 4, after the injection is finished, carrying out aeration and sampling operation to obtain the activated metallic titanium.
In some embodiments of the present invention, the clean metallic titanium is obtained by ultrasonically cleaning metallic titanium and vacuum-drying the metallic titanium.
In some embodiments of the present invention, in step 2, the mechanical pump is used to pump the system vacuum to below 100Pa, and then the molecular pump is turned on to perform the vacuum pumping operation, so that the system vacuum is less than 5 × 10 -4 Pa。
In the invention, the purity of the plasma is ensured by vacuumizing.
In some embodiments of the present invention, in step 3, the flow rate of the hydrogen gas or the isotopic gas thereof is 1 to 3sccm, or/and the power of the plasma power supply is 100 to 600W, or/and the bias voltage is 0 to 300V negative voltage.
In some embodiments of the invention, the hydrogen ions or isotopic ions thereof have an energy of greater than 3eV, or/and a flux of greater than 10 eV, during the plasma implantation process 19 ions/m 2 ·s。
In some embodiments of the invention, the titanium metal surface temperature is less than 400 ℃ during the plasma implantation treatment. The invention discovers that the titanium hydride has better environmental stability after being injected, and the desorption can be generated at the temperature of more than 400 ℃. In some embodiments of the present invention, in step 3, the time of the plasma implantation treatment is 0.5 to 3 hours, preferably 2 hours.
The activated metallic titanium prepared by the method of the invention.
The activated metallic titanium is applied to the preparation of hydrogen by catalyzing and electrolyzing water.
In some embodiments of the invention, the activated metallic titanium is used directly as an electrode for catalyzing the electrolysis of water to produce hydrogen;
or the activated metal titanium is used as a catalyst carrier for catalyzing and electrolyzing water to produce hydrogen.
Compared with the prior art, the invention has the following beneficial effects:
the invention has scientific design and ingenious conception, and creatively injects hydrogen or the isotopologue thereof into the alpha-Ti crystal lattice by using a plasma method, thereby effectively improving the performance of hydrogen production by titanium catalytic electrolysis of water.
Compared with the traditional wet chemistry method, the method disclosed by the invention has the advantages that the problems of pollution and uncontrollable sample surface are avoided, and the problem of post-treatment of acid-containing waste liquid is solved.
The method provides a simple, controllable and environment-friendly method for injecting hydrogen or isotopes thereof, effectively changes the local electronic structure of the metallic titanium, reduces the reaction energy barrier by changing the charge distribution of the surface of the atoms in the catalytic reaction, and achieves the effect of improving the catalytic activity. Experimental tests show that the metallic titanium sample activated by the method can effectively improve the hydrogen evolution performance of electrocatalytic decomposition water, and can also obviously improve the reaction activity of a catalytic system when being used as a catalyst carrier.
Drawings
FIG. 1 is a schematic view of an assembly of a plasma treated sample according to the present invention.
FIG. 2 is a microscopic morphology of hydrogen infused titanium metal foam prepared in example 1 of the present invention.
FIG. 3 is a thermal desorption spectrum of hydrogen infused titanium metal foam prepared in example 1 of the present invention.
FIG. 4 is a comparison of the linear voltammograms of the electrocatalytic decomposition of water in 1M KOH of the hydrogen infused titanium foam prepared in accordance with example 1 of the present invention and the original titanium foam.
FIG. 5 is a microscopic topography of hydrogen infused titanium foam prepared in example 3 of the present invention after deposition of CoPB nanoparticles as a carrier.
Detailed Description
All of the features disclosed in this specification, or all of the steps in any method or process so disclosed, may be combined in any combination, except combinations of features and/or steps that are mutually exclusive.
Any feature disclosed in this specification may be replaced by alternative features serving equivalent or similar purposes, unless expressly stated otherwise. That is, unless expressly stated otherwise, each feature is only an example of a generic series of equivalent or similar features.
Example 1
The embodiment discloses an activation method of metallic titanium, which specifically comprises the following steps:
the foamed metal titanium is ultrasonically cleaned in ethanol for 15 minutes, then is placed in a vacuum drying oven to be dried at the temperature of 60 ℃, and a sample is taken out after 10 hours.
Fixing the cleaned and dried foam metal titanium on the middle rear part of a plasma processing device by using a clamp, wherein the processing surface of the foam metal titanium is vertical to the direction of a plasma beam, as shown in figure 1;
starting a mechanical pump to pump the vacuum degree of the system to 10Pa, then starting a molecular pump to pump the vacuum degree of the system to 4.8 multiplied by 10 -4 Pa。
Hydrogen was introduced at a flow rate of 2sccm. The plasma microwave source was then turned on and the power was set at 300W. The bias voltage device is turned on, and the voltage is slowly adjusted to-110V from 0V, and the plasma hydrogen injection treatment is started.
After 2 hours, the hydrogen injection is finished, the bias voltage, the plasma microwave source, the hydrogen flow and the vacuum pump are closed in sequence, aeration is carried out after the surface temperature of the sample is reduced to 25 ℃, and the modified foam metal titanium is taken out to prepare the activated metal titanium, namely the hydrogen injection modified foam metal titanium. The microstructure of the hydrogen-implanted modified titanium foam prepared in the embodiment is shown in figure 2; from this figure, it can be seen that: the microscopic appearance of the alloy is not changed significantly after the hydrogen injection treatment. The thermal desorption spectrum of the hydrogen-injected modified foam metal titanium prepared in the embodiment is shown in the attached figure 3; from this figure, it can be seen that: the hydrogen is successfully injected into the titanium, and the hydrogen has better environmental stability after being injected, and the desorption can be carried out at the temperature of more than 400 ℃.
The electrochemical surface area of the hydrogen-infused modified titanium foam prepared in the embodiment is determined to be improved by three times compared with that of the original titanium foam.
The linear voltammogram of the hydrogen-infused modified titanium foam prepared in this example is shown in FIG. 4, which is the graph of electrocatalytic decomposition of water with the original titanium foam in 1M KOH. At 1M KOH, 10mA cm -2 The overpotential for water evolution by electrocatalytic decomposition of hydrogen under the current density condition is reduced by 210mV compared with the original foam metal titanium; the titanium hydrogen has better environmental stability after being injected, and can be desorbed only at the temperature of over 400 ℃.
The electrochemical surface area of the modified titanium foam was tested in this example according to the literature McCrory, c.c.l.; jung, s.; ferrer, i.m.; chatman, s.m.; peters, j.c.; jaramillo, T.F. Benchmarking hydrogen evolution reaction and oxygen evolution reaction electrolysis for sodium water splitting devices, journal of the American Chemical Society 2015,137 (13), 4347-4357, DOI.
Example 2
The embodiment discloses an activation method of metallic titanium, which specifically comprises the following steps:
the foamed metal titanium is ultrasonically cleaned in ethanol for 15 minutes, then is placed in a vacuum drying oven to be dried at the temperature of 60 ℃, and a sample is taken out after 10 hours.
Fixing the cleaned and dried foam metal titanium on the middle rear part of a plasma processing device by using a special fixture, wherein the processing surface of the foam metal titanium is vertical to the direction of a plasma beam, as shown in figure 1;
starting a mechanical pump to pump the vacuum degree of the system to 10Pa, then starting a molecular pump to pump the vacuum degree of the system to 4.8 multiplied by 10 -4 Pa。
Hydrogen was introduced at a flow rate of 2sccm. The plasma microwave source was then turned on and the power was set at 300W. The bias voltage device is turned on, slowly adjusted to-110V from 0V, and the plasma hydrogen injection treatment is started.
After 0.5 hour, the hydrogen injection is finished, the bias voltage, the plasma microwave source, the hydrogen flow and the vacuum pump are closed in sequence, aeration is carried out after the surface temperature of the sample is reduced to 25 ℃, and the modified foam metal titanium is taken out to prepare the activated metal titanium.
The activated metallic titanium prepared in this example was in a concentration of 10mA cm at 1M KOH -2 The overpotential of the water evolution of the electrocatalytic decomposition of the hydrogen under the current density condition is reduced by 108mV compared with the original foam metal titanium.
Example 3
The embodiment discloses an activation method of metallic titanium, which specifically comprises the following steps:
the foamed metal titanium is ultrasonically cleaned in ethanol for 15 minutes, then is placed in a vacuum drying oven to be dried at the temperature of 60 ℃, and a sample is taken out after 10 hours.
Fixing the cleaned and dried foam metal titanium on the middle rear part of a plasma processing device by using a special fixture, wherein the processing surface of the foam metal titanium is vertical to the direction of a plasma beam, as shown in figure 1;
starting a mechanical pump to pump the vacuum degree of the system to 10Pa, then starting a molecular pump to pump the vacuum degree of the system to4.8×10 -4 Pa。
Hydrogen was introduced at a flow rate of 2sccm. The plasma microwave source was then turned on and the power was set at 300W. The bias voltage device is turned on, and the voltage is slowly adjusted to-110V from 0V, and the plasma hydrogen injection treatment is started.
After 1 hour, the hydrogen injection is finished, the bias voltage, the plasma microwave source, the hydrogen flow and the vacuum pump are closed in sequence, aeration is carried out after the surface temperature of the sample is reduced to 25 ℃, and the modified foam metal titanium is taken out to prepare the activated metal titanium.
The activated metallic titanium prepared in this example was in a concentration of 10mA cm at 1M KOH -2 The overpotential for water decomposition and hydrogen evolution by electrocatalysis under the condition of current density is reduced by 136mV compared with the original foam metal titanium.
Example 4
The embodiment discloses an activation method of metallic titanium, which specifically comprises the following steps:
the foamed metal titanium is ultrasonically cleaned in ethanol for 15 minutes, then is placed in a vacuum drying oven to be dried at the temperature of 60 ℃, and the sample is taken out after 10 hours.
Fixing the cleaned and dried foam metal titanium on the middle rear part of a plasma processing device by using a special fixture, wherein the processing surface of the foam metal titanium is vertical to the direction of a plasma beam, as shown in figure 1;
starting a mechanical pump to pump the vacuum degree of the system to 10Pa, then starting a molecular pump to pump the vacuum degree of the system to 4.8 multiplied by 10 -4 Pa。
Hydrogen was introduced at a flow rate of 2sccm. The plasma microwave source was then turned on and the power was set at 300W. The bias voltage device is turned on, and the voltage is slowly adjusted to-110V from 0V, and the plasma hydrogen injection treatment is started.
After 3 hours, the hydrogen injection is finished, the bias voltage, the plasma microwave source, the hydrogen flow and the vacuum pump are closed in sequence, aeration is carried out after the surface temperature of the sample is reduced to 25 ℃, and the modified foam metal titanium is taken out to prepare the activated metal titanium.
The activated metallic titanium prepared in this example was in a concentration of 10mA cm at 1M KOH -2 The overpotential of the water produced by electrocatalytic decomposition of the water is higher than that of the original hydrogen produced by the electrocatalytic decomposition under the condition of current densityThe starting metallic foam titanium was reduced by 205mV.
Example 5
The embodiment discloses an activation method of metallic titanium, which specifically comprises the following steps:
the method comprises the following steps of ultrasonically cleaning a metal titanium sheet in ethanol for 15 minutes, then placing the metal titanium sheet in a vacuum drying oven to be dried at the temperature of 60 ℃, and taking out a sample after 10 hours.
Fixing the cleaned and dried metal titanium sheet to the middle rear part of the plasma processing device by using a special fixture, wherein the processing surface of the metal titanium sheet is vertical to the direction of a plasma beam.
Starting a mechanical pump to pump the vacuum degree of the system to 10Pa, then starting a molecular pump to pump the vacuum degree of the system to 4.5 multiplied by 10 -4 Pa。
Deuterium gas was introduced at a flow rate of 2sccm. The plasma microwave source was then turned on and the power was set at 300W. The biasing device was opened and slowly ramped from 0V to-140V. And starting timing to perform plasma deuterium injection treatment after the steps are completed.
After 2 hours, deuterium injection is completed, the bias voltage, the plasma microwave source, deuterium gas flow and the vacuum pump are closed in sequence, aeration is carried out after the surface temperature of the sample is reduced to 25 ℃, and the modified metallic titanium sheet is taken out, so that the activated metallic titanium, namely the deuterium-injected modified metallic titanium sheet, is prepared.
The electrochemical surface area of the metallic titanium sheet after deuterium plasma injection is determined to be improved by four times. At 1M KOH, 10mA cm -2 The overpotential for water decomposition and hydrogen evolution by electrocatalysis under the condition of current density is reduced by 320mV compared with the original titanium sheet.
Example 6
This example discloses experiments with the activated metallic titanium of the present invention as a substrate and depositing an active material on the substrate.
The activated titanium metal used in this example was prepared in accordance with the method of example 1.
And depositing Co-P-B nano particles on the surface of the hydrogen-injected foam metal titanium by adopting an electrodeposition method to obtain CoPB-TiFoam-H. The method specifically comprises the following steps: prepare 20mL of 1mM CoCl 2 ·6H 2 O,0.1M NaCl,0.25MNaH 2 PO 2 And 0.25M H 3 BO 3 The electrolyte formed by the method is deposited for 600 seconds at a constant voltage of-1.5 VAg/AgCl/sat.KCl by taking activated metal titanium as a working electrode, a platinum sheet as a counter electrode and Ag/AgCl/sat.KCl as a reference electrode.
The microstructure of the obtained CoPB-TiFoam-H is shown in figure 5, and the Co-P-B nano particles are uniformly distributed on the surface of the activated metallic titanium.
And depositing CoPB nanoparticles on the surface of the substrate by using non-activated metal titanium as the substrate, thereby obtaining CoPB-TiFoam.
Measured at 10mA cm in 1M KOH -2 Under the condition of current density, compared with CoPB-TiFoam, the overpotential for water evolution through electrocatalytic decomposition of CoPB-TiFoam-H prepared by the embodiment is reduced by 59mV.
The above embodiments are only preferred embodiments of the present invention, and are not intended to limit the scope of the present invention, but all changes that can be made by applying the principles of the present invention and performing non-inventive work on the basis of the principles shall fall within the scope of the present invention.

Claims (9)

1. A metallic titanium activation method is characterized in that hydrogen or hydrogen isotopes are injected into metallic titanium crystal lattices by a plasma method and applying bias voltage on the surface of the metallic titanium;
the method for activating the metallic titanium comprises the following steps:
step 1, fixing clean metal titanium in a plasma processing device, and enabling a processing surface of the metal titanium to be vertical to the direction of a plasma beam;
step 2, vacuumizing the plasma processing device;
step 3, introducing hydrogen or isotope gas thereof, turning on a plasma power supply, and then applying bias voltage to the surface of the metallic titanium to perform plasma injection treatment; the energy of hydrogen ions or isotope ions thereof is more than 3eV or the flux is more than 10 eV during the plasma injection treatment 19 ions/m 2 ·s；
And 4, after the injection is finished, carrying out aeration and sampling operation to obtain the activated metallic titanium.
2. The method according to claim 1, wherein the clean metallic titanium is obtained by ultrasonically cleaning metallic titanium and drying the metallic titanium in vacuum.
3. The method according to claim 1 or 2, wherein in the step 2, the mechanical pump is used to pump the system vacuum degree to be less than 100Pa, and then the molecular pump is started to perform the vacuum pumping operation, so that the system vacuum degree is less than 5 x 10 -4 Pa。
4. The method according to claim 1 or 2, wherein in step 3, the flow rate of the hydrogen gas or the isotopic gas thereof is 1-3sccm, or/and the power of the plasma power supply is 100-600W, or/and the bias voltage is 0-300V negative voltage.
5. The method according to claim 1 or 2, wherein the metallic titanium surface temperature is lower than 400 ℃ during the plasma injection treatment;
or/and the time of the plasma injection treatment is 0.5-3 hours.
6. The method of claim 5, wherein the plasma implantation treatment time is 2 hours.
7. Activated metallic titanium obtainable by the process according to any one of claims 1 to 6.
8. Use of the activated titanium metal of claim 7 in the catalytic electrolysis of water to produce hydrogen gas.
9. The use according to claim 8, wherein the activated metallic titanium is used directly as an electrode for catalytic electrolysis of water to produce hydrogen;
or the activated metal titanium is used as a catalyst carrier for catalyzing and electrolyzing water to produce hydrogen.
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