METHOD FOR MANUFACTURING OF A POROUS ELECTRODE MATERIAL

Abstract

The present invention relates to a method for manufacturing of a porous electrode material, wherein the porous electrode material comprises transition metal phosphide on a porous structure comprising transition metal. The method comprises contacting elemental phosphorous and a porous structure comprising transition metal, and heating, in an inert atmosphere, the contacted elemental phosphorous and the porous structure comprising transition metal to a temperature in the temperature range of 300 to 1100 C., thereby reacting at least a part of the phosphorous and at least a part of the transition metal under formation of transition metal phosphide on the surface of the porous structure, thereby forming the porous electrode material. The present invention further relates to a porous electrode material obtainable by the method.

Claims

1. Method for manufacturing of a porous electrode material, wherein the porous electrode material comprises transition metal phosphide on a porous structure comprising transition metal, the method comprising: providing elemental phosphorous separated from the porous structure comprising transition metal, evaporating elemental phosphorous by heating, thereby forming a phosphorous vapour, contacting the phosphorous vapour and the porous structure comprising transition metal, and heating, in an inert atmosphere, the contacted elemental phosphorous and the porous structure comprising transition metal to a temperature in the temperature range of 300 to 1100 C., thereby reacting at least a part of the phosphorous and at least a part of the transition metal under formation of transition metal phosphide on the surface of the porous structure, thereby forming the porous electrode material.

2. (canceled)

3. The method according to claim 1, wherein the inert atmosphere is provided by an inert gas or by vacuum.

4. (canceled)

5. The method according to claim 1, wherein the evaporating is by heating to a temperature in the range of 300 to 800 C.

6. The method according to claim 1, wherein the contacting is by flowing the phosphorous vapour by a stream of inert gas such that the phosphorous vapour is brought in contact with the transition metal.

7. The method according to claim 1, wherein the inert atmosphere is provided by an inert gas, preferably Ar or N.sub.2.

8. The method according to claim 1, wherein the transition metal is nickel, and the transition metal phosphide is selected from the group consisting of Ni.sub.3P, Ni.sub.7P.sub.3, Ni.sub.5P.sub.2, Ni.sub.2.55P, NiP.sub.3, NiP, Ni.sub.8P.sub.3, Ni.sub.12P.sub.5, Ni.sub.5P.sub.4, NiP.sub.2, Ni.sub.2P, and Ni.sub.5P.sub.4, or combinations thereof.

9. The method according to claim 1, wherein the transition metal is cobalt and the transition metal phosphide is selected from the group consisting of Co.sub.1.94P, Co.sub.1.95P, Co.sub.2P, CoP, CoP.sub.2, CoP.sub.3, CoP.sub.4 or combinations thereof..

10. The method according to claim 1, wherein the transition metal is copper, and the transition metal phosphide is selected from the group consisting of Cu.sub.3P, CuP.sub.2, Cu.sub.2P.sub.7, Cu.sub.0.97P.sub.0.03, Cu.sub.2.82P, Cu.sub.0.985P.sub.0.015, Cu.sub.2.82P, Cu.sub.2.872P, CuP.sub.10, or combinations thereof.

11. The method according to claim 1, wherein the heating is heating to a temperature in the temperature range of 400 to 800 C.

12. The method according to claim 1, wherein the heating takes place during 0.5 to 24 hours.

13. The method according to claim 1, wherein the porous structure comprising transition metal, is provided in the form of a foam having a maximum average pore size of 1 mm or below, preferably 800 micrometers or below, more preferably 500 micrometers or below, most preferably 300 micrometers or below.

14. The method according to claim 11, wherein the metal foam has a porosity in the range of 25 and 99%, preferably 50 to 98%.

15. A porous electrode material obtainable from the method according to claim 1.

16. The method according to claim 5, wherein the contacting is by flowing the phosphorous vapour by a stream of inert gas such that the phosphorous vapour is brought in contact with the transition metal.

17. The method according to claim 6, wherein the inert atmosphere is provided by an inert gas, preferably Ar or N.sub.2.

18. The method according to claim 7, wherein the transition metal is nickel, and the transition metal phosphide is selected from the group consisting of Ni.sub.3P, Ni.sub.7P.sub.3, Ni.sub.5P.sub.2, Ni.sub.2.55P, NiP.sub.3, NiP, Ni.sub.8P.sub.3, Ni.sub.12P.sub.5, Ni.sub.5P.sub.4, NiP.sub.2, Ni.sub.2P, and Ni.sub.5P.sub.4, or combinations thereof.

19. The method according to claim 7, wherein the transition metal is cobalt and the transition metal phosphide is selected from the group consisting of Co.sub.1.94P, Co.sub.1.95P, Co.sub.2P, CoP, CoP.sub.2, CoP.sub.3, CoP.sub.4 or combinations thereof.

20. The method according to claim 7, wherein the transition metal is copper, and the transition metal phosphide is selected from the group consisting of Cu.sub.3P, CuP.sub.2, Cu.sub.2P.sub.7, Cu.sub.0.97P.sub.0.03, Cu.sub.2.82P, Cu.sub.0.985P.sub.0.015, Cu.sub.2.82P, Cu.sub.2.872P, CuP.sub.10, or combinations thereof.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0042] FIG. 1 is schematic illustration of a method according to an embodiment.

[0043] FIG. 2 is schematic illustration of a method according to an embodiment.

[0044] FIG. 3 discloses a SEM image of a Ni foam illustrating its porous structure.

[0045] FIG. 4 discloses a SEM image of nickel phosphide on the surface of a Ni foam.

[0046] FIG. 5 discloses a high magnification SEM image of nickel phosphide on the surface of a Ni foam.

[0047] FIG. 6 shows an X-ray diffraction (XRD) pattern of a nickel phosphide electrode.

[0048] FIG. 7 shows the polarization curve for a nickel phosphide electrode.

[0049] FIG. 8 illustrates durability data for a nickel phosphide electrode.

[0050] FIG. 9 discloses low- and high-magnification SEM images of cobalt phosphide on the surface of a cobalt foam.

[0051] FIG. 10 shows an energy dispersive X-ray (EDX) spectrum of the cobalt foam after phosphorization.

[0052] FIG. 11 reveals an X-ray diffraction (XRD) pattern of a cobalt phosphide electrode.

[0053] FIG. 12 shows the polarization curve for a cobalt phosphide electrode.

[0054] FIG. 13 discloses low- and high-magnification SEM images of a copper phosphide on the surface of a copper foam.

[0055] FIG. 14 shows an energy dispersive X-ray (EDX) spectrum of the copper foam after phosphorization.

[0056] FIG. 15 shows the polarization curve for a copper phosphide electrode.

DETAILED DESCRIPTION

[0057] The present invention will now be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments of the invention are shown. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided for thoroughness and completeness, and fully convey the scope of the invention to the skilled person.

[0058] The method for manufacturing of a porous electrode material, comprising contacting elemental phosphorous and a porous structure comprising transition metal, and reacting phosphorous and transition metal under formation of transition metal phosphide on the surface of the porous structure, as described herein is an efficient method resulting in an efficient porous electrode material which can be used for efficient production of hydrogen. It will be shown that efficient electrode material for hydrogen production is produced. For example an electrode material manufactured from nickel and phosphorus is efficient and may be produced from low cost raw material. Further, long term durability is provided with the materials disclosed. The use of the porous structure comprising transition metal, such as for example nickel, with the methods of embodiments results in durable and self-supporting electrode materials. Further, the methods described herein are characterised by, for example, in that they comprises few steps and a few compounds.

[0059] With reference to FIG. 1, an embodiment of the method is discussed. FIG. 1 schematically illustrates a method 100 for manufacturing of a porous electrode material. The method 100 comprises contacting 102 elemental phosphorous and a porous structure comprising transition metal and heating 104, in an inert atmosphere, the contacted elemental phosphorous and the porous structure comprising transition metal to a temperature in the temperature range of 300 to 1100 C., thereby reacting at least a part of the phosphorous and at least a part of the transition metal under formation of transition metal phosphide on the surface of the porous structure, thereby forming the porous electrode material. It is realised that the electrode material may be used for manufacturing of electrodes, such as cathodes, or the material may be used directly as electrodes.

[0060] A simplified method for manufacturing of a porous electrode is thereby provided. Moreover, the direct phosphorization of the transition metal offers a simple and straightforward approach to manufacturing self-supported low-cost electrodes that may be used as HER electrodes. The method is moreover scalable and thereby cost-effective.

[0061] In the methods for manufacturing of a porous electrode material, metallic nickel and elemental phosphorous may be reacted in a solid state method or a gas-transport method. The nickel phosphide will form through a direct redox reaction between Ni metal and solid or gaseous P species, for instance, 12Ni+5P=Ni.sub.12P.sub.5, 2Ni+P=Ni.sub.2P, 5Ni+4P=Ni.sub.5P.sub.4. The driving force of the reaction is the transfer of electrons from the electropositive Ni metal to the electronegative P.

[0062] Solid State Method

[0063] With reference to FIG. 2, a method for manufacturing of a porous electrode material is discussed. The method 200 takes place inside a heatable reactor. The contacting 202 is by depositing of a powder of solid elemental phosphorous on a surface of a porous structure consisting of nickel. It is realised that instead of a powder, a paste of elemental phosphorous could have been deposited, and that instead of nickel, another suitable transition metal could have been used. The reactor is filled with inert gas, and heated 204 to 400 C. to 600 C., whereby the phosphorous is reacted with a part of the nickel on the surface of the porous structure, under formation of nickel phosphide. The nickel phosphide is formed on the surface of the porous structure. The resulting porous electrode material thus has nickel phosphide on the surface of a porous transition metal structure. The thus obtained porous material is efficient for use as an electrode in hydrogen production.

[0064] The reacting of the transition metal with the elemental phosphorous in the solid-state chemistry fashion may be referred to as a solid-state method as the transition metal and the elemental phosphorous are both in their solid states as they are brought in contact with each other.

[0065] According to one embodiment the inert atmosphere is provided by an inert gas or by vacuum. Chemical reactions other than the formation of transition metal phosphide are thereby mitigated. The inert gas may be Ar or N.sub.2.

[0066] In the following the method of manufacturing a porous electrode material comprising Ni.sub.xP.sub.y on a porous structure comprising Ni using the solid-state method will be described.

[0067] The elemental phosphorous (P0) for use in the solid state method may be in various forms as long as it comprises elemental phosphorus (i.e., P0). Preferably, the elemental phosphorus is amorphous red P. Hence a cost efficient and nontoxic elemental phosphorus is provided.

[0068] The nickel in the porous structure may be of different forms as long as it comprises metallic nickel (i.e., Ni0), and is capable of reacting with P0 to form nickel phosphides. The Ni compound may be, for example, commercially available porous nickel foam providing a large surface area for improved formation of nickel phosphide and improved catalytic properties.

[0069] The Ni foam may have an average porosity ranging between 50% and 98%. In a preferred embodiment, the average porosity of the Ni foam ranges between 70% and 98%; even more preferably, the average porosity of Ni foam ranges between 85% and 98%.

[0070] The maximum average pore size of the Ni foam may be 800 m. In a preferred embodiment, the maximum average pore size of the Ni foam is 500 m; even more preferably, the maximum average pore size of the nickel foam is 300 m. As an example, FIG. 3 discloses a scanning electrode image of a Ni foam illustrating its porous structure.

[0071] The solid-state method of the present invention is preferably carried out in a closed system under inert atmosphere of argon, nitrogen or vacuum.

[0072] The solid-state method may be carried out under a low stream of argon flow. The temperature of solid-state reaction may for instance be in the range of 300 to 1100 C., more preferably 400 to 600 C.; most preferably, it is about 500 C.

[0073] Looking at binary alloy nickel-phosphorus phase diagram, it may be concluded which temperature is necessary to achieve the thermodynamic equilibrium of the specific nickel phosphide compound so that the thermodynamically most stable modification is manufactured.

EXAMPLE 1 WITH SOLID STATE METHOD

[0074] In the phosphorization methods of the invention, a specific self-supported NiP/Ni composite or NiP electrodes was obtained by varying the Ni:P molar ratio, tempering temperature, and tempering time as will be describe in the following.

[0075] Ethanol-based wet paste containing of 0.1 g of P red was homogeneously added on top surface of about 0.6 g of Ni foam (corresponding to a Ni:P molar ratio of about 3:1) and left to dry. The obtained material was tempered at 400 C. for 6 h and then at 600 C. for 2 h in tube furnace with argon flow of 100 mL min.sup.1. Through the solid-state method a NiP/Ni composite electrode was obtained.

EXAMPLE 2 WITH SOLID STATE METHOD

[0076] A NiP electrode was manufactured with the solid-state method as described below.

[0077] For the preparation of the electrode, the procedure of Example 1 was repeated with the exception of that 0.3 g of P red (corresponding to a Ni:P molar ratio of about 1:1) was used.

[0078] It should be noted that the molar ratio of Ni:P may be used to vary the ratio of transition metal to transition metal phosphide in the porous electrode material. Hence the porous electrode material may comprise transition metal.

[0079] Gas Transport Method

[0080] In the following manufacturing of a porous electrode material using the gas transport method will be described. For the experiments disclosed the porous electrode material is manufactured with phosphor red and the porous structure comprising transition metal is provided by using a Ni, a Co or a Cu foam. The person skilled in the art realizes that other transition metals may also be used as discussed below.

[0081] In the first set of experiments using a Ni foam the gas transport method was carried out according to the following. Ni foam was purchased from Heze Jiaotong Group (110 ppi, 0.3 mm thick), and red phosphorous (P) was obtained from Sigma-Aldrich (97.0%). Prior to phosphorization, the Ni foam was cleaned by ultrasonication in 6 M HCl for 5 min to remove the surface oxide layer, washed sequentially by water and acetone, and finally dried at 50 C. for 10 min. Subsequently, a piece of Ni foam with an area of ca. 2.52.5 cm.sup.2 was loaded into a ceramic boat, with ca. 1 g of P red placed 2 cm away from the Ni foam in the upstream side. Afterwards, the boat was put into a tube furnace (Garbolite). The furnace was purged with nitrogen (N.sub.2, 99.999%) at a flow rate of 800 SCCM for 30 min, heated to 500 C. at 5 C. min.sup.1, and kept at this temperature for 6 h. The furnace was then cooled down to 250 C. at 5 C. min.sup.1 and maintained at this temperature for another 6 h. Finally, the furnace was naturally cooled down to room temperature. The N.sub.2 flow was maintained throughout the whole tempering process. The resultant foam was then washed sequentially with deionized water, ethanol and acetone, then dried in a N.sub.2 flow.

EXAMPLE 3

Evaluation of Integrated NiP Electrode with the Gas-Transport Method

[0082] With reference to FIGS. 3 to 8 nickel phosphide electrodes manufactured with the gas-transport method have been evaluated and are discussed. Electrochemical measurements were conducted at room temperature (25 C.) in a typical three-electrode cell using the as-synthesized self-supported nickel phosphide porous structure, or foam, as the working electrode, a graphite plate as the counter electrode and a saturated calomel electrode (SCE) as the reference. The electrolyte was 0.5 M H.sub.2SO.sub.4 solution (pH=0.28). For comparison, the electrocatalytic performance of a polished flat Pt sheet and a bare Ni foam was also evaluated. Before each electrochemical measurement, the electrolyte was deaerated by N.sub.2 bubbling for 30 min.

[0083] Scanning electron microscopy, SEM was used to evaluate the structure of the nickel phosphide formed using the gas transport method disclosed above.

[0084] FIG. 3 discloses a SEM image of a Ni foam prior to application of the gas-transport method and may be used for reference.

[0085] FIG. 4 discloses a SEM image of a Ni foam illustrating that the porous structure after using the gas transport method performed at 500 C. for 6 h as discussed above. Upon inspection of the Ni foam surface it may be deduced that the macroporous morphology of the initial porous Ni foam remains essentially unchanged, i.e. the porous structure of the Ni foam is maintained. The scanning electron image of FIG. 4 reveals, however, that a microstructure is formed on the surface of the Ni foam. FIG. 5 discloses a high magnification SEM image revealing the surface microstructure formed by the gas transport method. The SEM image illustrates that densely-packed nanosheets are formed on the surface of the Ni foam. For these conditions nanosheets having thicknesses ranging from several tens to one hundred nanometers are formed.

[0086] Scanning electron microscopy (SEM) examination on samples where the phosphorization was also carried out at other temperatures ranging from 400 C., to 800 C. while keeping other parameters unchanged, reveals that the sheet-like morphology only appears for phosphorization at temperatures ranging between 400 and 500 C.

[0087] To determine the composition of the nanostructured features, i.e. of the the nanosheets, energy dispersive X-ray (EDX) spectrum on the nanosheets were performed and verify that the nanosheets consist of Ni and P as no peaks from other elements were detected. FIG. 6 shows an X-ray diffraction (XRD) pattern revealing the phase constitutes of the nickel phosphide formed by the gas transport method, taking raw nickel foam as a reference. Quantitative analysis of XRD patterns (not shown) of the nickel phosphide nanosheets show that the sample is composed of a mixture of hexagonal Ni.sub.5P.sub.4 (ICDD no. 04-014-7901) and Ni.sub.2P (ICDD no. 04-003-1863), where Ni.sub.5P.sub.4 is the major component accounting for ca. 80 wt %. Notably, the intensity of the diffraction peaks from metallic Ni becomes fairly weak after phosphorization, indicating an almost complete conversion of Ni to nickel phosphide as a result of the gas-transport method according to this embodiment. Moreover, SEM-EDX mapping shows that Ni and P are uniformly distributed over the surface of the Ni foam.

[0088] To evaluate hydrogen evolution reaction (HER) performance, self-supported NiP electrodes obtained after gas-transport synthesis at 500 C. for 6 h was exposed to N.sub.2-saturated 0.5 M H.sub.2SO.sub.4 aqueous solution as the working electrode.

[0089] FIG. 7 shows the polarization curve for this self-supported nanostructured nickel phosphide (Ni.sub.5P.sub.4Ni.sub.2P nanosheet) electrode in 0.5 M H.sub.2SO.sub.4 with a scan rate of 10 mV s.sup.1. A bare Pt plate were also examined for comparison. An IR correction was made in the given LSV data to reflect the intrinsic behaviour of catalysts. The self-supported nickel phosphide electrode exhibits significantly improved cathodic current, revealing its greatly enhanced electrocatalytic activity toward HER. Although Pt depicts expected HER performance with near-zero overpotential, the directly architected nickel phosphide electrode also functions as an efficient HER cathode with a small onset overpotential of 54 mV and further negative potential leads to a rapid rise of hydrogen evolution cathodic current. Furthermore, this self-supported nickel phosphide electrode affords current densities of 10, 20 and 100 mA cm.sup.2 at overpotentials of 120, 140, and 200 mV, respectively. These overpotentials compare favourably to the behaviour of most previously reported non-precious HER catalysts in acidic solutions including Mo- and W-based sulphide catalysts.

[0090] Hence, efficient nickel phosphide electrodes for HER were obtained by the gas transport method.

[0091] The phosphide electrodes obtained by the gas transport method are moreover stable and durable as may be shown by performing an accelerated degradation test (ADT). After performing the ADT for 1000 continuous cycles, it is clear that this electrode merely exhibited a slight current decay, with an overpotential increased by less than 18 and 21 mV to achieve current densities of 10 and 100 mA cm.sup.2, respectively. This nickel phosphide electrode was also tested at a constant potential of 200 mV vs. RHE more than 70 h, as shown in FIG. 8. The catalytic electrode merely showed a slight decay in current as function of time, and finally reached to a stable state at 13 mA cm.sup.2. These results provide evidence that this self-supported nanostructured nickel phosphide catalytic electrode reveals an excellent catalytic activity and long-term durability for the HER.

[0092] According to another embodiment the manufacturing of a porous electrode material using the gas transport method comprises providing 0.1 g of amorphous red P as elemental phosphor which is heated in a first reaction zone in a tube furnace at a vaporisation temperature T.sub.1 of about 400 C. A porous structure consisting of about 0.6 g of Ni foam, corresponding to a Ni:P molar ratio of about 3:1, is further provided at a temperature T.sub.2 of 500 C. in a second reaction zone in the tube furnace. The first and second reaction zones are separated at a distance.

[0093] An Ar flow of 100 mL min.sup.1 may be used to feed the phosphorous vapour formed in the first reaction zone to the heated Ni foam in the second reaction zone. Hence the phosphorous vapour is brought in contact with the Ni foam such that nickel phosphide may be formed.

[0094] According to yet another embodiment the Ni:P molar ratio is about 1:1, i.e. 0.3 g of P red may be used in the previous embodiment.

[0095] It is realised that the porous transition metal phoshide electrodes provided according to embodiments provide efficient catalytic activity and long-term stability, and durability even in acidic medium.

[0096] The metal phosphide electrode may comprise Ni.sub.5P.sub.4Ni.sub.2P nanosheets which may be directly utilized as a cathode for electrocatalytic reactions.

EXAMPLE 4

Evaluation of Integrated CoP Electrode with the Gas-Transport Method

[0097] With reference to FIGS. 9 to 12 cobalt, Co, phosphide electrodes manufactured with the gas-transport method have been evaluated and are discussed.

[0098] FIG. 9 discloses low- and high-magnification SEM images of a Co foam illustrating that the porous structure after using the gas transport method performed at 500 C. for 3 h. The skilled person in the art, however, realizes that other temperature rages such as 400-800 C. may be used, such as a time duration of 0.5-24 h. Upon inspection of the Co foam surface it may be deduced that the macroporous morphology is preserved, i.e. the porous structure of the Co foam is maintained, see the low-magnification SEM image in the upper portion of FIG. 9. Microscopically, the foam surface is covered with randomly oriented nanorods, see the high-magnification SEM image in the lower portion of FIG. 9.

[0099] FIG. 10 shows an energy dispersive X-ray (EDX) spectrum of the cobalt foam after phosphorization in red phosphorous vapour at 500 C. for 3 h. The EDX spectrum verifies that the formed porous structure consists of

[0100] Co and P as no peaks from other elements were detected.

[0101] FIG. 11 reveals an X-ray diffraction (XRD) pattern of a cobalt phosphide foam. Diffractions from CoP.sub.2, Co.sub.2P and CoP.sub.3 were detected, verifying that the resulting porous cobalt phosphide foam has mixed crystal phases comprising CoP.sub.2, Co.sub.2P and CoP.sub.3, with CoP.sub.2 being the major phase.

[0102] To evaluate hydrogen evolution reaction (HER) performance, self-supported CoP electrode obtained after gas-transport synthesis at 500 C. for 3 h was exposed to acidic and alkaline solutions. FIG. 12 shows the electrocatalytic activity of the fabricated porous cobalt phosphide foam towards hydrogen evolution in both acidic and alkaline solution. In the upper diagram of FIG. 12 the polarization curve for a cobalt phosphide electrode exposed to N.sub.2-saturated 0.5 M H.sub.2SO.sub.4 aqueous solution as the working electrode is shown. In the lower diagram of FIG. 11 a cobalt phosphide electrode exposed to 1.0 M KOH aqueous solution as the working electrode is shown. From the measurements it is clear that the directly architected cobalt phosphide electrode also functions as an efficient HER cathode with a small onset overpotential and where further negative potential leads to a rapid rise of hydrogen evolution cathodic current.

[0103] These results provide evidence that this self-supported nanostructured cobalt phosphide catalytic electrode reveals an excellent catalytic activity for the HER. Hence, efficient cobalt phosphide electrodes for HER were obtained by the gas transport method.

EXAMPLE 5

Evaluation of Integrated CuP Electrode with the Gas-Transport Method

[0104] With reference to FIGS. 13 to 15 copper, Cu, phosphide electrodes manufactured with the gas-transport method have been evaluated and are discussed.

[0105] FIG. 13 discloses low- and high-resolution SEM images of a Cu foam illustrating that the porous structure after using the gas transport method performed at 500 C. for 6 h. The skilled person, in the art, however, realizes that other temperature rages such as 400-800 C. may be used for example 0.5-24 h. Upon inspection of the Cu foam it may be deduced that the macroporous morphology is preserved, i.e. the porous structure of the Cu foam is maintained, see the low-magnification SEM image in upper portion of FIG. 13. Microscopically, the foam surface is covered with a high density of short nanorods, see the high-magnification SEM image lower portion of FIG. 13.

[0106] FIG. 14 shows an energy dispersive X-ray (EDX) spectrum of the copper foam after phosphorization in red phosphorous vapour at 500 C. for 6 h. The EDX spectrum verifies that the formed porous structure consists of Cu and P as no peaks from other elements were detected. Hence, an efficient manufacturing of copper phosphide electrodes was also obtained by the gas transport method.

[0107] To evaluate hydrogen evolution reaction (HER) performance, self-supported CuP electrode obtained after gas-transport synthesis at 500 C. for 6 h was exposed to 0.5 M H.sub.2SO.sub.4. FIG. 15 shows the electrocatalytic activity of the fabricated porous copper phosphide foam towards hydrogen evolution in 0.5M H.sub.2SO.sub.4. From the measurement it is clear that the directly architected copper phosphide electrode also functions as an efficient HER cathode with a small onset HER overpotential of 84 mV and where further negative potential leads to a rapid rise of hydrogen evolution cathodic current.

[0108] In the above experiments the transition metals Ni, Co, and Cu have been exemplified. The skilled person in the art, however, realizes that other transition metals such as Sc, Ti, V, Cr, Mn, Fe, or Zn may be used when providing a porous electrode material comprising transition metal phosphide on a porous structure comprising transition metal.

[0109] To this end, the transition metal may be selected from the group of transition metals of the periodic table.

[0110] The wording transition metal shall be understood as an element whose atom has a partially filled d sub-shell, or which can give rise to cations with an incomplete d sub-shell. The transition metals therefore comprise any element in the d-block, i.e. atoms of the elements having between 1 and 10 d electrons, of the periodic table, which includes groups 3 to 12 on the periodic table. The f-block lanthanide and actinide series are, however, also to be understood as transition metals also referred to as inner transition metals.

[0111] It is further realised that, for example, experimental parameters, materials or compounds referred to or used with reference to an example with the solid state method may be relevant also with regard to the gas transport method, and vice versa.

[0112] The person skilled in the art further realizes that the present invention by no means is limited to the preferred embodiments described above. On the contrary, many modifications and variations are possible within the scope of the appended claims. Additionally, variations to the disclosed embodiments can be understood and effected by the skilled person in practicing the claimed invention, from a study of the drawings, the disclosure, and the appended claims. In the claims, the word comprising does not exclude other elements or steps, and the indefinite article a or an does not exclude a plurality. The mere fact that certain measures are recited in mutually different dependent claims does not indicate that a combination of these measured cannot be used to advantage.