METHOD OF BOOSTING HYDROGEN EVOLUTION ACTIVITY OF ELECTROCATALYSTS

Abstract

The present invention refers to methods of increasing the catalytic efficieny of Hydrogen Evolution Reactions (HER) electrocatalysts with a low external magnetic field. The present invention further includes electrochemical cells having an external magnetic field. The electrocatalyst is a metal or a compound with partially filled d-orbitals, more preferred a ferromagnetic or paramagnetic material with partially filled d-orbitals.

Claims

1. A process for enhancing a catalytic effect of a catalyst for an electrochemical hydrogen evolution reaction, comprising exposing the catalyst to an external magnetic field of between 65×10.sup.−6 mT and ≤170 mT during the hydrogen evolution reaction.

2. The process of claim 1, wherein the catalyst is a metal or compound with partially filled d-orbitals.

3. The process of claim 1, wherein the catalyst is a ferromagnetic or paramagnetic material.

4. The process of one of claim 1, wherein the catalyst is a ferromagnetic metal, ferromagnetic intermetallic compound, ferromagnetic transition metal oxide, ferromagnetic transition metal sulfide, ferromagnetic Heusler alloy, paramagnetic metal, paramagnetic intermetallic compound or paramagnetic transition metal phosphide.

5. The process of claim 4, wherein the ferromagnetic metal is selected from the group consisting of Fe, Co and Ni.

6. The process of claim 4, wherein the ferromagnetic intermetallic compound is selected from the group consisting of materials comprising two or more elemental metals of defined proportions which still show room temperature ferromagnetism.

7. The process of claim 4, wherein the ferromagnetic metal oxide is selected from the group consisting of compounds comprising oxygen and one or more metallic elements.

8. The process of claim 4, wherein the ferromagnetic metal sulfide is selected from the group consisting of compounds comprising sulfur and one or more metallic elements.

9. The process of claim 4, wherein the ferromagnetic Heusler alloy has a composition of TT′Z (half-Heusler) or T.sub.2T′R (full-Heusler), wherein T and T′ are selected from the group consisting of transition metals and R is an element from IUPAC group 13, 14 or 15.

10. The process of claim 4, wherein the paramagnetic metal is selected from the group consisting of Pt, Pd, Ru, Ir, Rh, Ag, Mo, Y, and W.

11. The process of claim 4, wherein the paramagnetic intermetallic compound is selected from the group consisting of materials comprising two or more elemental metals which still exhibit room temperature paramagnetism.

12. The process of claim 4, wherein the paramagnetic transition metal phosphide is selected from the group consisting of compounds comprising phosphorus and one or more metallic elements.

13. An electrochemical cell comprising an anode, a cathodic working electrode and an external magnetic field of ≤170 mT for increasing the efficiency of a hydrogen evolution reaction (HER).

14. The process of claim 6, wherein the materials comprising two or more elemental metals of defined proportions which still show room temperature ferromagnetism are a binary phase intermetallic compound of the formula
A.sub.xT.sub.y, wherein A=Fe, Co, or Ni, and T is selected from the group consisting of transition metals and x and y independently from one another represent an integer from 1 to 8.

15. The process of claim 14, wherein the binary phase intermetallic compound is selected from one or more of Fe.sub.3Cr, Fe.sub.3Ga.sub.4, Fe.sub.3Pt, FeRh, CoGa, CoPt, Co.sub.3Ti, Ni.sub.3Fe, Ni.sub.3Mn or NiPt.

16. The process of claim 7, wherein the ferromagnetic metal oxide is a binary metal oxide having the formula T.sub.xO.sub.y, wherein T is selected from the group consisting of transition metals; or a ternary metal oxide having the formula T.sub.xT′.sub.1-xO.sub.y, wherein T and T′ are independently selected from the group consisting of transition metals which exhibit ferromagnetism at the working temperature of the HER-cell and x and y independently selected from one another and represent an integer from 1 to 8.

17. The process of claim 16, wherein the ferromagnetic metal oxide is selected from one or more of Fe.sub.3O.sub.4, Fe.sub.2O.sub.3, NiO, Co.sub.3O.sub.4, ZnFe.sub.2O.sub.4, NiFeZnO.sub.4, MnFe.sub.2O.sub.4, CoFe.sub.2O.sub.4 and NiFe.sub.2O.sub.4.

18. The process of claim 8, wherein the ferromagnetic metal sulfide comprises a. binary metal oxides having the formula T.sub.xS.sub.y, wherein T is selected from the group consisting of transition metals; and/or b. ternary metal oxides have the formula T.sub.xT′.sub.1-xS.sub.y, wherein T and T′ are selected from the group consisting of transition metals which exhibit ferromagnetism at the working temperature of the HER-cell and c. wherein x and y independently from one another represent an integer from 1 to 8.

19. The process of claim 18, wherein the ferromagnetic metal sulfide is selected from one or more of Fe.sub.3S.sub.4, Fe.sub.7S.sub.8, Ni.sub.3S.sub.4, Co.sub.3S.sub.4, NiFe.sub.2S.sub.4, ZnFe.sub.2S.sub.4 and NiFeZnS.sub.4.

20. The process of claim 9, the ferromagnetic Heusler alloy is selected from one or more of Mn.sub.2NiSb, Ni.sub.2MnGa, Co.sub.2MnGa, Cu.sub.2MnSb, NiCrSi, NiCrGe and NiCrGa.

21. The process of claim 11, wherein the paramagnetic intermetallic compound is PtRu and/or PtIr.

22. The process of claim 12, wherein the paramagnetic transition metal phosphide is NbP, MoP, WP and/or WP.sub.2.

23. The electrochemical cell of claim 13, wherein the external magnetic field surrounds the cell and the cathodic working electrode and said external magnetic field is generated by a permanent magnet or electromagnet.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0012] The accompanying drawings are included to provide a further understanding of the present invention. The drawings illustrate exemplary embodiments of the present invention and, together with the description, serve to explain the principles of the present invention.

[0013] FIG. 1 shows an exemplary experimental set-up for the production of hydrogen through electrochemical water splitting in the presence of a magnetic field.

[0014] FIG. 2 shows the distance depended strength of magnetic field. The distance is measured between the indicated catalyst and the magnet.

[0015] FIG. 3 shows a comparison of the linear polarization curves of Ni foam with and without the magnetic field.

[0016] FIG. 4 shows the HER activity of Ni foam with and without the magnetic field at a fixed overpotential.

[0017] FIG. 5 shows a comparison of the HER activity of Ni plates with and without a magnetic field at a fixed overpotential.

[0018] FIG. 6 shows a comparison of the HER activity of a Co.sub.2MnGa single crystal with and without a magnetic field at a fixed overpotential.

[0019] FIG. 7 shows a comparison of the HER activity of Pt/C powder with and without a magnetic field at a fixed overpotential.

[0020] FIG. 8 shows a summary of the increase in HER efficiency for various electrocatalysts in the presence of a magnetic field.

DETAILED DESCRIPTION OF THE INVENTION

[0021] The present invention provides a simple method to increase the activity of HER catalyst with a magnetic field that is larger than the average magnetic field of the earth (which is about 65×10.sup.−6 mT). It was found that the catalytic activity of electrocatalysts can be increased by as much as 700% with only a small magnetic field of ≤170 mT. This dramatic enhancement of HER catalytic efficiency under a small magnetic field occurs in metals or compounds with partially filled d-orbitals.

[0022] For the hydrogen evolution reaction in water (electrolysis), the cathode is covered with the electrocatalyst and connected with electrical power. A negative potential is applied to the cathode and electrons are transferred to the cathode across the electrical circuit, and then injected into the electrocatalysts. The electrons are then further injected into the adsorbates, typically H.sup.+ or H.sub.2O to complete the reduction process. H.sub.2 bubbles are then produced continually at a given potential. The physical properties of the electrocatalysts, like electrical conductivity and carrier mobility, are extremely important for the HER catalytic activity.

[0023] In the electrochemical hydrogen evolution, the reaction which takes place at the cathode side can be described as 2H.sup.++2e.sup.−.fwdarw.H.sub.2. Theoretically, the minimum potential needed to start the reaction is 1.23 V under standard conditions (1 bar, 25° C.). However, in addition to the thermodynamics requirement, a larger potential (generally >1.6 V) is needed to actually drive the reaction. Part of the extra potential is due to the resistance of the electrolyte, electrodes, and the external circuit. Yet, the most important contribution comes from the overpotential (η) associated with driving the kinetics of the HER at the cathode interface. An electrocatalyst increases the rate of reaction by lowering the activation energy. Thus, the reaction occurs at a smaller potential.

[0024] Without wishing to be bound by this theory it is assumed that the HER process is governed by the d-band theory. In the HER process, hydrogen is first adsorbed on the active sites of the catalyst by the formation of a bond. The bonding is a result of the coupling between the H 1s-orbital and the metal d-orbitals. The HER efficiency is then to some extent decided by the strength of this coupling (bond). In addition, the HER process requires the transfer of one electron to the adsorbed hydrogen ions to complete the reduction reaction. This electron originates from the metal d-orbitals.

[0025] Electrons have two basic properties, spin and charge. Both of them need to be transferred in the HER process. For metals or compounds with partially filled d-orbitals, these electrons carry local magnetic moments and can “feel” an external magnetic field. Accordingly, the transfer of such electrons from d-orbitals will be influenced by a magnetic field which in turn will, therefore, have an impact on the HER efficiency.

[0026] Accordingly, the present method of increasing the electrochemical activity of catalysts for the Hydrogen Evolution Reactions (HER) is applicable to metals and compounds with partially filled d-orbitals, preferably ferromagnetic metals, ferromagnetic intermetallic compounds, ferromagnetic transition metal oxides, ferromagnetic transition metal sulfides, and ferromagnetic Heusler alloys. Yet, the method is also applicable to paramagnetic metals, paramagnetic intermetallic compounds, paramagnetic transition metal phosphides in an electrochemical cell having an anode, a cathodic working electrode, and an external magnetic field that circumscribing the cell and the cathodic working electrode.

[0027] In a preferred embodiment the ferromagnetic metals are selected from the group consisting of Fe, Ni, and Co. These metals have unpaired electrons in the d-orbitals and exhibit ferromagnetism due to the existence of long-range magnetic order.

[0028] In another preferred embodiment the ferromagnetic intermetallic compounds are selected from the group consisting of materials comprising two or more elemental metals of defined proportions (x and y) and still showing room temperature ferromagnetism. Preferred binary phase intermetallic compounds are those of the formula A.sub.xB.sub.y, wherein A=Fe, Co, or Ni, and B is selected from the group consisting of transition metals and x and y independently from one another represent an integer from 1 to 8. Typical binary phase intermetallic compounds which can be used in the present invention are Fe.sub.3Cr, Fe.sub.3Ga.sub.4, Fe.sub.3Pt, FeRh, CoGa, CoPt, Co.sub.3Ti, Ni.sub.3Fe, Ni.sub.3Mn, NiPt, etc.

[0029] In another preferred embodiment the ferromagnetic metal oxides are selected from the group consisting of compounds comprising oxygen and one or more metallic elements. The binary metal oxides have the formula of T.sub.xO.sub.3, wherein T is selected from the group consisting of transition metals. The ternary metal oxides have the formula T.sub.xT′.sub.1-xO.sub.y, wherein T and T′ are independently selected from the group consisting of transition metals which exhibit ferromagnetism at the working temperature of the HER-cell. x and y independently from one another represent an integer from 1 to 8 in the above formulae. Typical ferromagnetic metal oxide compounds which can be used in the present invention are Fe.sub.3O.sub.4, Fe.sub.2O.sub.3, NiO, Co.sub.3O.sub.4, ZnFe.sub.2O.sub.4, NiFeZnO.sub.4, MnFe.sub.2O.sub.4, CoFe.sub.2O.sub.4, NiFe.sub.2O.sub.4, etc.

[0030] In another preferred embodiment the ferromagnetic metal sulfides are selected from the group consisting of compounds comprising sulfur and one or more metallic elements. Binary metal sulfides have the formula T.sub.xS.sub.y, wherein T is selected from the group consisting of transition metals; ternary metal sulfides have the formula T.sub.xT′.sub.1-xS.sub.y, wherein T and T′ are selected from the group consisting of transition metals which exhibit ferromagnetism at the working temperature of the HER-cell. x and y independently from one another represent an integer from 1 to 8 in the above formulae. Typical ferromagnetic metal sulfide compounds which can be used in the present invention are Fe.sub.3S.sub.4, Fe.sub.7S.sub.8, Ni.sub.3S.sub.4, Co.sub.3S.sub.4, NiFe.sub.2S.sub.4, ZnFe.sub.2S.sub.4, NiFeZnS.sub.4, etc.

[0031] In another preferred embodiment the ferromagnetic Heusler alloys have a composition of TT′Z (half-Heusler) or T.sub.2T′R (full-Heusler), wherein T and T′ are selected from the group consisting of transition metals and R is in element from IUPAC group 13, 14 or 15. Typical ferromagnetic Heusler alloys which can be used in the present invention are Mn.sub.2NiSb, Ni.sub.2MnGa, Co.sub.2MnGa, Cu.sub.2MnSb, NiCrSi, NiCrGe, NiCrGa, etc. They exhibit ferromagnetism above 300 K.

[0032] In another preferred embodiment the paramagnetic metal is selected from the group consisting of Pt, Pd, Ru, Ir, Rh, Ag, Mo, Y, and W.

[0033] In another preferred embodiment the paramagnetic intermetallic compound is selected from the group consisting of materials comprising two or more elemental metals which still exhibit room temperature paramagnetism. Typical paramagnetic intermetallic compounds which can be used in the present invention are PtRu, PtIr, etc.

[0034] In another preferred embodiment the paramagnetic transition metal phosphides are selected from the group consisting of compounds comprising phosphorus and one or more metallic elements. Typical paramagnetic transition metal phosphides which can be used in the present invention are NbP, MoP, WP, WP.sub.2, etc.

[0035] It was very surprising that the increase in electrochemical activity occurred already at a magnetic field strength as low as ≤170 mT. It can be assumed that the increase of HER activity by a magnetic field is a result of the Magneto Hydrodynamic Effects (MHD). This would imply that the bigger the applied magnetic field, the faster of desorption of hydrogen bubbles and also the transport of hydrogen ions to the surface of the catalyst. Accordingly, it was assumed that an increase in magnetic field strength inevitably goes along with an increase in HER activity. Surprisingly, the catalysts defined and selected in the present invention work even better at lower magnetic field strength, e.g. at 170 mT, which is against all previous understanding. Without wishing to be bound by this theory it is believed that this is caused by modifying the spin structure of the catalysts, rather than the hydrogen bubbles and solution. Catalysts with unfilled d-orbitals have umpired electrons, the spin orientation of which can easily be controlled by a small magnetic fields, even as lower as 200 mT and lower.

[0036] The magnetic field strength in the present invention can be varied e.g. by varying the distance of the catalyst from a permanent magnet as shown in FIG. 2 or by using an electromagnet with variable magnetic field strength. The magnetic field strength at a given distance can be measured with a magnetometer.

Examples

[0037] The invention is explained in more detail below with reference to examples.

HER Experimental Setup

[0038] The experiment setup is shown in FIG. 1. The assessment of HER catalytic activities is performed on an Autolab PGSTAT302N potentiostat. A conventional three-electrode cell configuration was employed. A Ag/AgCl (3 M KCl) electrode was used as the reference electrode, and a graphite rod was used as a counter electrode. The electrolyte was 1 M KOH solution purified with Ar. The corresponding linear sweep voltammograms of various electrocatalysts were recorded with a scan rate of 1 mV/s. All potentials were referenced to a Reverse Hydrogen Electrode (RHE). For the HER activity assessment with an external magnetic field, a permanent NdFeB magnet (supermagnet, S-70-35-N) is used.

Preparation of Electrocatalysts

[0039] High-quality single bulk crystals of NbP are grown via a chemical vapor transport reaction using an iodine transport agent. A polycrystalline powder of NbP is synthesized by direct reaction of niobium and red phosphorus within an evacuated fused silica tube for 48 h at 800° C. The growth of bulk single crystals of NbP is then initialized from this powder by chemical vapor transport in a temperature gradient, starting from 850° C. (source) to 950° C. (sink) and a transport agent with a concentration of 13.5 mg cm.sup.−3 iodine (Alfa Aesar 99.998%).

[0040] Single crystals of Co.sub.2MnGa were grown using the Bridgman Stockbarger crystal growth technique. The polycrystalline sample was synthesized first by induction melting from high-quality stoichiometric amounts of elemental cobalt (99.999%), manganese (99.999%) and gallium (99.999%) in an alumina crucible. The induction-melted sample is then crushed into powder form and packed in a custom-designed sharp-edged alumina tube, which was sealed in a tantalum tube. The sample was heated to 1523 K and sintered for 10 h to ensure the homogeneity of the melt, and then slowly cooled to 1023 K.

[0041] For the preparation of Pt/C and Ni nano-powders for HER measurement, 8 mg of Pt/C or Ni powder were dispersed in 1 mL of solvent (Nafion solution (5 wt. %)/water/ethanol mixture, v/v=0.1:2.4:2.5). After ultrasonication, an aliquot of a 3 μL dispersion was pipetted onto a carbon paper (purchased from ZOLTEK™ Co. Ltd). After drying at 60° C. for 10 min, the carbon cloth with electrocatalysts can serve as the working electrode directly.

[0042] For the catalytic activity assessment of single crystals, e.g. NbP, or Co.sub.2MnGa, these were attached to a Cu wire with silver paint. After drying at 80° C. for 2 h, they can be used as working electrode directly.

Experimental Details

[0043] In the measurement process, all the catalysts are cycled to reach a stable state. The current is measured at a given potential first and measured again at the same conditions in the presence of a magnet. All measurements were performed at room temperature (about 23° C.).

[0044] FIG. 1 shows an exemplary experimental set-up for the production of hydrogen through electrochemical water splitting in the presence of a magnetic field. The experimental set-up includes an Ag/AgCl (3 M KCl) reference electrode, a graphite counter electrode, and the electrocatalysts as the working electrode. The applied magnetic field can be controlled by the distance between the hard magnet and the working electrode.

[0045] FIG. 2 shows the distance depended strength of magnetic field. The distance is measured between the indicated catalyst and the magnet. The magnetic field is measured by magnetometer.

[0046] FIG. 3 shows a comparison of the linear polarization curves of Ni foam with and without the magnetic field. It can be seen that a smaller potential is needed to deliver the same current density in the presence of a magnetic field.

[0047] FIG. 4 shows the HER activity of Ni foam with and without a magnetic field at a fixed overpotential. It can be seen that the current densities changed accordingly with and without a magnetic field. The current density is increased by 700% with a magnetic field of 170 mT.

[0048] FIG. 5 shows a comparison of the HER activity of Ni plates with and without a magnetic field at a fixed potential of −0.24 V vs RHE. The catalytic efficiency is increased by 25% with a magnetic field of 113 mT.

[0049] FIG. 6 shows a comparison of the HER activity of Co.sub.2MnGa with and without a magnetic field at a fixed potential of −0.33 V vs RHE. The HER catalytic efficiency is increased by 10% with a magnetic field of 39 mT.

[0050] FIG. 7 shows a comparison of the HER activity of Pt/C powder with and without a magnetic field at a fixed overpotential. The catalytic efficiency is increased by 32.4% with a magnetic field of 56 mT.

[0051] FIG. 8 shows a summary of the increase in HER efficiency for various electrocatalysts in the presence of a magnetic field.