阅读说明：本技术 具有铜铁矿氧化物abo2的用于析氢反应（her）的电催化剂 (With delafossite oxide ABO2Electrocatalyst for Hydrogen Evolution Reaction (HER) of ) 是由 C·费尔泽 G·李 A·麦肯齐 S·金 于 2019-09-19 设计创作，主要内容包括：本发明涉及包含具有式ABOx的化合物的材料,其中x为>1.5且≤2.5,A独立地选自IUPAC第10和11族的过渡金属,和B独立地选自IUPAC第6、7、8或9族的过渡金属或IUPAC第13族的主族元素,作为用于析氢反应(HER)的高度活性催化剂。(The invention relates to a material comprising a compound having the formula ABOx, wherein x is >1.5 and ≤ 2.5, A is independently selected from IUPAC group 10 and 11 transition metals, and B is independently selected from IUPAC group 6, 7, 8 or 9 transition metals or IUPAC group 13 main group elements, as a highly active catalyst for Hydrogen Evolution Reactions (HER).)

HER catalytic material comprising a compound having formula (I)

ABOx (I)

Wherein

x is more than 1.5 and less than or equal to 2.5,

a is independently selected from transition metals of IUPAC groups 10 and 11, and

b is independently selected from a transition metal of IUPAC group 6, 7, 8 or 9 or a main group element of IUPAC group 13.

2. Catalytic material according to claim 1, wherein

x is 2, and

a is independently selected from: pt, Pd or Ag, and

b is independently selected from: co, Al, Cr, Fe, In, Nd or Rh.

3. Catalytic material according to claim 1 or 2, wherein

The compound is PdCoO₂Or PtCoO₂。

4. Process for the manufacture of a compound according to formula (I)

ABOx (I)

Wherein

x is more than 1.5 and less than or equal to 2.5,

a is independently selected from transition metals of IUPAC groups 10 and 11, and

b is independently selected from transition metals of IUPAC group 6, 7, 8 or 9 or main group elements of IUPAC group 13

By mixing the "A" -halide with the "B" -oxide and heating the mixture to 600-1000 ℃.

5. Use of a compound according to formula (I) as a catalyst

ABOx (I)

Wherein

x is more than 1.5 and less than or equal to 2.5,

a is independently selected from transition metals of IUPAC groups 10 and 11, and

b is independently selected from a transition metal of IUPAC group 6, 7, 8 or 9 or a main group element of IUPAC group 13.

6. Use according to claim 5 as HER catalyst.

Prior Art

US4748144A discloses mixed oxides having a delafossite-type crystal lattice structure for the conversion of synthesis gas into linear alcohols and aldehydes. The mixed oxide may be represented by the formula: cu_xM_aFe_bO_2xWherein M is selected from Cr and Al, and a and b are equal or almost equal to x.

EP2127731A1 provides hydrothermally treated NaAlO₂And Ag₂O to obtain Pyrite type AgAlO₂A material. The material can be used as a catalyst for burning carbon without corroding the supporting honeycomb structure.

US2008/O112870a1 provides compounds free of precious metal elements for ammonia (NH)₃) And Carbon Oxide (CO) oxidation. The compounds comprise a basic (alkaline earth) component (Mg, Ba or K), a transition metal (V, Cr, Mo, Mn, Fe, Co, Ni, Cu, Zn, Ag or combinations thereof) and a metal oxide support.

US20090321244a1 discloses a photocatalyst comprising an element selected from the group consisting of: cu, Al, Ti, Ga, Cd, Zn, W, Fe, Sn, Si, In, or any combination thereof. Exemplary catalyst compounds include CuAlO₂、TiO₂、CuO、Cu₂O、NiO、GaAs、GaP、CdSe、ZnO、WO₃、Fe₂O₃、SnO₃、SiC、CuGaO₂And CulnO₂Or any combination thereof. It can convert water to hydrogen and oxygen, and more specifically, to hydrogen and oxygen using sunlight.

Trari et al International Journal of Hydrogen Energy,2004 reported that delafossite CuAlO₂And (4) synthesizing. It can be used as hydrogen evolution catalyst. It only works in alkaline media and no photoactivity is observed at pH less than 7.

Y. kim et al ball. korean chem. soc.2014 reported the synthesis of Ga from Ga by high temperature solid state synthesis₂O₃And CuO to synthesize polycrystalline CuGaO with delafossite structure₂And (3) granules. Using synthetic CuGaO₂The pellets act as photoelectrodes and the reduction of photoelectrochemical water to molecular hydrogen under irradiation with UV light is demonstrated to be at a higher potential than the flat band potential.

EP-2407419-a 1 describes a solution by separating an oxygen-evolving photocatalyst and a hydrogen-evolving photocatalyst by a layer of electrically conductive separator.

US-A-2012/0145532 discloses the use of broad spectrum excitation of noble metal core/semiconductor shell hybrid nanoparticles for unassisted photocatalytic water splitting. The metal core/semiconductor shell composite nanoparticles comprise a noble metal (e.g., Au, Ag, Pt, Pd, Cu,or noble metal alloy) core coated with a wide bandgap semiconductor photocatalyst (e.g., TiO) transparent to optical excitation in the visible and Near Infrared (NIR) spectral ranges coincident with the plasma absorption band of the metal core₂、ZnS、Nb₂O₅)。

US-A-2015/0010463 relates to A photocatalyst for the generation of hydrogen from water using visible light irradiation comprising nanocrystalline cobalt (II) oxide nanoparticles.

Object of the Invention

It is an object of the present invention to provide a more equivalent and more efficient catalyst for Hydrogen Evolution Reactions (HER). It is a particular object of the invention to improve the intrinsic electrochemical activity by optimizing the conductivity and carrier mobility for HER catalysts. This will facilitate electron transfer between the catalyst surface and the adsorbate, which in turn will accelerate the reaction kinetics of the HER. At the same time the catalysts should have a high catalytic activity towards HER, so that they can be used for large-scale hydrogen production. It would be preferable to provide a catalyst as close to the most effective as possible, for example Pt, which requires only 30mV of overpotential to deliver 10mA cm^-2The current density of (1). Furthermore, the cost of such catalysts should be lower than the cost of known catalysts, in particular lower than the cost of pure platinum. In addition, the catalysts should exhibit high chemical stability and durability to allow stable and extended lifetime of the photo/electrochemical cells, so that they can generate hydrogen for several days or even months in succession.

Summary of The Invention

The present invention provides HER catalytic materials comprising compounds having the formula ABO_x(I) A ferrihydrite oxide compound. In the formula (I)

x is between 1.5 and 2.5 and is preferably 2.

A is independently selected from transition metals of groups 10 and 11 of IUPAC; and

b is independently selected from a transition metal of IUPAC group 6, 7, 8 or 9 or a main group element of IUPAC group 13. The present invention also provides a simple way to economically and large-scale produce these delafossite oxides of formula (I).

The catalyst can be used directly as a hydrogen reduction electrode in a photo/electrochemical cell. The catalyst shows remarkable properties in acidic media, with low overpotential and excellent stability over time. The catalyst according to the invention operates at a much lower overpotential than pure Pt at high current densities.

Brief description of the drawings

FIG. 1: PdCoO₂The crystal structure of (1).

FIG. 2 a: PdCoO₂SEM image of single crystal.

FIG. 2 b: PdCoO₂Magnified SEM image of single crystal.

FIG. 3: EDS analysis of single crystals.

FIG. 4: PdCoO₂Resistance temperature relationship of the single crystal.

FIG. 5: images of electrocatalytic systems.

FIG. 6: cu line, 20% Pt/C and PdCoO₂HER polarization curve of single crystal.

FIG. 7: polarization curves in a large window of applied potential.

FIG. 8: 20% Pt/C and PdCoO₂Tafel plot of single crystal.

FIG. 9: PdCoO₂The current response of the electrocatalyst is timed at the following overpotential with current-time (I-t): 50mV in the initial test, and 40mV after two weeks of exposure in air.

Detailed Description

The invention relates to a HER catalytic material comprising a compound having the delafossite structure of formula (I)

ABOx (I)

Wherein

x is more than 1.5 and less than or equal to 2.5,

a is independently selected from transition metals of IUPAC groups 10 and 11, and

b is independently selected from a transition metal of IUPAC group 6, 7, 8 or 9 or a main group element of IUPAC group 13.

In a preferred embodiment

X is 2, and

a is independently selected from: pt, Pd or Ag, and

b is independently selected from: co, Al, Cr, Fe, In, Nd or Rh.

Optimization ofSelecting a delafossite oxide compound PdCoO₂And PtCoO₂。PdCoO₂And PtCoO₂Has a layered structure and is crystallized in a trigonal space group by [ A ]]Layer and [ BO₂]An alternating stacked configuration of plates along the c-axis. Most delafossite oxides are insulators, but some are, for example, PdCoO₂、PdCrO₂Or PtCoO₂Is an excellent metal. The in-plane conductivity at room temperature is only about 3 μ Ω cm, which is even higher than that of pure metals such as Pd, Cu and Au. However, their carrier density is about 1.6 x 10²²cm^-3. This is one third of the 3d transition metal. This results in a long mean free path length of up to 0.6nm, which is the longest of any known large carrier density metals. Considering that the "B" element is much cheaper than platinum and that oxygen is free, the cost of the catalyst can be reduced by as much as 75%. However, HER activity is even higher than that in>10mA cm^-2Pure platinum activity at high operating current densities.

The "A" -halide, e.g. chloride, bromide or iodide, can be mixed with the "B" -oxide, e.g. by co-milling the two compounds, preferably in an inert gas (e.g. N)₂Ar) atmosphere for 10 to 60 minutes to manufacture the delafossite oxide catalyst according to the present invention. The mixed powder is then heated to 600-. Finally, the composition is cooled to room temperature at a rate of 70-120 deg.C/hr, preferably 80-100 deg.C/hr, most preferably at about 90 deg.C/hr. This reaction is preferably carried out in a sealed tube, for example a quartz tube, preferably at 10^-3And 10^-4Pa between Pa.

General Properties

The electrocatalysts of the invention exhibit very low resistivity at room temperature, which is 5The temperature range of-300K is in the range of 0.05-3 μ Ω cm. This promotes easy electron transfer between the catalyst and the electrolyte. Furthermore, the present electrocatalyst shows higher activity under acidic conditions than Pt foils. Delivering 10mA/cm²The overpotential of the current density of (a) is only 33 mV. The tafel slope is as low as 30mV/dec in acidic (pH ═ 0) media. All these values are lower than the values for Pt foil (10 mA/cm)²71mV, Tafel slope of 74mV/dec) and even comparable to nano Pt/C catalyst (10 mA/cm)²The lower 28mV, Tafel slope 34 mV/dec). The exchange current density was determined to be 0.795mA/cm²This is higher than the exchange current density of the Pt/C catalyst (which is 0.518 mA/cm)²). The high chemical stability and electrochemical activity of the electrocatalyst did not change even after 3 months of exposure of the compound to air.

The electrocatalyst of the invention is composed of compounds having the structure ABOx delafossite, where x is>1.5 and 2.5, a is independently selected from transition metals of IUPAC groups 10 and 11, and B is independently selected from transition metals of IUPAC groups 6, 7, 8 or 9 or main group elements of IUPAC group 13. For example, the ABOx compound may be grown on a conductive substrate such as Ni foam, carbon cloth, or may be mixed with graphene to improve mobility and conductivity. However, it has been unexpectedly discovered that the ABOx compounds of the invention can be used directly as working electrodes in single crystal form. The electrodes in this case have a thickness of about 0.5 to 1.5X 0.5 to 3.0X 0.05 to 1.0mm³Preferably about 1X 2X 0.1mm³The size of (c). The monocrystalline electrode can then be attached to a wire, such as a Cu wire, for example with silver paint.

Examples

The present invention is explained in more detail below with reference to examples.

Reagent grade PdCl₂The powders of (99.99 +% purity, Alfa Aesar) and CoO (99.995% purity, Alfa Aesar) were milled together under an inert gas atmosphere for about one hour. Then at 5X 10^-4The mixed powder was sealed in a quartz tube under vacuum of Pa. The sealed quartz tube was heated to 800 ℃ for 5 hours in a shaft furnace and cooled down to 740 ℃ at a rate of 7.5 ℃/hour and held at this temperature for 30 hours. Finally, the furnace was removed from the furnace at a rate of 90 ℃/hourCooling to room temperature at 740 ℃.

Analytical method

An X-ray powder diffraction pattern was obtained from a D8 advanced X-ray diffractometer (Bruker, AXS) using Cu ka radiation. The microstructure of the sample was examined by scanning electron microscopy (SEM, FEI Quanta 200F) with energy dispersive X-ray spectroscopy (EDX) capability. Transmission measurements were performed in a 4He cryostat (Quantum Design) using standard four probe ac techniques.

HER catalytic measurements were performed on an Autolab PGSTAT302N using an impedance module electrochemical workstation with a conventional three-electrode cell configuration. An Ag/AgCl (3M KCl) electrode was used as a reference electrode, and a carbon rod was used as a counter electrode. The electrolyte was 0.5M H₂SO₄The solution was purged with Ar before use. Using PdCoO₂The single crystal electrode recorded a linear sweep voltammogram at a sweep rate of 1 mV/S. At 50mA/cm in initial testing²The stability test was performed for 24 hours. To check the chemical stability of the catalyst, the same test was repeated again two weeks after exposing the crystals to air. All potentials were referenced to the counter hydrogen electrode (RHE).

Composition and structure

Synthesis of PdCoO₂Single crystal and cleaning the product with boiling alcohol to remove it from the unreacted CoO and from the CoCl₂And (5) separating the powder. FIG. 1 shows PdCoO₂The crystal structure of (1). It consists of two-dimensional layers in which CoO's are edge-connected₆The octahedrons are connected through an O-Pd-O dumbbell. PdCoO₂The Co atoms in the octahedral sites of (a) are in a non-magnetic low spin state. It is a trigonal system with space group R-3m (space group number 166).

FIG. 2a shows a typical PdCoO₂SEM image of single crystal. The crystals have a flat surface with a metallic luster. The steep steps on the crystal surface can be clearly seen from fig. 2b, indicating lateral growth and layered structure. This means that the exposed planar surfaces are a-b surfaces and are constructed along the (alon) c axis.

Figure 3 shows the EDS spectrum of the investigated crystals. The chemical compositions were determined to be Pt, Co and O with a stoichiometric ratio close to 1:1:2, further indicating the high purity of the synthesized crystals.

Physical transmission properties

Fig. 4 shows the in-plane resistivity temperature relationship of a single crystal. The resistivity decreases with decreasing temperature over the entire temperature range, indicating metallic behavior. The resistivity at room temperature was only 2.1 μ Ω cm, which is lower than all reported oxide metals. The residual resistivity ratio ρ 300K/ρ 15K is generally 50 to 60, indicating high purity of the sample.

Evaluation of electrocatalytic Activity

Figure 5 shows a three-electrode electrocatalytic system. PdCoO₂The single crystal was attached to a Cu wire with silver paint and used directly as the working electrode. 0.5M H₂SO₄The solution was used as an electrolyte and purged with Ar gas for 30 minutes before measurement. The surface area of the single crystal was determined to be about 0.008cm²。

In FIG. 6, Cu wires, commercially available Pt/C and PdCoO are shown₂HER polarization curve of electrocatalyst. It can be seen that the Cu line is inactive in the measuring potential range. Commercial Pt/C requires 30mV overpotential to deliver 10mA/cm²The current density of (1). PdCoO₂The value of the single crystal is only 33 mV. Of more interest, for PdCoO₂Whereas the overpotential for transferring larger current densities is much lower. FIG. 7 shows PdCoO in a larger potential window₂Polarization curve of (2). It only needs 112mV overpotential to realize 600mA/cm²The current density of (1).

The tafel slope and exchange current density were obtained by fitting the experimental data with the butler-volmer equation (fig. 8). Pt/C and PdCoO₂The Tafel slopes of (a) were 32 and 30mV/dec, respectively. Exchange Current Density vs PdCoO₂And 0.795mA/cm²This is also higher than the exchange current density of Pt/C (0.68 mA/cm)²). These experimental data clearly demonstrate PdCoO₂Is a high activity HER catalyst.

Long term chemical and electrochemical stability was tested and is shown in figure 9. Using an overpotential of 50mV, the catalyst delivered about 50mA/cm²Current density of and remains stableThe time was taken for 24 hours. The single crystal was exposed to air for 2 weeks and the same test was repeated. The electrode was stable for 48h with an overpotential of 50 mV. This indicates the excellent stability of the single crystal catalyst.