EP3077332A1

EP3077332A1 - Metal chalcogenide thin layer electrode, method for production thereof and use thereof

Info

Publication number: EP3077332A1
Application number: EP14820763.2A
Authority: EP
Inventors: Michael Lublow; Anna Fischer; Matthias Driess; Thomas Schedel-Niedrig; Marcel-Philip LÜCKE
Original assignee: Technische Universitaet Berlin
Current assignee: Technische Universitaet Berlin
Priority date: 2013-12-04
Filing date: 2014-12-04
Publication date: 2016-10-12
Also published as: JP2017503084A; DE102013224900A1; US10526716B2; WO2015082626A1; US20160305035A1

Abstract

The invention relates to a method for producing a metal chalcogenide thin layer electrode, comprising the steps: (a) bringing a metal or metal oxide into contact with an elementary halogen in a non-aqueous solvent, generating a metal halogenide bond in the solution, (b) connecting a negative electrical voltage to an electrically conductive or semiconductive substrate which is in contact to the solution from step (a), and (c) during and/or after step (b), bringing the substrate into contact with an elementary chalcogen, forming a metal chalcogenide layer on the substrate. The invention furthermore relates to a metal chalcogenide thin layer electrode which can be produced by the method and use thereof as an anode for oxygen release in (photo)electrochemical water-splitting.

Description

description

Metal chalcogenide thin-film electrode, process for their preparation and

use

The invention relates to a method for producing a metal chalcogenide thin-film electrode, to a metal chalcogenide thin-film electrode producible by the method and to its use for electrochemical water splitting.

The cost-effective and environmentally friendly production of hydrogen by means of (photo) - electrochemical water splitting (H ₂ 0 -> H ₂ + Vi 0 ₂ ) represents a key challenge for the production of alternative fuels, such as fuel cells. During the electrolysis, two partial reactions take place at the electrodes, whereby the reduction of protons to hydrogen takes place at the cathode (2 H ⁺ + 2 e ^" -> H ₂ ) and at the anode the oxidation of oxygen (0 ^{2 ~} -> Vi 0 ₂ + 2 e ^" ). For good overall efficiency, both partial reactions should proceed at a high and comparable rate. At present, the anodic oxygen evolution (also: OER for oxygen evolution reaction) is the limiting reaction, which is why improved electrode materials are desired for this purpose. Particularly desirable are photoactive anode materials which allow for solar powered photoelectrochemical water splitting. In order to lower the overpotential to the anode, improved catalytic electrode materials are sought.

Transition-metal oxides represent a particularly active class of materials for (photo) electrochemical oxygen evolution in water-splitting electrode systems (Cook et al., Chem. Rev. 1 10 (2010), pp. 6474-6502; Walter et al., Chem. Rev 1 10, (2010), pp. 6446-6473). The preparation of suitable electrodes is usually based on the oxidation (under anodic conditions) of metal precursors, ie on the deposition of metals by way of the electrode position on an electrode (the substrate) and their oxidation in the presence of water. For example, the electrochemical deposition of RuO ₂ films on an FTO substrate from an aqueous RuCl ₃ solution is known (Tsuji et al., Electrochim. Acta 56, (201 1), pp. 2009-2016).

Another approach is the electrophoretic transport of previously chemically or electrochemically formed metal oxide clusters onto an electrode surface. For example, a method for the electrodeposition of Ti0 ₂ films on a platinum cathode in Kamada et al. (Kamada et al., Electrochimica Acta 47 (2002), 3309-3313). In this case, a titanium sacrificial anode is used as counterelectrode to the platinum cathode acting as a substrate for Ti0 ₂ deposition, and the reaction is carried out in acetone containing traces of H ₂ O in the presence of iodine (I ₂ ). In this case, titanium is oxidized by oxidation with iodine with the participation of water to Ti0 ²⁺ , dissolved from the sacrificial anode and transported due to the electric field in the direction of the cathode. There, deposition takes place at the Pt cathode as TiO (OH) ₂ and release of H ₂ and subsequent conversion into TiO ₂ . To effect the electrophoretic transport of the titanyl ions to the cathode, this approach requires an electrically conductive cathode.

It is furthermore known from the literature that metal oxide formation (in solution) under reducing conditions can take place in the coupling reaction of organic molecules (ketones) to olefins, referred to as the McMurry reaction (McMurry & Fleming, J. Am. Chem. Soc. 96 (1974) ), Pp. 4708-4709). Here, a combination of LiAlH ₄ and TiCl _{3 is} used, in which the lithium aluminum hydride Ti (+ III) partially reduced to Ti (+ II), which in turn reacts with the ketone. Titanium dioxide is released as a by-product.

The invention is based on the object of proposing a method for producing a metal chalcogenide thin-film electrode for electrocatalytic oxygen evolution in the context of electrochemical water splitting, which is simple to perform and ideally based on inexpensive starting materials. The electrodes that can be generated by the process should have good activity in terms of electrocatalytic oxygen evolution, ideally being photoactive. In addition, the generated metal chalcogenide layer should have a high stability.

These tasks are wholly or partially followed by a method of producing a

A metal chalcogenide thin-film electrode, a corresponding electrode which can be produced by the process and its use with the features of the independent claims.

The method according to the invention for producing a metal chalcogenide thin-film electrode comprises the steps:

(a) contacting a metal or metal oxide with an elemental halogen in a nonaqueous solvent to form a metal halide compound in the solution, (b) applying a negative voltage to an electrically conductive or semiconducting substrate in contact with the solution of step (a), and

(c) during and / or after step (b) contacting the substrate with a

elemental chalcogen to form a Metallchalkogenidschicht on the substrate.

According to the invention, a metal halide compound in solution is thus intermediately generated from the metal or metal oxide from which the later metal chalcogenide layer is to be formed (step a), the metal or metal oxide being partially dissolved. Subsequently, the electrochemical complexing and deposition (step b) by the substrate in which the thin film is to be deposited, is occupied in the metal halide-containing solution with a negative voltage, that is connected to an anode cathodic. The negative charge of the substrate, in contrast to the known electrophoretic deposition does not lead to the formation of an electric field, which directs a particle migration, but to the fact that the substrate acts as an electron transfer agent in the electrochemical reduction reaction. With particular advantage, the metal is thus deposited by reduction on the substrate in step (b) and the substrate is an electron carrier due to the negative voltage during the reduction. Contacting the deposited film with the elemental chalcogen in step (c) (during or after step b) eventually results in formation of the metal chalcogenide compound.

Simultaneously and / or subsequently, the elemental chalcogen is reduced by taking up electrons from the negative cathode (substrate) and reacts with the metal cations of the metal halide to form the corresponding metal chalcogenide, which is deposited on the metal chalcogenide

Surface of the substrate separates. The process results in the formation of a highly compact and very stable metal chalcogenide layer on the substrate. The metal chalcogenide layer thus produced has a high electrochemical anodic oxygen evolution activity in electrochemical water splitting.

Preferably, a metal is used which is capable of forming a metal halide compound in which the metal is in the +2 or higher oxidation state, that is, can bind two or more halide anions. Compared to metals that can be present only monovalent (oxidation state +1), lead two- or higher-grade metals surprisingly higher chalcogenide. This is probably due to a better complexing of the bivalent or higher metal cation by the solvent used. In a preferred embodiment of the invention, the metal is a transition metal. Preferably, it is selected from the group consisting of iron (Fe), cobalt (Co) and nickel (Ni) and mixtures and alloys comprising or consisting of these. The alloy or mixture may also contain metals for which halide formation at room temperature is not documented, such as chromium (Cr) or manganese (Mn). These metals are also co-deposited by means of the method according to the invention as a metal chalcogenide. As a result, Mischmetallchalkogenidschichten can be deposited, for example, mixed oxides of various metals, whereby the catalytic properties of the electrode can be modified.

A particular advantage of the method is the fact that metallic solids can be used as the starting metal, in particular industrial metals or scrap metals. Thus, inexpensive raw materials, if necessary after chemical or mechanical purification of the metal, can be used as the starting material.

In the context of the present invention, the chalcogen is preferably elemental oxygen, elemental sulfur or elemental selenium, and thus metal oxide, metal sulfide or metalloid can be used in the process according to the invention Metallselenidschichten be generated. Among the preferred generated metal oxides nickel oxide Ni _x O _y, cobalt oxide Co _x O _y, and iron oxides Fe _x O _y are, in particular. Various metal sulfides have appropriate photoactive substrates particularly good electrocatalytic properties, so that they photovoltaic in the Iron sulphides, such as iron disulphide FeS ₂ (pyrite), or various CuZnSnS compounds, such as kesterite Cu ₂ (Zn, Fe) SnS ₄ , can be used here, in contrast to the state of the art, the hydrogen sulphide for the production use appropriate sulfides offer t the inventive method a less toxic preparation route.

The substrate itself does not chemically participate in the various reactions of the process, in particular it does not serve as a sacrificial anode as in the prior art as a supplier of the metal or other reaction components. For the electrochemical deposition of the metal chalcogenide and for later use as an electrode, it is only necessary that the substrate is electrically conductive or semiconducting and can function as an electron dispenser. For example, the substrate used is fluorine doped tin oxide (FTO for fluorine doped tin oxide). Alternatively, an n-type semiconductor material is used as a substrate, which generates holes under the action of light, ie is photoactive. n-type semiconductor materials are particularly suitable as photoanode for the evolution of oxygen in the electrolysis of water. The holes generated on exposure to light are transported from the substrate into the metal chalcogenide layer to reach from there the solid / electrolyte interface and to catalyze the oxidation of O ² to ^"0 _second particular, silicon is used as n-type semiconductor material for the substrate n-doped in Question.

In the deposition of the metal oxide film, oxide-free, conductive substrates are particularly preferred in order to avoid a reductive dissolution of the substrate and a concomitant formation of water. Silicon (etched) therefore represents a preferred choice both for the cathode on which the film is to be deposited and for the anode which acts as an electron acceptor to complete the closed circuit. In order to ensure as much solvent as possible in the solvent during the process, it is advantageous to seal the electrochemical cell from which the metal oxide film is deposited from the environment (i.e., ambient air) to prevent ingress of water from atmospheric moisture. With this embodiment of the invention, moreover, the formation of carbon dioxide from carbon dioxide in the air can be prevented.

For the metal halide production in step (a) of the process, an elemental halogen is used. Suitable elemental halogens include in particular iodine l ₂ , which can be used as a solid, or bromine Br ₂ , which can be bubbled as a gas into the solvent. Preferably, crystalline iodine is used.

As the nonaqueous solvent, an organic solvent is preferably used. The organic solvent particularly preferably has a carbonyl group (CO) or cyanide group (CN). It is believed that such solvents, the metal cation of the halide compound with the lone pairs of carbonyl or electron

Coordinate cyanide and thus activate for subsequent reaction with the cathodically generated Chalkogenidanion. In addition, it has surprisingly been observed that the solvent participates in the reaction with co-deposition of carbon or carbon-containing compounds. The proportion of carbon and / or the carbonaceous compounds in the metal chalcogenide layer produced is up to 30 atomic percent. The proportion of carbon and / or carbonaceous compounds in the thin layer derived from the solvent leads to an unexpected densification of the metal chalcogenide thin layer and thus to improved stability and tightness. The tightness is of particular interest in the use of a semiconductor material as a substrate, typically protected against contact with an aqueous electrolyte in an electrochemical cell must become. In addition, the incorporation of carbon and / or carbonaceous compounds in the thin film can improve charge transport between substrate and metal chalcogenide.

The process is carried out with the greatest possible exclusion of water, since this inhibits the formation of metal chalcogenides. Preferably, the amount of water in the non-aqueous solvent used is at most 0.2% by weight, more preferably at most 0.1% by weight.

In a preferred embodiment, contained residues of water are expelled from the solvent prior to deposition and / or prior to the formation of the haloiodide. This is preferably done by a pre-electrolysis, wherein, for example, two electrodes are introduced into the already halogen-containing solvent. Applying a voltage to the two electrodes (in particular in the range of 5 to 20 V, preferably 7 to 12 V, particularly preferably 10 V), the residual water is decomposed, thereby takes place at one of the electrodes (the anode) oxidation, while At the other electrode (the cathode) molecular hydrogen is produced, which leaves the electrolyte as gas.

The contacting of the electrochemically modified substrate with the elemental chalcogen for metal chalcogenide formation can take place in various ways. On the one hand, the chalcogen may already be present in the solvent or be added to it actively. For example, the solvent may contain traces of dissolved oxygen or oxygen may be introduced into the solution by stirring. In the case of using sulfur or selenium as the chalcogen, elemental sulfur or elemental selenium may be added to the solution. Alternatively, the chalcogen may be in the atmosphere, such as oxygen, which is present in the atmosphere anyway, or actively added to the atmosphere. In this case, after its removal from the solution, the substrate comes into contact with the atmosphere after the step (b) and thus with the chalcogen, so that the metal chalcogen is formed on the surface of the substrate. This procedure is particularly suitable if a metal oxide layer is to be produced and thus the atmospheric oxygen can be used.

In a preferred embodiment of the invention, after formation of the metal chalcogenide layer on the substrate, a chemical or electrochemical aftertreatment of the deposited layer takes place for stabilization, for example to increase the oxidation state of the metal cation. This can be done, for example, by electrochemical processing in aqueous hydroxide-containing electrolytes.

In a particularly preferred embodiment of the invention, after formation of the metal chalcogenide layer on the substrate or after the above-mentioned (electro) chemical aftertreatment, a thermal aftertreatment takes place. Here, the microstructure of the substrate and deposited thereon Metallchalkogenidschicht at temperatures in the range of 150 to 800 ° C, in particular from 150 to 500 ° C, preferably from 200 to 400 ° C, for a period of 1 min to 10 h, in particular for a Treated for 1 to 30 minutes. The thermal aftertreatment, also referred to as "armealing", leads to an increase in the crystallinity and / or the photoactivity of the deposited layer The specific conditions are based primarily on the chalcogen and the desired crystallinity thereof.

Another aspect of the invention relates to a metal chalcogenide thin-film electrode, which can be produced by the method according to the invention. The electrode comprises an electrically conductive or semiconductive substrate and a thin layer of a metal chalcogenide compound deposited thereon. The electrode produced by the method according to the invention is characterized in particular by the fact that carbon and / or compounds of the carbon can be detected in the metal chalcogenide thin film produced. The proportion of carbon and / or the carbonaceous compound (s) in the metal chalcogenide layer produced is up to 30 atomic percent. The carbon leads to increased strength and density of the thin film. In this way, both the charge transport from the substrate to the metal chalcogenide can be optimized and the stability of the substrate can be increased. The latter is particularly of particular interest when using a semiconductor material which typically needs to be protected from contact with an aqueous electrolyte. The metal chalcogenide thin-film electrode according to the invention is therefore characterized by improved stability. The thin-film electrode according to the invention has layer thicknesses of the metal chalcogenide layer in the range of 50 to 1000 nm, in particular in the range of 100 to 500 nm. In addition, the deposited layer has a nanostructured surface morphology with average sizes of the electron microscopic recognizable

Structural elements in the range <500 nm.

A further aspect of the present invention relates to the use of the metal chalcogenide thin-film electrode according to the invention as electrode for the evolution of oxygen for electrochemical water splitting under an applied external potential or under illumination. In other words, the electrode is preferably used as an anode in the water used electrolysis. In particular, if the substrate is a photoactive semiconductor, such as n-doped silicon, the electrode for the photoelectrochemical water splitting, so as a photoanode can be used. The heterostructure of the photoactive semiconductor substrate and metal chalcogenide layer deposited thereon allows holes to be transported from the semiconductor into the metal chalcogenide layer under light supply in order to reach the solid / electrolyte interface therefrom.

Further preferred embodiments of the invention will become apparent from the remaining, mentioned in the dependent claims characteristics.

The various embodiments of the invention mentioned in this application are, unless otherwise stated in the individual case, advantageously combinable with each other.

The invention will be explained below in embodiments with reference to the accompanying drawings. Show it:

Figure 1 morphology and electrochemical properties of inventive

Metal oxide FTO thin film electrodes after cathodic deposition of Ni (a), Co (b), Fe (c) and Cu (d);

FIG. 2 results of the chemical analysis of a Ni _x O _y deposited on Si (1 1 1)

Layer; a) XPS before and after anodic use, b) EDX;

Figure 3 Results of the chemical analysis of a deposited on Si (1 1 1)

COxOy layer; a) XPS before and after anodic use, b) EDX;

Figure 4 Results of the chemical analysis of a deposited on Si (1 1 1)

Fe _x O _y layer; a) XPS before and after anodic use, b) EDX;

Figure 5 Results of the chemical analysis of a deposited on Si (1 1 1)

Cu (0) layer; a) XPS before and after anodic use, b) EDX;

FIG. 6 shows investigations of a Ni _x O _y / Si (100) thin-film electrode; a) electricity

Voltage behavior during photoelectrochemical oxygen evolution with continuous illumination (solid curve) and periodic illumination (broken curve); b) SEM uptake in Tilt; c) S EM image in plan view; d) TEM image in

Top view;

FIG. 7 shows SEM photographs of a Ni _x O _y / Si (100) thin-film electrode; prepared a) in anhydrous solution according to the invention and b) in a solvent mixture with 25 vol .-% H ₂ 0;

FIG. 8 Analysis of a Fe / Si / Ni / Cr / Co / Mn oxide layer deposited on FTO; a)

SEM images before and after a thermal aftertreatment; b) EDX analysis;

FIG. 9 Electrochemical investigation of a tempered Fe / Si / Ni / Cr / Co / Mn

Oxide / FTO electrode for electrochemical oxygen evolution; left) dark reaction at an external voltage of 0-1, 4 V; right) intermittent illumination at a constant applied potential of 0.65 V);

The inventive method will be explained in more detail below. In this case, for the sake of clarity, the use of iodine as halogen, of oxygen as chalcogen and of a metal solid as supplier for the metal of the metal chalcogenide layer is assumed, but without limiting the invention thereto.

In an optional step 1, a metal is cleaned of any surface contamination and / or oxide or hydroxide layers on the surface. The cleaning step may be done mechanically, for example by using abrasive materials such as abrasive paper or the like. Alternatively, the cleaning can be carried out by a chemical treatment in which, for example, oxide-dissolving reactions are carried out. The metal used is preferably a metallic solid, which may be derived in particular from industrial or scrap metals. For use come solids of any geometry, for example in the form of sheets, powders or other. In chemical terms, metals comprising or consisting of iron, cobalt and / or nickel are preferably used.

In step 2, metal halide formation takes place, here metal iodide formation. For this purpose, the optionally purified in step 1 metal is placed in a non-aqueous solvent having a water content of at most 0.2 wt .-%. Preferably, the solvent used is acetone or Acetonitrile used. The solvent is a halogen, here crystalline iodine, in a mass ratio of solvent: iodine of at least 1: 1 or higher iodine added. Preferably, the mixture is exposed to ultrasound to better

To achieve thorough mixing. The reaction is carried out for a period of at least 5 minutes, preferably at room temperature. It is assumed that in this case the iodine, with partial release of metal from the solid to the corresponding metal iodide in the solution, for example, according to the following equation:

M (0) + - »Ml ₂

In the next step 3, an electrochemical processing takes place. For this purpose, two electrically conductive or semiconductive electrodes are brought into contact with the solution containing metal iodide from step 2, after the remaining solid metal body has been removed therefrom. One of these electrodes serves as a substrate for the thin-film electrode to be produced, while the other represents the counter-electrode for the electrochemical processing. The substrate electrode consists for example of a metal or a metal alloy, FTO, n-doped silicon or carbon. The counterelectrode can basically consist of the same or a different material than the substrate electrode. A voltage is applied to the electrodes, wherein the substrate electrode is covered with a negative voltage, that is, switched as a cathode. The applied voltage is <-2 volts, more preferably in the range of -5 to -10 volts, the sign referring to the substrate electrode on which the metal oxide film is to be deposited. The electrochemical deposition is preferably carried out at room temperature. The reaction time depends on the thickness of the metal oxide layer to be deposited and depends on the applied voltage.

Without wishing to be bound by any particular theory, it is assumed that the metal iodide in the solution is coordinated by the organic solvent, in particular its carbonyl or cyanide groups, to form organometallic complexes. These complexes show a high reactivity towards free oxygen, which is already present in traces in the solvent or in the ambient air. The oxygen is reduced at the cathodic (ie negatively) polarized substrate electrode to accept 0 ^{2 "} anions, which react with the metal halide to form the corresponding metal oxide, resulting in a direct deposition of the metal oxide on the substrate (see the following reaction equations). It is possible that a reaction with oxygen and the associated deposition of metal oxide only occurs on later contact with the atmospheric oxygen after the still wet, negatively polarized electrode has been removed from the solution. ^_{_1/2} 0 ₂ + e ^"-" O ^{2 "}

O ^{2 "} + x MI -> M _x O _y

Without the individual chemical processes having been elucidated, the organic solvent appears to take part in the reactions in such a way that significant amounts of carbon and / or carbonaceous material are contained in the metal oxide layer produced

Connections are deposited with.

Subsequently, the removal of the substrate electrode takes place with the layer deposited thereon from the solvent / iodide bath. This is preferably carried out under dry nitrogen, in order to allow the evaporation of any formed hydrogen iodide under exclusion of atmospheric moisture.

In an optional subsequent step 4, a chemical or electrochemical aftertreatment of the deposited layers takes place with the aim of increasing the stability of the metal oxide layer. In particular, the aim of the aftertreatment is to increase the oxidation state of the metal, that is to further oxidize it. For this purpose, the electrode may for example be introduced into an aqueous hydroxide-containing electrolyte solution and processed electrochemically.

In a further optional step 5, a thermal aftertreatment of the electrode takes place to increase the crystallinity of the deposited metal chalcogenide layer. For this purpose, the electrode is tempered at temperatures in the range of 150 to 800 ° C for a period of 1 minute to 10 hours.

The metal chalcogenide thin-film electrodes obtained by the method according to the invention are distinguished by particularly dense and stable metal chalcogenide layers, which are also carbonaceous.

Examples

measurement methods

XPS. X-ray photoelectron spectroscopy (XPS) was performed for the chemical analysis of the samples. The assignment of core level lines to specific oxidation states was made using published data (Chastain & King (Ed.), Handbook of X-Ray Photoelectron Spectrospcopy, Physical Electronics, Minnesota, USA, 1995).

EDX.

Energy dispersive X-ray analysis (EDX) was used for elemental chemical analysis both integrally, i. averaging over the entire sample surface, as well as locally, i. with lateral resolution (smallest resolution limit about 100 nm) carried out on the scanning electron microscope. The excitation energies were chosen so that the expected element-specific K and L lines of the elements could be detected, i. E. between 3 keV and 10 keV. The assignment of the measured X-ray lines was carried out automatically with the aid of database values by the control software (NSS 2.2, Thermo Fisher Scientific, USA).

Electrochemical characterization

The electrodes prepared in the examples were tested in a standard electrochemical cell for their suitability for oxygen production in 0.1 mol / l NaOH (pH 13). For this purpose, the samples were measured either in a three-electrode configuration with a Pt counterelectrode and an Ag / AgCl reference electrode or in a two-electrode configuration with short-circuiting of the Pt counter and Ag / AgCl reference electrode. The potential was each controlled with a potentiostat (VSP, BioLogic, France).

For photochemical investigations, illumination was done with a W-l white light source (MI-150, Dolan-Jenner, The Netherlands) via fiberglass optics.

Example 1: Preparation of a NixO _y / FTO electrode

As a metallic solid 2 cm ^{2 of} a high-purity Ni metal foil (Goodfellow Corp. USA, purity> 99.95 wt .-%) in a mixture of acetone (15 ml, w (H ₂ 0) <0.2%) and iodine crystal powder ( 80 mg). This mixture was mixed for 5 min in an ultrasonic bath at 37 kHz. During this treatment, the temperature rose from room temperature to about 35 ° C. Subsequently, the metal foil was removed from the solution.

FTO films (Solaronix, Switzerland, sheet resistance 7 cm ² , 3 × 1.5 cm) were pre-cleaned with acetone. One FTO sample was used as the cathode (substrate) and a second as the counter electrode (Anode) placed at a distance of 5-10 mm from each other in the acetone solution. A potential of 10 V was applied between the substrate and counter electrodes for 5 minutes.

Subsequently, the substrate electrode was removed from the solution and dried.

Example 2: Preparation of a COxO _y / FTO electrode

The preparation was carried out as in Example 1 except that 2 cm ^{2 of} a highly pure co-metal foil (Goodfellow Corp. USA, purity> 99.95% by weight) was used as the metallic solid.

Example 3: Preparation of a FexOy / FTO Electrode

The preparation was carried out as in Example 1 except that 2 cm ^{2 of} a high-purity Fe metal foil (Goodfellow Corp. USA, purity> 99.95% by weight) was used as the metallic solid.

Example 4: Preparation of a Cu / FTO Electrode

The preparation was carried out as in Example 1, except that 2 cm ^{2 of} a high-purity copper metal foil (Goodfellow Corp. USA, purity> 99.95% by weight) was used as the metallic solid.

Examples 5-8: preparation of various MxO _y / Si (100) electrodes

The preparation was carried out as in Examples 1-4, except that 2 cm ^{2 of} an n-type Si (100) wafer (ABC Company, Germany, doping N _D ~ 6 × 10 ¹⁵ ) was used as the substrate electrode (cathode). For pretreatment, the Si (100) wafer was prepurified with ethanol and water and then chemically etched in a solvent mixture of hydrofluoric acid (50%) and ethanol (HF: C ₂ H ₅ OH = 3: 1) for 30 s and 10 s, rinsed occasionally with water and then dried with N ₂ . The counterelectrode used was 1 -3 FTO as in Examples 1.

Examples 9-12: Preparation of various MxO _y / Si (1 1 1 VEIektroden

The preparation was carried out as in Examples 1 to 4, except that in each case 2 cm ^{2 of} an n-type Si (11 1) wafer (ABC Company, Germany, doping N _D ~ 6 × 10 ¹⁵ ) were used as the substrate electrode (cathode) has been. For pretreatment, the Si (1 1 1) wafer was prepurified with ethanol and water and then first with NH ₄ F (100 s) and finally with hydrofluoric acid (50%, 10 min) chemically etched and then dried with N ₂ . The counterelectrode used was 1 -3 FTO as in Examples 1.

Example 13: Preparation of a mixed oxide / FTO electrode

The preparation was carried out as in Example 1, except that 2 cm ^{2 of} a steel alloy of the metals Fe / Si / Ni / Cr / Co / Mn was used as the metallic solid. Further, unlike Example 1, the sample was annealed after drying at 300 ° C for 10 minutes.

Example 14: Preparation of a CoO / ZnO / CoZnO / Si Electrode

The preparation was carried out as in Example 1, except that chemically synthesized CoZnO nanoparticles were used as metal source and Si (100) n-doped as substrate.

The substrates and metals used in Examples 1 to 14 are shown in Table 1

compiled.

Table 1 :

Comparative Example 1: Preparation of a NixO _y / Si (100) electrode in the presence of water The preparation was carried out as described in Example 5 using a Ni metal foil and crystalline iodine, except that instead of the acetone, a solvent mixture of acetone and 25% by volume of H ₂ O was used.

Comparative Example 2: Preparation of FexOy / Si (100) Electrode in the Presence of Water

The preparation was carried out as described in Example 7, except that instead of the acetone, a solvent mixture of acetone and 25% by volume of H ₂ 0 was used.

Characterization of the produced metal oxide thin-film electrodes

Figure 1 a) to d) shows the current densities as a function of the applied potential of the thin-film electrodes obtained in Examples 1 to 4 during the evolution of oxygen in a 0.1 M NaOH solution, which in the dark between 0 and 2 volts against Ag / AgCl measured in a three-electrode configuration. For comparison, the behavior of pure FTO is shown as a dashed curve in the respective graph. The nickel, cobalt and iron oxides show a clear activity with respect to the evolution of oxygen (FIGS. 1 a) to c)). The overpotentials determined from the curves range between 340 and 420 mV, with the cobalt and nickel oxide electrodes having the highest activity and the iron oxide electrode having the lowest activity. The copper electrode, on the other hand, becomes active only at high external potentials (FIG. 1 d)). Oxygen evolution was confirmed by electrochemical differential mass spectroscopy (DEMS).

SEM images of the respective surfaces are also shown in FIGS. 1 a) to d). They confirm a surface morphology with roughness in the nanometer range.

In Figures 2 to 5, the results of the chemical analyzes of the deposited metal oxide layers on Si (1 1 1) according to Examples 9 to 12 are shown. In this case, the results of the XPS examination of the metal oxide layer after their deposition (upper graph in each case) and after use of the electrode for the electrochemical acid evolution (in each case the lower graph) are shown in a). In b) of FIGS. 2 to 5, the results of the EDX measurements of the metal oxide layers after their production (before electrochemical use) are respectively shown. The assignment of individual XPS signals to certain oxidation states was made more difficult by electrostatic charging of the fresh oxide layers after their preparation (see in each case FIGS. 2 a) to 5 a) above). In contrast, after the use of the electrodes for the electrochemical evolution of oxygen, an assignment to different oxidation states of the metals was possible (see in each case FIGS. 2 a) to 5 a) below). For example, the results in Figure 2 a) show the simultaneous presence of Ni ₂ O ₃ and NiO within the

Information depth of the method of about 2 to 3 nm.

The EDX results for nickel, cobalt and iron demonstrate the presence of bound oxygen in the form of the corresponding oxides (see Figures 2 to 4 b)). In the case of copper, only a comparatively small proportion of oxygen is detectable in the deposited layer (FIG. 5 b)), which indicates, in accordance with the XPS analysis, the predominant deposition of metallic copper Cu (0). As expected, this is associated with the low activity with regard to the evolution of oxygen (see FIG. It is believed that the lack of deposition of copper oxide is associated with the property of copper to form only monovalent iodides Cul during manufacture. By way of a one-electron transfer from the cathode, the formation of metallic copper appears to be preferred over the complex formation in the organic solvent and subsequent oxidation.

Interestingly, in all thin films produced carbon is detectable (Figure 2 b) to 5 b)), which probably originates from the solvent used (acetone).

The example of the Ni _x O _y / Si (100) thin-film electrode produced according to Example 5 shows the photoelectrocatalytic behavior in FIG. 6 a). The solid curve shows the current-voltage behavior for continuous lighting and the broken curve shows the current-voltage behavior for periodic lighting. The measurements were each in a three-electrode configuration. It can be seen that the inventive

Ni _x O _y / Si (100) thin film electrode has good photoactivity. In the dark, however, it is inactive even at an applied voltage of 2 volts, resulting from the drop in the

Current density after switching off the light emerges.

FIGS. 6 b), c) and d) show SEM and TEM images of the Ni _x O _y / Si (100) thin-film electrode from Example 5, respectively. It can be seen that the nickel oxide layer has a roughness in the nanometer range and a layer thickness of about 100 to 150 nm. FIG. 7 shows the product according to Comparative Example 1 in which the solution contained 25% by volume of water for the comparison of the Ni _x O _y / Si (100) thin-film electrode produced in accordance with the anhydrous method according to the invention from Example 5 (FIG. 7b) ). It can be seen that the presence of water largely prevents layer formation. Only single Ni, O and C containing islands are observable (confirmed by EDX analysis).

A similar result was obtained in Comparative Example 2 with iron. Again, the inhibitory influence of water on the film formation was clearly visible. The resulting flat islands allowed the analysis by EDX, which was also able to detect Fe, O and C in the deposited islands (results not shown).

FIG. 8 shows the results of the analysis of the metal oxide layer according to Example 13 (before and after the thermal aftertreatment) using as a starting material for the metal a steel alloy containing, in addition to the main constituents iron and chromium, additions of nickel, cobalt, manganese and silicon , In the EDX analysis shown in FIG. 8 b), it should be noted that the energy range is from 0 to 5 keV at the top and from 5 to 10 keV at the bottom. Shown is the steel starting material (curve I), the metal oxide thin layer after its deposition (curve II) and after its annealing at 300 ° C for 10 minutes (curve III). The EDX analysis shows that all elements contained in the steel are deposited as an oxide form on the FTO substrate.

FIG. 9 shows the electrochemical characterization of the same sample as in FIG. 8 as an anode for the evolution of oxygen. In this case, the current-voltage behavior is shown on the left with an applied external voltage between 0 and 1, 4 V without exposure to light. The electrode exhibits an oxygen evolution overvoltage of about 300 mV, confirming its electrocatalytic activity. The measurement at an applied constant potential of 0.65 volts with intermittent illumination is shown on the right side of FIG. This measurement confirms an existing photoactivity of the electrode.

The thin film formed by Example 14 using CoZnO nanoparticles as the starting material for the thin film to be deposited was also analyzed (results not shown). The analysis showed two distinct, distinct layers. Immediately on the n-Si (100) substrate, a thin film of the oxides CoO and ZnO could be identified, which also contained portions of carbon. On this amorphous CoO / ZnO / C layer, a second layer consisting of deposited CoZnO particles corresponding to the starting material was detectable. It is believed that the two thin films of this heterostructure are generated on different reaction paths. In this case, the metal oxide particles are partially dissolved in contact with the iodine-containing solution, wherein the metallic components go as metal iodides in solution. The subsequent electrochemical treatment produces (in a rapid reaction phase) the amorphous carbonaceous barrier layer on the substrate. In contrast, the unresolved remaining oxide particles are deposited (in a slower reaction phase) on this boundary layer by electrophoretic transport.

Example 14 shows that chemically synthesized powder-produced metal oxides can be deposited on substrate by the method so that an (amorphous) protective layer is formed on the substrate. This allows the corrosion-free operation of the resulting substrate / oxide heterostructure. This is particularly advantageous in light-assisted water splitting using sensitive semiconductor substrates.

As a by-product of the iron oxide film formation in Example 3 under o.a. cathodic conditions left a dispersion of black particles in solution. These particles showed paramagnetic properties, i. they were attracted to the magnetic field of a permanent magnet without being permanently magnetized, as in ferromagnetism. For the particles in solution, this means that they redisperse as the external magnetic field is removed. The method can thus also be used to produce nanoparticles of iron or other metallic materials.

Claims

claims

1 . A method of making a metal chalcogenide thin film electrode comprising the steps of:

(a) contacting a metal or metal oxide with an elemental halogen in a non-aqueous solvent to form a metal halide compound in the solution,

(b) applying a negative voltage to an electrically conductive or semiconducting substrate in contact with the solution of step (a), and

(c) during and / or after step (b) contacting the substrate with an elemental chalcogen to form a metal chalcogenide layer on the substrate.

2. The method of claim 1, wherein the metal is capable of forming a metal halide compound in which the metal is in the +2 or higher oxidation state.

3. The method according to any one of the preceding claims, wherein in step (b) the metal is deposited by reduction on the substrate and the substrate is an electron transfer agent due to the negative voltage in the reduction.

4. The method according to any one of the preceding claims, wherein the metal comprises at least one transition metal, in particular selected from the group consisting of iron, cobalt and nickel, or a mixture or alloy comprising or consisting thereof.

5. The method according to any one of the preceding claims, wherein the metal is a metallic solid, in particular an industrial metal or scrap metal.

6. The method according to any one of the preceding claims, wherein the elemental chalcogen, elemental oxygen, elemental sulfur or elemental selenium is.

7. The method according to any one of the preceding claims, wherein the substrate comprises an n-type semiconductor material, in particular n-doped silicon, or fluorine-doped tin oxide (FTO).

8. The method of claim 1, wherein the elemental halogen is iodine (l ₂ ) or bromine (Br ₂ ).

9. The method according to any one of the preceding claims, wherein the non-aqueous

Solvent is an organic solvent, in particular a carbonyl group or cyanide having organic solvent, preferably acetone or acetonitrile.

10. The method according to any one of the preceding claims, wherein a water content in the non-aqueous solvent is at most 0.2 wt .-%.

1 1. The method of any one of the preceding claims, wherein contacting the substrate with the chalcogen is accomplished by the presence of the chalcogen in the solution or by contacting the substrate with a chalcogen-containing atmosphere.

12. The method according to any one of the preceding claims, comprising the step: (d)

thermal aftertreatment of the substrate having the metal chalcogenide layer.

13. A metal chalcogenide thin film electrode comprising an electrically conductive or

semiconducting substrate and a thin film deposited thereon

Metallchalkogenidverbindung, prepared or prepared according to any one of claims 1 to 1 1.

The metal chalcogenide thin film electrode of claim 12, wherein the metal chalcogenide layer comprises carbon or a carbonaceous compound.

15. Use of a metal chalcogenide thin-film electrode according to claim 13 or 14 as an electrode for the evolution of oxygen for electrochemical water splitting.