CN117403093A - Method for preparing high-entropy alloy by irradiation of organic liquid phase laser at normal temperature and normal pressure - Google Patents
Method for preparing high-entropy alloy by irradiation of organic liquid phase laser at normal temperature and normal pressure Download PDFInfo
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- CN117403093A CN117403093A CN202311272815.0A CN202311272815A CN117403093A CN 117403093 A CN117403093 A CN 117403093A CN 202311272815 A CN202311272815 A CN 202311272815A CN 117403093 A CN117403093 A CN 117403093A
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000007791 liquid phase Substances 0.000 title claims abstract description 26
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 26
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 24
- 239000002105 nanoparticle Substances 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 12
- 239000012467 final product Substances 0.000 claims abstract description 10
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 9
- 230000001678 irradiating effect Effects 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000003760 magnetic stirring Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 9
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 230000033228 biological regulation Effects 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 239000005751 Copper oxide Substances 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims description 2
- 229910000457 iridium oxide Inorganic materials 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001887 tin oxide Inorganic materials 0.000 claims description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 description 9
- 230000007246 mechanism Effects 0.000 description 7
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- 239000010931 gold Substances 0.000 description 4
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- 230000015572 biosynthetic process Effects 0.000 description 3
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- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
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- 238000000354 decomposition reaction Methods 0.000 description 2
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- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 238000000441 X-ray spectroscopy Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- -1 carrier Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000010895 photoacoustic effect Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
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- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
- C22C1/1026—Alloys containing non-metals starting from a solution or a suspension of (a) compound(s) of at least one of the alloy constituents
Abstract
The invention discloses a method for preparing high-entropy alloy by using normal-temperature and normal-pressure organic liquid phase laser irradiation, which is characterized in that 2-5mg of metal or noble metal nano particles and non-noble metal oxide nano particles are weighed and respectively added into organic reagents such as ethanol, acetone and methanol or mixed liquid thereof, and uniformly dispersed by sufficient ultrasonic and magnetic stirring; and (3) preparing 532nm or 355nm wave band nanosecond pulse laser, and irradiating the uniformly mixed colloidal solution for 20 minutes to obtain a high-entropy alloy final product with non-uniform size. The metal and oxide particles which are uniformly mixed are dispersed in the organic liquid phase medium through common irradiation for the first time, so that the series high-entropy alloy is prepared by a one-step method.
Description
Technical Field
The invention relates to a method for preparing high-entropy alloy, in particular to a method for preparing high-entropy alloy by organic liquid phase laser irradiation at normal temperature and normal pressure.
Background
The high-entropy alloy (HEA) is a revolutionary brand new material which is obtained in recent years and is vigorously developed, unlike binary or ternary alloys which have been developed relatively mature at present. In the high-entropy alloy material, various elements (more than or equal to 5) can be mixed according to a proper proportion, and a single-phase solid solution or intermetallic compound is formed under the stabilization action of configuration entropy. Because the elements in the components have respectively different element sizes, electron arrangement and crystal structures, the alloy monocrystal formed by uniformly mixing the elements can show rich surface electron structures and a large amount of lattice distortion, so that the alloy monocrystal has various excellent physical and chemical characteristics such as high temperature resistance (high entropy effect), high hardness (lattice distortion effect), high thermal stability (delayed diffusion effect), high catalytic activity (cocktail effect) and the like.
In the prior art:
the method for preparing the metal nanoparticles is mainly divided into two types, namely "Top-down": breaking up the bulk into nano-scale materials by using physical methods, and "Bottom-up": chemical methods of reducing metal ion salt precursors to elemental species. The most commonly developed wet chemistry method can control nanoparticle size, morphology, but is only suitable for preparing binary and small amounts of ternary nano alloy particles. This is because the simultaneous decomposition or reduction of a plurality of ionic salts is difficult due to the large difference in the reduction potential and thermal decomposition temperature of the ionic salts of each metal element in the precursor. As the elements increase, the final product tends to phase separate. The high-entropy alloy particles prepared by the low-temperature ball milling method are always bigger and lower.
At present, a reasonable synthesis mode is to control the formation of high-entropy alloy through the dynamics of rapid temperature rise and rapid temperature reduction, and a carbon thermal shock method and a rapid moving bed pyrolysis method are commonly used. However, the method mostly needs complicated operation steps, has high energy consumption to realize rapid heating and cooling, and can realize the load synthesis of the high-entropy alloy nano particles only by depending on carriers.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a simple, safe and quick method for preparing high-entropy alloy by irradiating organic liquid phase laser at normal temperature and normal pressure, so as to solve the technical problems in the prior art.
The invention aims at realizing the following technical scheme:
the invention relates to a method for preparing high-entropy alloy by organic liquid phase laser irradiation at normal temperature and normal pressure, which comprises the following steps:
weighing 2-5mg of metal or noble metal nano particles and non-noble metal oxide nano particles, respectively adding the metal or noble metal nano particles and the non-noble metal oxide nano particles into an organic reagent, uniformly dispersing the metal or noble metal nano particles by sufficient ultrasonic and magnetic stirring, wherein the selection of the nano particles is related to the distribution of element types in a final product;
and (3) preparing 532nm or 355nm wave band nanosecond pulse laser, and irradiating the uniformly mixed colloidal solution for 20 minutes to obtain a high-entropy alloy final product with non-uniform size, wherein the selection and parameter regulation of the laser wave band are related to the capability of reducing oxide particles.
Compared with the prior art, the method for preparing the high-entropy alloy by the normal-temperature normal-pressure organic liquid phase laser irradiation provided by the invention prepares a series of high-entropy alloys by the laser irradiation in an organic liquid phase at normal temperature and normal pressure, utilizes the photothermal effect of pulse laser and nano particles and a reduction mechanism generated by an organic liquid phase medium under the photothermal effect, and firstly prepares the series of high-entropy alloys by commonly irradiating metal and oxide particles which are dispersed in the organic liquid phase medium and uniformly mixed.
Drawings
FIG. 1 is a schematic diagram of preparing a high-entropy alloy based on an organic liquid phase laser irradiation technique according to an embodiment of the present invention;
FIG. 2 is a TEM spectrum of a high-entropy alloy prepared by an organic liquid phase laser irradiation technique according to an embodiment of the present invention;
FIG. 3 is an EDS spectrum of AuIrRuCuCo according to an embodiment of the present invention;
fig. 4 is an EDS spectrum of AuPtFeCoNi of an embodiment of the invention.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention; it will be apparent that the described embodiments are only some embodiments of the invention, but not all embodiments, which do not constitute limitations of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention.
The terms that may be used herein will first be described as follows:
the term "and/or" is intended to mean that either or both may be implemented, e.g., X and/or Y are intended to include both the cases of "X" or "Y" and the cases of "X and Y".
The terms "comprises," "comprising," "includes," "including," "has," "having" or other similar referents are to be construed to cover a non-exclusive inclusion. For example: including a particular feature (e.g., a starting material, component, ingredient, carrier, formulation, material, dimension, part, means, mechanism, apparatus, step, procedure, method, reaction condition, processing condition, parameter, algorithm, signal, data, product or article of manufacture, etc.), should be construed as including not only a particular feature but also other features known in the art that are not explicitly recited.
The term "consisting of … …" is meant to exclude any technical feature element not explicitly listed. If such term is used in a claim, the term will cause the claim to be closed, such that it does not include technical features other than those specifically listed, except for conventional impurities associated therewith. If the term is intended to appear in only a clause of a claim, it is intended to limit only the elements explicitly recited in that clause, and the elements recited in other clauses are not excluded from the overall claim.
What is not described in detail in the embodiments of the present invention belongs to the prior art known to those skilled in the art. The specific conditions are not noted in the examples of the present invention and are carried out according to the conditions conventional in the art or suggested by the manufacturer. The reagents or apparatus used in the examples of the present invention were conventional products commercially available without the manufacturer's knowledge.
The invention relates to a method for preparing high-entropy alloy by organic liquid phase laser irradiation at normal temperature and normal pressure, which comprises the following steps:
weighing 2-5mg of metal or noble metal nano particles and non-noble metal oxide nano particles, respectively adding the metal or noble metal nano particles and the non-noble metal oxide nano particles into an organic reagent, uniformly dispersing the metal or noble metal nano particles by sufficient ultrasonic and magnetic stirring, wherein the selection of the nano particles is related to the distribution of element types in a final product;
and (3) preparing 532nm or 355nm wave band nanosecond pulse laser, and irradiating the uniformly mixed colloidal solution for 20 minutes to obtain a high-entropy alloy final product with non-uniform size, wherein the selection and parameter regulation of the laser wave band are related to the capability of reducing oxide particles.
The time for irradiating the uniformly mixed colloidal solution by the nanosecond pulse laser is 20 minutes.
The organic reagent comprises a mixed solution of any one or more of the following: ethanol, acetone or methanol.
The metal or noble metal nanoparticles comprise Au, ir, ru and/or Pt, and the metal oxides involved comprise copper oxide, iron oxide, cobalt oxide, nickel oxide, aluminum oxide, iridium oxide, ruthenium oxide, zinc oxide, molybdenum oxide, tungsten oxide and/or tin oxide.
In summary, according to the method for preparing the high-entropy alloy by using the normal-temperature and normal-pressure organic liquid-phase laser irradiation, the high-entropy alloy can be simply and efficiently prepared by using a one-step method at normal temperature and normal pressure, and the metal nano particles can be quickly heated and melted by using the nanosecond pulse laser from top to bottom to act on the surfaces of the metal nano particles. The high temperature nano particles can quickly decompose the organic medium in the environment to generate reductive small molecules. Meanwhile, non-noble metal nano particles which are jointly dispersed in an organic medium with metal nano particles are reduced into corresponding non-noble metal simple substances from bottom to top under the synergistic effect of laser irradiation heating and reducing micromolecules. And then high-frequency nanosecond pulse laser continuously irradiates to act on the mixed colloid dispersed in the organic medium, so that each element metal particle in the solution is rapidly melted and alloyed, and is coagulated and nucleated to grow under an organic liquid medium ultra-fast quenching mechanism, and finally, the high-entropy alloy is rapidly synthesized in a dynamic scale.
The invention organically combines the technical characteristics of preparing metal nano particles from top to bottom and from bottom to top, prepares the high-entropy alloy by a liquid phase laser irradiation one-step method, and widens the general technical path for rapidly and efficiently preparing the high-entropy alloy.
In order to more clearly demonstrate the technical scheme and the technical effects provided by the invention, the following detailed description of the embodiments of the invention is given by way of specific examples.
Example 1
The specific experimental schematic diagram is shown in fig. 1: weighing metal nano particles with proper mass, respectively adding the non-noble metal oxide nano particles into an organic reagent such as ethanol, and uniformly dispersing the metal nano particles by sufficient ultrasonic and magnetic stirring. And (3) preparing nanosecond pulse laser with proper parameters, and irradiating the uniformly mixed colloidal solution for 20 minutes to obtain a high-entropy alloy final product with nonuniform size.
To characterize the morphology of the product, a Transmission Electron Microscope (TEM) analysis was first performed on the sample, and the results were shown in fig. 2, with the final product being single crystal spheres assembled into chain-like monodispersed spheres.
To further explore the generality of this experiment, we irradiated Au and IrO dispersed in ethanol under the same parameters of laser conditions, respectively 2 ，RuO 2 ，CuO，Co 2 O 3 Mixture and mixture of Au and Pt Fe 2 O 3 ，Co 2 O 3 NiO mixture.
Subsequently, we selected and prepared two samples respectively, and carried out X-ray spectroscopy EDS (as shown in fig. 3 and 4) on the metal single crystal, and found that the AuIrRuCuCo and AuPtFeCoNi elements in the two samples are uniformly distributed in the single crystal particles formed by the two samples respectively. Therefore, the experiment designed by the invention successfully prepares the gold-based high-entropy single crystal solid solution alloy with uniform element distribution, is applicable to a wide variety of metal particles and oxides, and is a universal high-entropy alloy preparation method.
The invention prepares the series high-entropy alloy by laser irradiation in an organic liquid phase at normal temperature and normal pressure, utilizes the photothermal effect of pulse laser and nano particles and a reduction mechanism generated by an organic liquid phase medium under the photothermal effect, and firstly prepares the series high-entropy alloy by commonly irradiating and dispersing uniformly mixed metal and oxide particles in the organic liquid phase medium, thereby realizing a one-step method. The nanosecond pulse laser acts on substances to generate high temperature and high pressure only in the local area of the nano particles, and the organic liquid phase medium is rapidly quenched and cooled. Not only provides natural excellent conditions for the dynamic control of the high-entropy alloy, but also avoids the introduction of large-range high-temperature and high-pressure environments and redundant chemical substances, thereby improving the operability and safety of the whole experiment. The finally prepared high-entropy alloy has stable physical and chemical properties, clean surface and wide applicable element range, and is expected to show different potential in the fields of mechanics, energy conversion and biology. The synthesis method is safe, convenient, green, efficient and high in universality. Not only provides a new way and thought for the preparation and application of the high-entropy alloy, but also expands the new application of the liquid phase laser irradiation technology. The metal oxide also includes MoO 3 、WO 3 、SnO 2 Etc., in the patent as IrO 2 ，RuO 2 ，CuO，Co 2 O 3 ，Fe 2 O 3 The oxide such as NiO is exemplified.
The nanosecond pulse laser irradiates the surface of the metal nano particle, so that the metal nano particle can be quickly heated and melted through the photo-acoustic effect within the nanosecond time scale. Under such mechanisms, the melted metal nanoparticle surface promotes the decomposition of organic liquid media (e.g., common organic solvents such as ethanol, methanol, acetone, etc.) to produce reducing small molecules. Meanwhile, non-noble metal oxide nano particles which are jointly dispersed in an organic medium with metal nano particles are reduced into a non-noble metal simple substance under the combined action of pulse laser irradiation and reductive small molecules generated by an organic reagent. In addition, the special rapid heating up and rapid quenching mechanism of the organic liquid phase medium by nanosecond pulse laser irradiation are ideal conditions for preparing the high-entropy alloy. By combining the mechanisms, the mixed colloid solution of noble metal and non-noble metal uniformly dispersed in the organic solvent is irradiated by nanosecond pulse laser, and the preparation of the high-entropy alloy can be simply, conveniently and rapidly realized by only one step at normal temperature and normal pressure.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions easily contemplated by those skilled in the art within the scope of the present invention should be included in the scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims. The information disclosed in the background section herein is only for enhancement of understanding of the general background of the invention and is not to be taken as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art.
Claims (4)
1. The method for preparing the high-entropy alloy by the organic liquid phase laser irradiation at normal temperature and normal pressure is characterized by comprising the following steps:
weighing 2-5mg of metal or noble metal nano particles and non-noble metal oxide nano particles, respectively adding the metal or noble metal nano particles and the non-noble metal oxide nano particles into an organic reagent, uniformly dispersing the metal or noble metal nano particles by sufficient ultrasonic and magnetic stirring, wherein the selection of the nano particles is related to the distribution of element types in a final product;
and (3) preparing 532nm or 355nm wave band nanosecond pulse laser, and irradiating the uniformly mixed colloidal solution for 20 minutes to obtain a high-entropy alloy final product with non-uniform size, wherein the selection and parameter regulation of the laser wave band are related to the capability of reducing oxide particles.
2. The method for preparing high-entropy alloy by irradiation of organic liquid phase laser at normal temperature and pressure according to claim 1, wherein the time for irradiation of the uniformly mixed colloidal solution by the nanosecond pulse laser is 20 minutes.
3. The method for preparing high-entropy alloy by irradiation of organic liquid phase laser at normal temperature and pressure according to claim 1, wherein the organic reagent comprises a mixed solution of any one or more of the following: ethanol, acetone or methanol.
4. The method for preparing high-entropy alloy by irradiation of organic liquid phase laser at normal temperature and pressure according to claim 1, wherein the metal or noble metal nanoparticles comprise Au, ir, ru and/or Pt, and the metal oxide comprises copper oxide, iron oxide, cobalt oxide, nickel oxide, aluminum oxide, iridium oxide, ruthenium oxide, zinc oxide, molybdenum oxide, tungsten oxide and/or tin oxide.
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