CN109647397B - Method for preparing tungsten trioxide/Pt nano composite material by utilizing tungsten trioxide color-changing performance - Google Patents
Method for preparing tungsten trioxide/Pt nano composite material by utilizing tungsten trioxide color-changing performance Download PDFInfo
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- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 35
- 239000000463 material Substances 0.000 title claims abstract description 32
- 230000008021 deposition Effects 0.000 claims abstract description 30
- 239000007783 nanoporous material Substances 0.000 claims abstract description 14
- 239000003792 electrolyte Substances 0.000 claims abstract description 12
- 229910021607 Silver chloride Inorganic materials 0.000 claims abstract description 9
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims abstract description 9
- 238000002845 discoloration Methods 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 7
- 239000010439 graphite Substances 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000004140 cleaning Methods 0.000 claims abstract description 5
- 238000007781 pre-processing Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 36
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000000151 deposition Methods 0.000 description 25
- 230000008859 change Effects 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 238000004070 electrodeposition Methods 0.000 description 5
- 239000002086 nanomaterial Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 238000000861 blow drying Methods 0.000 description 3
- 239000004567 concrete Substances 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000005137 deposition process Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000000231 atomic layer deposition Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000004729 solvothermal method Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6527—Tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
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Abstract
A method for preparing a tungsten trioxide/Pt nano composite material by utilizing the discoloration performance of tungsten trioxide, relating to WO3A preparation method of Pt nano composite material. Aims to solve the problem of the existing synthetic WO3The Pt/nano composite material has the problems of complicated steps and high energy consumption. The method comprises the following steps: firstly, preprocessing: mixing WO3The nanopore material is used as a working electrode, graphite is used as a counter electrode, Ag/AgCl is used as a reference electrode, and negative voltage is applied; secondly, deposition: removing the reference electrode and the counter electrode, pouring out the electrolyte, adding the deposition solution, and standing in a dark place; thirdly, cleaning and drying: mixing WO3Taking out the nano-porous material, washing and drying to obtain the WO3A Pt nanocomposite material. The method has simple steps and short deposition time, and the prepared WO3The Pt/nano composite material has more excellent electrocatalytic performance. The invention is used for preparing WO3A Pt nanocomposite material.
Description
Technical Field
The invention relates to a WO3A preparation method of Pt nano composite material.
Background
At present, many methods for synthesizing WO have been proposed3Methods of/Pt nanocomposites, including chemical vapor deposition, atomic layer deposition, hydrothermal methods, solvothermal methods, and electrodeposition. However, these methods have certain problems. Although the chemical vapor deposition method can obtain a thin film plating layer with high purity, it has high working temperature, requires specialized equipment, increases cost, and is not simple enough. Atomic layer deposition, while controlled to a single atomic layer, requires specialized equipment and cumbersome steps. The hydrothermal method and the solvothermal method are similar, and require subsequent complicated washing, centrifuging, drying and other steps, and the experimental process basically requires a continuous high-temperature environment.
The electrodeposition process is that under the action of an external voltage, cations in the deposition solution are reduced to metal atoms on the surface of the substrate and attached to the surface of the electrode, and the process of applying the voltage is the deposition process. Electrodeposition requires constant application of voltage and consumes a lot of energy.
Disclosure of Invention
The invention aims to solve the problem of the existing synthetic WO3The problems of complicated steps and large energy consumption of the method of the Pt nano composite material are solved, and the method is beneficial to providingBy using WO3Preparation of WO with color-changing Properties3A method for preparing Pt nanocomposite material.
The method for preparing the tungsten trioxide/Pt nano composite material by utilizing the discoloration performance of the tungsten trioxide comprises the following steps:
firstly, preprocessing:
under the voltage of 40-45V, taking the W sheet as an anode and the Pt electrode as a cathode, and carrying out anodic oxidation for 1-2h to obtain WO3A nanoporous material;
mixing WO3The nanopore material is used as a working electrode, graphite is used as a counter electrode, Ag/AgCl is used as a reference electrode, the electrolyte is a dilute acid solution, and a negative voltage of 0.3-0.5V is applied for more than 30 s; at this time WO3To blue;
secondly, deposition: removing the reference electrode and the counter electrode, pouring out the electrolyte, immediately adding the deposition solution, placing in a dark place, and standing for 0.5-2 h;
thirdly, cleaning and drying: mixing WO3Taking out the nano-porous material, washing with deionized water, and blow-drying to obtain WO3A Pt nanocomposite material.
Further, the dilute acid solution is HClO with the concentration of 0.01-1mol/L4Solutions of
Further, the deposition solution is H2PtCl6And H2SO4Mixed liquor of composition or H2PtCl6And (3) solution.
Further, H in the mixed solution2PtCl6Has a concentration of 5mmol/L, H2SO4The concentration of (2) is 0.5 mol/L.
Further, said H2PtCl6H in solution2PtCl6The concentration of (2) was 5 mmol/L.
The principle of the invention is as follows:
different from the existing electrodeposition method, the method only applies voltage to change the color of the film, and the color change principle is that electrons and H with small diameter are generated under the action of an electric field+、Li+Isosingly charged positive ions from WO3Both sides of the film enter the film, and the injected electrons combine W with6+Reduction of ions to W5+Generation of W6+And W5+Small polaron transitions between ions, resulting in a color change. The deposition principle of the method is that during the color recovery process, W5+Is changed into W6+Loss of electrons, Pt in the deposition solution4+It is likely that the electrons will be captured to form elemental Pt, which is deposited on WO3Surface of WO formation3a/Pt composite material.
The invention has the beneficial effects that:
the method has simple steps and short deposition time, and obviously reduces the content of the impurities in WO3The complexity of the process for depositing Pt on the substrate.
The method only applies negative voltage to other electrolyte to change the electrolyte into blue, and then the electrolyte is put into the deposition solution, and the WO with deposited Pt can be obtained without external extra energy injection in the whole deposition process3Nanocomposite and good dispersion of deposited Pt particles, WO prepared3The Pt/nano composite material has more excellent electrocatalytic performance.
High-end professional equipment is not needed, the requirements on conditions such as temperature and pressure are not needed, external energy injection is not needed in the deposition process, the speed is high, the energy is saved, and the cost is low.
Drawings
FIG. 1 shows WO of example 13SEM pictures after deposition;
FIG. 2 shows WO in example 23SEM photograph before deposition;
FIG. 3 shows WO in example 13EDS test results of Pt nano materials;
FIG. 4 shows WO of example 13The Pt nano material linear scanning potential test result;
FIG. 5 shows WO in example 13The Pt nano material cyclic voltammetry test result.
Detailed Description
The technical solution of the present invention is not limited to the following specific embodiments, but includes any combination of the specific embodiments.
The first embodiment is as follows: the method for preparing the tungsten trioxide/Pt nano composite material by utilizing the discoloration performance of the tungsten trioxide comprises the following steps:
firstly, preprocessing:
under the voltage of 40-45V, taking the W sheet as an anode and the Pt electrode as a cathode, and carrying out anodic oxidation for 1-2h to obtain WO3A nanoporous material;
mixing WO3The nanopore material is used as a working electrode, graphite is used as a counter electrode, Ag/AgCl is used as a reference electrode, the electrolyte is a dilute acid solution, and a negative voltage of 0.3-0.5V is applied for more than 30 s;
secondly, deposition: removing the reference electrode and the counter electrode, pouring out the electrolyte, immediately adding the deposition solution, placing in a dark place, and standing for 0.5-2 h;
thirdly, cleaning and drying: mixing WO3Taking out the nano-porous material, washing with deionized water, and blow-drying to obtain WO3A Pt nanocomposite material.
Different from the existing electrodeposition method, the method only applies voltage to change the color of the film, and the color change principle is that electrons and H with small diameter are generated under the action of an electric field+、Li+Isosingly charged positive ions from WO3Both sides of the film enter the film, and the injected electrons combine W with6+Reduction of ions to W5+Generation of W6+And W5+Small polaron transitions between ions, resulting in a color change. The deposition principle of the method is that during the color recovery process, W5+Is changed into W6+Loss of electrons, Pt in the deposition solution4+It is likely that the electrons will be captured to form elemental Pt, which is deposited on WO3Surface of WO formation3a/Pt composite material.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the dilute acid solution is HClO with the concentration of 0.01-1mol/L4And (3) solution. The rest is the same as the first embodiment.
The third concrete implementation mode: the first difference between the present embodiment and the specific embodiment is: the dilute acid solution is HClO with the concentration of 0.1mol/L4And (3) solution. The rest is the same as the first embodiment.
The fourth concrete implementation mode: this embodiment and the detailed descriptionThe first or second different is: the deposition solution is H2PtCl6And H2SO4Mixed liquor of composition or H2PtCl6And (3) solution. The other is the same as in the first or second embodiment.
The fifth concrete implementation mode: the fourth difference between this embodiment and the specific embodiment is that: h in the mixed solution2PtCl6Has a concentration of 5mmol/L, H2SO4The concentration of (2) is 0.5 mol/L. The rest is the same as the fourth embodiment.
The sixth specific implementation mode: the fourth difference between this embodiment and the specific embodiment is that: said H2PtCl6H in solution2PtCl6The concentration of (2) was 5 mmol/L. The rest is the same as the fourth embodiment.
The following examples are given to illustrate the present invention, and the following examples are carried out on the premise of the technical solution of the present invention, and give detailed embodiments and specific procedures, but the scope of the present invention is not limited to the following examples.
Example 1:
the method for preparing the tungsten trioxide/Pt nano composite material by utilizing the discoloration performance of the tungsten trioxide comprises the following steps:
firstly, preprocessing:
under the voltage of 40V, taking a W sheet as an anode and a Pt electrode as a cathode, and anodizing for 1h to obtain WO3A nanoporous material;
mixing WO3The nanopore material is used as a working electrode, graphite is used as a counter electrode, Ag/AgCl is used as a reference electrode, and the electrolyte is HClO of 0.1mol/L4Applying negative voltage of 0.3V for 30s to the solution; at this time WO3To blue;
secondly, deposition: removing the reference electrode and the counter electrode, pouring out the electrolyte, immediately adding the deposition solution, placing in a dark place, and standing for 0.5 h; the deposition solution is 5mmol/L H2PtCl6A solution;
thirdly, cleaning and drying: mixing WO3Taking out the nano-porous material, washing with deionized water, and blow-drying to obtain WO3Pt nanocompositeAnd (5) synthesizing the materials.
For the WO prepared in this example3The Pt nanocomposites were tested as follows:
(I) SEM test:
FIG. 1 is WO3Scanning electron micrograph (magnification 20000 times) after deposition, and FIG. 2 shows WO3Scanning electron micrograph before deposition (magnification 20000 times). SEM test results show that deposition is in WO3The surface of the nanopore has Pt particles. FIG. 3 is WO3EDS test results of/Pt nano-materials.
TABLE 1
The results of the EDS tests were collated to give the elemental composition of the product of table 1, with the results in table 1 indicating that the material consists of W, O, Pt, C being primarily due to surface adsorbed contaminants and motor oil in a scanning electron microscope.
(II) linear scanning potential test:
at 0.5mol H2SO4In the test solution, the area of the working electrode is 1cm2WO3The counter electrode is a graphite electrode, the reference electrode is Ag/AgCl, the counter electrode is converted into a hydrogen standard electrode, and the test result is shown in figure 4, and in figure 4- - -represents WO3- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -3ED-represents WO3-BD. Nanocomposite WO obtained after deposition of Pt by the process3Pt-BD and pure WO3And electrodeposited nanocomposite WO3Compared with Pt-ED materials, the initial overpotential is reduced to 71mV, namely the hydrogen evolution performance is greatly improved, and clean energy H is easier to generate2And the observation in experiments revealed that the nanocomposite WO obtained after the deposition of Pt by the method3Pt-BD capable of producing H2The speed is faster, and the hydrogen evolution material can solve the problems of energy and pollution. WO illustrating the preparation of the process3The Pt/nano composite material has more excellent catalytic performance.
(III) Cyclic voltammetry test
At 0.1mol/L H2SO4+0.2mol/L CH3In the OH solution, the area of the working electrode is 1cm2WO3The counter electrode is a graphite electrode, the reference electrode is Ag/AgCl, and the test results are shown in figure 5 and figure 5-WO3- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -3ED-represents WO3-BD. Nanocomposite WO obtained after deposition of Pt by the process3Pt-BD and pure WO3And electrodeposited nanocomposite WO3There are two distinct peaks in the cyclic voltammogram compared to the Pt-ED material, the peak at 0.583V (V vs. Ag/AgCl) being due to the material pair CH3The oxidation of OH, at a peak of 0.423V (V vs. Ag/AgCl), is due to the removal of carbon species that cause CO poisoning, indicating that pure WO3And electrodeposited nanocomposite WO3the/Pt-ED material has no oxidation effect on methanol, and the nano composite WO obtained after the Pt is deposited by the method3The Pt-BD has good oxidation effect on methanol. WO illustrating the preparation of the process3The Pt/nano composite material has more excellent catalytic performance.
Claims (5)
1. A method for preparing tungsten trioxide/Pt nano composite material by utilizing tungsten trioxide discoloration performance is characterized by comprising the following steps:
firstly, preprocessing:
under the voltage of 40-45V, taking the W sheet as an anode and the Pt electrode as a cathode, and carrying out anodic oxidation for 1-2h to obtain WO3A nanoporous material;
mixing WO3The nanopore material is used as a working electrode, graphite is used as a counter electrode, Ag/AgCl is used as a reference electrode, the electrolyte is a dilute acid solution, and a negative voltage of 0.3-0.5V is applied for more than 30 s;
secondly, deposition: removing the reference electrode and the counter electrode, pouring out the electrolyte, immediately adding the deposition solution, placing in a dark place, and standing for 0.5-2 h; the deposition solution is H2PtCl6And H2SO4Mixed liquor of composition or H2PtCl6A solution;
thirdly, cleaning and drying: mixing WO3Taking out the nano-porous material, washing with deionized water, and blowingDrying to obtain WO3A Pt nanocomposite material.
2. The method for preparing tungsten trioxide/Pt nanocomposite material by utilizing tungsten trioxide discoloration property as claimed in claim 1, wherein said dilute acid solution is HClO of 0.01-1mol/L4And (3) solution.
3. The method for preparing tungsten trioxide/Pt nanocomposite material by utilizing tungsten trioxide discoloration property as claimed in claim 1, wherein said dilute acid solution is 0.1mol/L HClO4And (3) solution.
4. The method for preparing tungsten trioxide/Pt nanocomposite material by utilizing tungsten trioxide discoloration property according to claim 1, wherein H is contained in the mixed solution2PtCl6Has a concentration of 5mmol/L, H2SO4The concentration of (2) is 0.5 mol/L.
5. The method for preparing tungsten trioxide/Pt nanocomposite material according to claim 1, wherein the H is selected from the group consisting of2PtCl6H in solution2PtCl6The concentration of (2) was 5 mmol/L.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1974890A (en) * | 2006-11-24 | 2007-06-06 | 大连理工大学 | Nanometer porous tungsten trioxide material and its prepn and application |
| CN101157033A (en) * | 2007-11-02 | 2008-04-09 | 中国科学院上海硅酸盐研究所 | A mesoporous Pt/WO* electro-catalyst and its preparing method |
| CN103022520A (en) * | 2011-09-27 | 2013-04-03 | 中国科学院大连化学物理研究所 | Fuel-cell catalyst Pt/WO3 and application thereof |
| CN109126767A (en) * | 2018-09-28 | 2019-01-04 | 南昌航空大学 | WO applied to degradation Florfenicol3Nanometer sheet and preparation method |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1974890A (en) * | 2006-11-24 | 2007-06-06 | 大连理工大学 | Nanometer porous tungsten trioxide material and its prepn and application |
| CN101157033A (en) * | 2007-11-02 | 2008-04-09 | 中国科学院上海硅酸盐研究所 | A mesoporous Pt/WO* electro-catalyst and its preparing method |
| CN103022520A (en) * | 2011-09-27 | 2013-04-03 | 中国科学院大连化学物理研究所 | Fuel-cell catalyst Pt/WO3 and application thereof |
| CN109126767A (en) * | 2018-09-28 | 2019-01-04 | 南昌航空大学 | WO applied to degradation Florfenicol3Nanometer sheet and preparation method |
Non-Patent Citations (1)
| Title |
|---|
| Formation of Subsurface W5+ Species in Gasochromic Pt/WO3 Thin Films Exposed to Hydrogen;Pedro Castillero et al.;《J. Phys. Chem. C 》;20170626(第121期);第15719-15727页 * |
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