CN113042032B - Tungsten oxide photocatalyst with efficient heterogeneous junction and preparation method and application thereof - Google Patents
Tungsten oxide photocatalyst with efficient heterogeneous junction and preparation method and application thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 67
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910001930 tungsten oxide Inorganic materials 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 60
- 230000001699 photocatalysis Effects 0.000 claims abstract description 31
- 238000011065 in-situ storage Methods 0.000 claims abstract description 8
- 230000007704 transition Effects 0.000 claims abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 46
- 229910052783 alkali metal Inorganic materials 0.000 claims description 15
- -1 alkali metal tungstate Chemical class 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 12
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical group [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 4
- AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 13
- 238000000926 separation method Methods 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 description 21
- 238000004519 manufacturing process Methods 0.000 description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 15
- 239000001257 hydrogen Substances 0.000 description 15
- 229910052739 hydrogen Inorganic materials 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000004108 freeze drying Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- QWMFKVNJIYNWII-UHFFFAOYSA-N 5-bromo-2-(2,5-dimethylpyrrol-1-yl)pyridine Chemical compound CC1=CC=C(C)N1C1=CC=C(Br)C=N1 QWMFKVNJIYNWII-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical group [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- 229910052724 xenon Inorganic materials 0.000 description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000002256 photodeposition Methods 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000006193 liquid solution Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000002127 nanobelt Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
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- 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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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
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Abstract
本发明涉及光催化剂技术领域，尤其涉及一种具有高效异相结的氧化钨光催化剂及其制备方法和应用。本发明提供的光催化剂，包括WO3·0.33H2O和在所述WO3·0.33H2O原位相变的m‑WO3，所述WO3·0.33H2O和m‑WO3的界面形成异相结。在本发明中，WO3·0.33H2O和m‑WO3能够形成高效异相结，极大地促进了光生电子和空穴的分离，从而提高了本发明所述光催化剂的光催化活性；同时，由于WO3·0.33H2O和m‑WO3同为WO3体系，使WO3·0.33H2O和m‑WO3更容易满足能级匹配的条件，且两组分近似的电子结构能使光生电子在异相结中更容易实现迁移，从而提高光催化分解水的活性。
The invention relates to the technical field of photocatalysts, in particular to a tungsten oxide photocatalyst with high-efficiency heterogeneous junctions, a preparation method and application thereof. The photocatalyst provided by the present invention comprises WO 3 ·0.33H 2 O and m-WO 3 which undergoes in-situ phase transition in said WO 3 ·0.33H 2 O, said WO 3 ·0.33H 2 O and m-WO 3 The interface forms a heterogeneous junction. In the present invention, WO 3 0.33H 2 O and m-WO 3 can form a highly efficient heterogeneous junction, which greatly promotes the separation of photogenerated electrons and holes, thereby improving the photocatalytic activity of the photocatalyst of the present invention; At the same time, since WO 3 ·0.33H 2 O and m-WO 3 are both WO 3 systems, it is easier for WO 3 ·0.33H 2 O and m-WO 3 to meet the conditions of energy level matching, and the two components have similar electronic The structure can make it easier for photogenerated electrons to migrate in the heterogeneous junction, thereby improving the activity of photocatalytic water splitting.
Description
技术领域technical field
本发明涉及光催化剂技术领域，尤其涉及一种具有高效异相结的氧化钨光催化剂及其制备方法和应用。The invention relates to the technical field of photocatalysts, in particular to a tungsten oxide photocatalyst with high-efficiency heterogeneous junctions, a preparation method and application thereof.
背景技术Background technique
在众多分解水制备氢能的方法中，光催化分解水被广泛认为是简单、易操作的制氢方法。近些年来，虽然已经公开了一些光催化剂，如中国专利CN109261215A公开了一种光催化分解水制备氢气的催化剂，其公开的石墨烯负载的金属铂催化剂的制氢能力最高为0.8μmol/h，中国专利CN111229260A公开了一种用于可见光下分解水制氢的硫化镉纳米颗粒和二硫化钼纳米带异质结构催化剂及其制备方法，其公开的异质结催化剂IDE的制氢能力最高为203.7μmol/(h·g)，但是可以高效地进行光催化分解水的光催化剂并不多见，主要原因为：催化剂的电子和空穴对分离困难。现有技术一般通过提高催化剂的晶化度、担载助催化剂、进行掺杂改性等方法，使催化剂的电子和空穴对有较好的分离效果，但是这些因素的改善，对光催化活性的提高有限。Among the many methods for water splitting to produce hydrogen energy, photocatalytic water splitting is widely considered as a simple and easy-to-operate method for hydrogen production. In recent years, although some photocatalysts have been disclosed, for example, Chinese patent CN109261215A discloses a catalyst for photocatalytically decomposing water to produce hydrogen. Chinese patent CN111229260A discloses a cadmium sulfide nanoparticle and molybdenum disulfide nanobelt heterostructure catalyst and its preparation method for decomposing water to produce hydrogen under visible light. The hydrogen production capacity of the disclosed heterojunction catalyst IDE is up to 203.7 μmol/(h g), but there are few photocatalysts that can efficiently photocatalytically split water. The main reason is that it is difficult to separate the electron and hole pairs of the catalyst. In the prior art, the electron and hole pairs of the catalyst have a better separation effect by improving the crystallinity of the catalyst, loading co-catalysts, and doping modification. However, the improvement of these factors has a negative effect on the photocatalytic activity. improvement is limited.
氧化钨基半导体光催化剂作为光催化剂具有可见光吸收、易制备等优点，但是，氧化钨基半导体光催化剂也由于较高的光生载流子复合几率的问题限制了其在光催化领域的发展。Tungsten oxide-based semiconductor photocatalysts have the advantages of visible light absorption and easy preparation as photocatalysts. However, the high recombination probability of photogenerated carriers limits the development of tungsten oxide-based semiconductor photocatalysts in the field of photocatalysis.
发明内容Contents of the invention
本发明的目的在于提供一种具有高效异相结的氧化钨光催化剂及其制备方法和应用，本发明提供的光催化剂具有较高的光催化分解水的活性。The object of the present invention is to provide a tungsten oxide photocatalyst with high-efficiency heterogeneous junction and its preparation method and application. The photocatalyst provided by the present invention has higher photocatalytic water splitting activity.
为了实现上述发明目的，本发明提供以下技术方案：In order to achieve the above-mentioned purpose of the invention, the present invention provides the following technical solutions:
本发明提供了一种具有高效异相结的氧化钨光催化剂，包括WO3·0.33H2O和在所述WO3·0.33H2O原位相变的m-WO3，The present invention provides a tungsten oxide photocatalyst with a high-efficiency heterogeneous junction, including WO 3 ·0.33H 2 O and m-WO 3 that undergoes an in-situ phase transition in the WO 3 ·0.33H 2 O,
所述WO3·0.33H2O和m-WO3的界面形成异相结。The interface of WO 3 ·0.33H 2 O and m-WO 3 forms a heterogeneous junction.
优选的，所述WO3·0.33H2O和m-WO3的质量比为(4～9)：(1～6)。Preferably, the mass ratio of WO 3 ·0.33H 2 O to m-WO 3 is (4-9):(1-6).
本发明提供了上述技术方案所述的具有高效异相结的氧化钨光催化剂的制备方法，包括以下步骤：The present invention provides a method for preparing a tungsten oxide photocatalyst with a high-efficiency heterogeneous junction described in the above technical solution, comprising the following steps:
将碱金属钨酸盐与水混合，得到的碱金属钨酸盐水溶液进行第一次水热反应，得到WO3·0.33H2O；Mix the alkali metal tungstate with water, and the obtained alkali metal tungstate aqueous solution undergoes the first hydrothermal reaction to obtain WO 3 ·0.33H 2 O;
将所述WO3·0.33H2O与水混合，得到的WO3·0.33H2O水溶液进行第二次水热反应，得到所述光催化剂。The WO 3 ·0.33H 2 O is mixed with water, and the obtained WO 3 ·0.33H 2 O aqueous solution is subjected to a second hydrothermal reaction to obtain the photocatalyst.
优选的，所述碱金属钨酸盐为钨酸钠或钨酸钾。Preferably, the alkali metal tungstate is sodium tungstate or potassium tungstate.
优选的，所述碱金属钨酸盐水溶液的质量浓度为0.01～0.03g/mL。Preferably, the mass concentration of the alkali metal tungstate aqueous solution is 0.01-0.03 g/mL.
优选的，所述第一次水热反应和第二次水热反应的pH值独立的为0.5～1.5。Preferably, the pH values of the first hydrothermal reaction and the second hydrothermal reaction are independently 0.5-1.5.
优选的，所述第一次水热反应和第二次水热反应的温度独立的为180～200℃。Preferably, the temperatures of the first hydrothermal reaction and the second hydrothermal reaction are independently 180-200°C.
优选的，所述第一次水热反应的时间为3～6h，所述第二次水热反应的时间为1～48h。Preferably, the time for the first hydrothermal reaction is 3-6 hours, and the time for the second hydrothermal reaction is 1-48 hours.
本发明提供了上述技术方案所述的具有高效异相结的氧化钨光催化剂或上述技术方案所述制备方法得到的具有高效异相结的氧化钨光催化剂在光催化分解水中的应用。The present invention provides the application of the tungsten oxide photocatalyst with high-efficiency heterogeneous junction described in the above technical solution or the application of the tungsten oxide photocatalyst with high-efficiency heterogeneous junction obtained by the preparation method described in the above technical solution in photocatalytic water decomposition.
优选的，所述光催化剂在光催化分解水体系中的质量浓度为0.001～0.005g/mL。Preferably, the mass concentration of the photocatalyst in the photocatalytic water splitting system is 0.001-0.005 g/mL.
本发明提供了一种具有高效异相结的氧化钨光催化剂，包括WO3·0.33H2O和在所述WO3·0.33H2O原位相变的m-WO3，所述WO3·0.33H2O和m-WO3的界面形成异相结。在本发明中，所述WO3·0.33H2O为正交相，导带位置为-0.53eV，价带位置为2.67eV，所述m-WO3为单斜相，导带位置为-0.03eV，价带位置为2.77eV，WO3·0.33H2O和m-WO3的导带和价带的位置适宜，能够形成高效异相结，WO3·0.33H2O和m-WO3形成的异相结中“结”的构建极大地促进了光生电子和空穴的分离，从而提高了本发明所述光催化剂的光催化活性；同时，由于WO3·0.33H2O和m-WO3同为WO3体系，使WO3·0.33H2O和m-WO3更容易满足能级匹配的条件，且两组分近似的电子结构能使光生电子在异相结中更容易实现迁移，显著的提高了WO3·0.33H2O中光生电子和m-WO3中光生空穴的分离效率，从而提高光催化分解水的活性。根据实施例的结果表明，本发明提供的光催化剂在光催化分解水时，产氢速率为0.3～0.7μmol/h，产氧速率为6.8～7.7μmol/h。The present invention provides a tungsten oxide photocatalyst with a high-efficiency heterogeneous junction, including WO 3 ·0.33H 2 O and m-WO 3 in-situ phase-transformed in the WO 3 ·0.33H 2 O, and the WO 3 · The interface of 0.33H 2 O and m-WO 3 forms a heterogeneous junction. In the present invention, the WO 3 ·0.33H 2 O is an orthorhombic phase, the conduction band position is -0.53eV, and the valence band position is 2.67eV, and the m-WO 3 is a monoclinic phase, and the conduction band position is - 0.03eV, the valence band position is 2.77eV, the position of the conduction band and valence band of WO 3 ·0.33H 2 O and m-WO 3 is suitable, and can form an efficient heterogeneous junction, WO 3 ·0.33H 2 O and m-WO The construction of the "junction" in the heterogeneous junction formed by 3 greatly promotes the separation of photogenerated electrons and holes, thereby improving the photocatalytic activity of the photocatalyst of the present invention; at the same time, due to WO 3 ·0.33H 2 O and m -WO 3 is both a WO 3 system, which makes it easier for WO 3 ·0.33H 2 O and m-WO 3 to meet the conditions of energy level matching, and the similar electronic structure of the two components can make it easier for photogenerated electrons in heterogeneous junctions The migration is realized, and the separation efficiency of photogenerated electrons in WO 3 ·0.33H 2 O and photogenerated holes in m-WO 3 is significantly improved, thereby improving the activity of photocatalytic water splitting. According to the results of the examples, the photocatalyst provided by the present invention has a hydrogen production rate of 0.3-0.7 μmol/h and an oxygen production rate of 6.8-7.7 μmol/h when photocatalytically decomposing water.
本发明还提供了所述光催化剂的制备方法，通过水热反应在WO3·0.33H2O原位相变生成m-WO3，制备方法简单，易实施。The present invention also provides a preparation method of the photocatalyst, wherein m-WO 3 is generated by in-situ phase transformation of WO 3 ·0.33H 2 O through hydrothermal reaction, and the preparation method is simple and easy to implement.
附图说明Description of drawings
图1为实施例3所述光催化剂的XRD图；Fig. 1 is the XRD figure of photocatalyst described in embodiment 3;
图2为实施例1～3和对比例1～2所述光催化剂的组分占比图；Fig. 2 is the component proportion figure of photocatalyst described in embodiment 1～3 and comparative example 1～2;
图3为实施例1～3和对比例1～2所述光催化剂的产氢活性测试图；Fig. 3 is the hydrogen production activity test figure of photocatalyst described in embodiment 1～3 and comparative example 1～2;
图4为实施例1～3和对比例1～2所述光催化剂的产氧活性测试图。Fig. 4 is a test diagram of the oxygen production activity of the photocatalysts described in Examples 1-3 and Comparative Examples 1-2.
具体实施方式Detailed ways
本发明提供了一种具有高效异相结的氧化钨光催化剂，包括WO3·0.33H2O和在所述WO3·0.33H2O原位相变的m-WO3，所述WO3·0.33H2O和m-WO3的界面形成异相结。The present invention provides a tungsten oxide photocatalyst with a high-efficiency heterogeneous junction, including WO 3 ·0.33H 2 O and m-WO 3 in-situ phase-transformed in the WO 3 ·0.33H 2 O, and the WO 3 · The interface of 0.33H 2 O and m-WO 3 forms a heterogeneous junction.
本发明提供的光催化剂包括WO3·0.33H2O，所述WO3·0.33H2O导带位置为-0.53eV，价带位置为2.67eV；本发明提供的光催化剂包括m-WO3，所述m-WO3的导带位置为-0.03eV，价带位置为2.77eV；在本发明中，所述WO3·0.33H2O和m-WO3的界面形成异相结，所述光催化剂的异相结的构建极大地促进了光催化剂的光生电子和空穴的分离，从而提高了光催化剂的光催化活性。The photocatalyst provided by the present invention includes WO 3 ·0.33H 2 O, the conduction band position of said WO 3 ·0.33H 2 O is -0.53eV, and the valence band position is 2.67eV; the photocatalyst provided by the present invention includes m-WO 3 , the conduction band position of the m-WO 3 is -0.03eV, and the valence band position is 2.77eV; in the present invention, the interface of the WO 3 ·0.33H 2 O and m-WO 3 forms a heterogeneous junction, so The construction of the heterogeneous junction of the photocatalyst greatly promotes the separation of the photogenerated electrons and holes of the photocatalyst, thereby improving the photocatalytic activity of the photocatalyst.
本发明对所述光催化剂中WO3·0.33H2O和m-WO3的质量比没有特殊要求，在本发明中，所述WO3·0.33H2O和m-WO3的质量比优选为(4～9)：(1～6)，更优选为(4.5～7)：(2～5)，最优选为(5～6)：(3～4)。The present invention has no special requirements on the mass ratio of WO 3 .0.33H 2 O and m-WO 3 in the photocatalyst. In the present invention, the mass ratio of WO 3 .0.33H 2 O and m-WO 3 is preferably (4-9): (1-6), more preferably (4.5-7): (2-5), most preferably (5-6): (3-4).
本发明提供了上述技术方案所述的具有高效异相结的氧化钨光催化剂的制备方法，包括以下步骤：The present invention provides a method for preparing a tungsten oxide photocatalyst with a high-efficiency heterogeneous junction described in the above technical solution, comprising the following steps:
将碱金属钨酸盐与水混合，得到的碱金属钨酸盐水溶液进行第一次水热反应，得到WO3·0.33H2O；Mix the alkali metal tungstate with water, and the obtained alkali metal tungstate aqueous solution undergoes the first hydrothermal reaction to obtain WO 3 ·0.33H 2 O;
将所述WO3·0.33H2O与水混合，得到的WO3·0.33H2O水溶液进行第二次水热反应，得到所述光催化剂。The WO 3 ·0.33H 2 O is mixed with water, and the obtained WO 3 ·0.33H 2 O aqueous solution is subjected to a second hydrothermal reaction to obtain the photocatalyst.
在本发明中，如无特殊说明，所用原料均为本领域技术人员熟知的市售产品。In the present invention, unless otherwise specified, the raw materials used are commercially available products well known to those skilled in the art.
本发明将碱金属钨酸盐与水混合，得到的碱金属钨酸盐水溶液进行第一次水热反应，得到WO3·0.33H2O；在本发明中，所述碱金属钨酸盐优选为钨酸钠或钨酸钾，更优选为钨酸钠，最优选为二水合钨酸钠；所述碱金属钨酸盐水溶液的质量浓度优选为0.01～0.03g/mL，更优选为0.015～0.025g/mL。In the present invention, the alkali metal tungstate is mixed with water, and the obtained alkali metal tungstate aqueous solution undergoes the first hydrothermal reaction to obtain WO 3 ·0.33H 2 O; in the present invention, the alkali metal tungstate is preferably It is sodium tungstate or potassium tungstate, more preferably sodium tungstate, most preferably sodium tungstate dihydrate; the mass concentration of the alkali metal tungstate aqueous solution is preferably 0.01～0.03g/mL, more preferably 0.015～ 0.025g/mL.
在本发明中，所述第一次水热反应的pH值优选为0.5～1.5，更优选为0.8～1.2，所述第一次水热反应的pH值优选通过pH调节剂调节得到，所述pH调节剂优选包括强酸，所述强酸优选包括硝酸或盐酸，所述强酸的质量浓度为10～30％。In the present invention, the pH value of the first hydrothermal reaction is preferably 0.5-1.5, more preferably 0.8-1.2, and the pH value of the first hydrothermal reaction is preferably adjusted by a pH regulator, the The pH regulator preferably includes a strong acid, the strong acid preferably includes nitric acid or hydrochloric acid, and the mass concentration of the strong acid is 10-30%.
在本发明中，所述第一次水热反应的温度优选为180～200℃，更优选为180℃；所述第一次水热反应的时间优选为3～6h，更优选为4～5h。In the present invention, the temperature of the first hydrothermal reaction is preferably 180-200°C, more preferably 180°C; the time of the first hydrothermal reaction is preferably 3-6h, more preferably 4-5h .
在本发明中，所述第一次水热反应优选在鼓风干燥箱中进行，本发明对所述第一次水热反应的具体实施方式没有任何特殊的限定，采用本领域技术人员熟知的过程进行即可。In the present invention, the hydrothermal reaction for the first time is preferably carried out in an air blast drying oven. The present invention does not have any special restrictions on the specific implementation of the hydrothermal reaction for the first time. The process can proceed.
在本发明中，所述碱金属钨酸盐通过第一次水热反应首先生成H2WO4，H2WO4继续与水反应形成水和氧化物WO3·0.33H2O。In the present invention, the alkali metal tungstate first generates H 2 WO 4 through the first hydrothermal reaction, and H 2 WO 4 continues to react with water to form water and oxide WO 3 ·0.33H 2 O.
本发明通过控制第一次水热反应过程中的pH值、水热时间和水热反应温度，得到水和氧化物WO3·0.33H2O。The present invention obtains water and oxide WO 3 ·0.33H 2 O by controlling the pH value, hydrothermal time and hydrothermal reaction temperature in the first hydrothermal reaction process.
本发明优选对所述第一次水热反应的固体产物进行后处理，得到所述WO3·0.33H2O，在本发明中，所述后处理优选包括依次进行：洗涤和干燥，在本发明中，所述洗涤的溶剂优选为乙醇和强酸的混合溶液，所述乙醇和强酸的质量比优选为200mL：100μL，所述强酸优选与上述所述pH调节所用强酸的种类的保护范围相同，在此不在赘述，在本发明中，所述洗涤的次数优选为3～5次，更优选为4次。本发明优选对所述洗涤后的固体产物进行干燥，在本发明中，所述干燥优选为冷冻干燥，所述冷冻干燥的温度优选为-50～-60℃，所述冷冻干燥的时间优选为10～30h，更优选为12～20h。In the present invention, the solid product of the first hydrothermal reaction is preferably post-treated to obtain the WO 3 ·0.33H 2 O. In the present invention, the post-treatment preferably includes: washing and drying in sequence. In the invention, the solvent for the washing is preferably a mixed solution of ethanol and a strong acid, the mass ratio of the ethanol to the strong acid is preferably 200mL:100μL, and the strong acid is preferably the same as the type of strong acid used for pH adjustment described above. No need to go into details here, in the present invention, the number of times of washing is preferably 3-5 times, more preferably 4 times. In the present invention, the washed solid product is preferably dried. In the present invention, the drying is preferably freeze-drying, the freeze-drying temperature is preferably -50 to -60°C, and the freeze-drying time is preferably 10-30h, more preferably 12-20h.
得到WO3·0.33H2O后，本发明将WO3·0.33H2O与水混合，得到的WO3·0.33H2O水溶液进行第二次水热反应，得到所述光催化剂；在本发明中，所述WO3·0.33H2O水溶液的质量浓度优选为0.012～0.05g/mL，更优选为0.02～0.03g/mL；在本发明中，所述水优选为去离子水。After obtaining WO 3 ·0.33H 2 O, the present invention mixes WO 3 ·0.33H 2 O with water, and the obtained WO 3 ·0.33H 2 O aqueous solution undergoes a second hydrothermal reaction to obtain the photocatalyst; In the invention, the mass concentration of the WO 3 ·0.33H 2 O aqueous solution is preferably 0.012-0.05 g/mL, more preferably 0.02-0.03 g/mL; in the invention, the water is preferably deionized water.
在本发明中，所述第二次水热反应的pH值优选与第一次水热反应的pH值的保护范围相同，在此不再赘述。In the present invention, the pH value of the second hydrothermal reaction is preferably within the same protection range as the pH value of the first hydrothermal reaction, which will not be repeated here.
在本发明中，所述第二次水热反应的温度优选为180～200℃，更优选为200℃；所述第二次水热反应的时间优选为1～18h，更优选为12～24h。In the present invention, the temperature of the second hydrothermal reaction is preferably 180-200°C, more preferably 200°C; the time of the second hydrothermal reaction is preferably 1-18h, more preferably 12-24h .
在本发明中，所述WO3·0.33H2O在第二次水热反应时原位相变生成m-WO3，得到所述光催化剂，本发明通过控制第二次水热反应过程中的pH值和水热反应温度，得到m-WO3相。在本发明中，所述光催化剂中m-WO3相的含量与所述第二次水热反应的时间正相关，随着第二次水热反应时间的增长，所述光催化剂中m-WO3相的含量变大。In the present invention, the WO 3 ·0.33H 2 O undergoes an in-situ phase transition during the second hydrothermal reaction to generate m-WO 3 to obtain the photocatalyst. pH value and hydrothermal reaction temperature, the m-WO 3 phase was obtained. In the present invention, the content of the m- WO3 phase in the photocatalyst is positively correlated with the time of the second hydrothermal reaction, and as the second hydrothermal reaction time increases, the m-WO3 phase in the photocatalyst The content of WO 3 phase becomes larger.
在本发明中，所述第二次水热反应优选在鼓风干燥箱中进行，本发明对所述第二次水热反应的具体实施方式没有任何特殊的限定，采用本领域技术人员熟知的过程进行即可。In the present invention, the second hydrothermal reaction is preferably carried out in an air blast drying oven. The present invention does not have any special restrictions on the specific implementation of the second hydrothermal reaction. The process can proceed.
本发明优选对所述第二次水热反应的固体产物进行后处理，得到所述光催化剂，在本发明中，所述后处理优选与第一次水热反应的后处理的保护范围相同，在此不再赘述。In the present invention, the solid product of the second hydrothermal reaction is preferably post-treated to obtain the photocatalyst. In the present invention, the post-treatment is preferably in the same scope of protection as the post-treatment of the first hydrothermal reaction. I won't repeat them here.
本发明提供的制备方法制备得到的光催化剂形成的异相结中m-WO3是由WO3·0.33H2O原位相变而成，使WO3·0.33H2O和m-WO3更容易满足能级匹配的条件，显著的提高了WO3·0.33H2O中光生电子和m-WO3中光生空穴的分离效率，从而提高光催化分解水的活性。In the heterogeneous junction formed by the photocatalyst prepared by the preparation method provided by the present invention, m-WO 3 is formed by in-situ phase transformation of WO 3 ·0.33H 2 O, so that WO 3 ·0.33H 2 O and m-WO 3 It is easier to meet the condition of energy level matching, which significantly improves the separation efficiency of photogenerated electrons in WO 3 ·0.33H 2 O and photogenerated holes in m-WO 3 , thereby improving the activity of photocatalytic water splitting.
本发明提供了上述技术方案所述的具有高效异相结的氧化钨光催化剂或上述技术方案所述制备方法得到的具有高效异相结的氧化钨光催化剂在光催化分解水中的应用。The present invention provides the application of the tungsten oxide photocatalyst with high-efficiency heterogeneous junction described in the above technical solution or the application of the tungsten oxide photocatalyst with high-efficiency heterogeneous junction obtained by the preparation method described in the above technical solution in photocatalytic water decomposition.
在本发明中，所述光催化剂在光催化分解水体系中的质量浓度优选为0.001～0.005g/mL，更优选为0.002～0.004g/mL；在本发明中，所述光催化分解水体系的光源优选为疝气灯，所述疝气灯的功率优选为300W；在本发明中，所述光催化分解水体系优选包括光催化分解水制氢体系或光催化分解水制氧体系。In the present invention, the mass concentration of the photocatalyst in the photocatalytic water splitting system is preferably 0.001 to 0.005 g/mL, more preferably 0.002 to 0.004 g/mL; in the present invention, the photocatalytic water splitting system The light source is preferably a xenon lamp, and the power of the xenon lamp is preferably 300W; in the present invention, the photocatalytic water splitting system preferably includes a photocatalytic water splitting hydrogen production system or a photocatalytic water splitting oxygen production system.
在本发明中，所述光催化分解水制氢体系优选包括光催化剂、助催化剂、牺牲剂和水，所述水优选为去离子水；在本发明中，所述助催化剂优选为单质铂或氯铂酸，在本发明中，所述助催化剂的质量和水的体积比优选为(0.3～0.6)g：100mL，在本发明中，所述牺牲剂优选为甲醇，所述牺牲剂和水的体积比优选为(1～2)：10。In the present invention, the photocatalytic water splitting hydrogen production system preferably includes a photocatalyst, a cocatalyst, a sacrificial agent and water, and the water is preferably deionized water; in the present invention, the cocatalyst is preferably elemental platinum or Chloroplatinic acid, in the present invention, the mass of described promoter and the volume ratio of water are preferably (0.3～0.6) g: 100mL, in the present invention, described sacrificial agent is preferably methanol, described sacrificial agent and water The volume ratio of is preferably (1-2):10.
在本发明中，所述光催化分解水制氧体系优选包括光催化剂、牺牲剂和水，所述水优选为去离子水；在本发明中，所述牺牲剂优选为硝酸银，所述牺牲剂的质量浓度优选为0.001～0.002g/mL。In the present invention, the photocatalytic water splitting oxygen generation system preferably includes a photocatalyst, a sacrificial agent and water, and the water is preferably deionized water; in the present invention, the sacrificial agent is preferably silver nitrate, and the sacrificial agent is preferably silver nitrate. The mass concentration of the agent is preferably 0.001-0.002 g/mL.
下面将结合本发明中的实施例，对本发明中的技术方案进行清楚、完整地描述。显然，所描述的实施例仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solutions in the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Apparently, the described embodiments are only some of the embodiments of the present invention, but not all of them. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.
实施例1Example 1
在搅拌的条件下，将0.9896g二水合钨酸钠和50mL去离子水混合至全部溶解后，滴加质量浓度为20％的HNO3，使混合体系的pH值为0.5，在180℃水热反应4小时，用EtOH-HNO3(体积为200mL：100μL，其中，硝酸体积浓度为0.05％的)混合液洗涤4次，在-55℃冷冻干燥16h，得到WO3·0.33H2O。Under the condition of stirring, mix 0.9896g of sodium tungstate dihydrate and 50mL of deionized water until completely dissolved, then add HNO 3 with a mass concentration of 20% dropwise to make the pH of the mixed system 0.5. Reacted for 4 hours, washed 4 times with EtOH-HNO 3 (volume 200 mL: 100 μL, nitric acid volume concentration: 0.05%) mixture, and freeze-dried at -55°C for 16 hours to obtain WO 3 ·0.33H 2 O.
将0.62g WO3·0.33H2O和50mL去离子水混合至全部溶解后，滴加HNO3，使混合体系的pH值为1，在200℃下水热反应4小时，用EtOH-HNO3混合液洗涤4次，在-55℃下冷冻干燥16h，得到所述光催化剂，记为NWO-1，NWO-1中WO3·0.33H2O和m-WO3的质量比为87：13。Mix 0.62g WO 3 ·0.33H 2 O and 50mL deionized water until completely dissolved, then add HNO 3 dropwise to make the pH of the mixed system 1, react hydrothermally at 200°C for 4 hours, and mix with EtOH-HNO 3 The photocatalyst was obtained by washing with liquid for 4 times and freeze-drying at -55°C for 16 hours, which was denoted as NWO-1. The mass ratio of WO 3 ·0.33H 2 O and m-WO 3 in NWO-1 was 87:13.
实施例2Example 2
在搅拌的条件下，将0.9896g二水合钨酸钠和50mL去离子水混合至全部溶解后，滴加质量浓度为20％的HNO3，使混合体系的pH值为1.5，在180℃水热反应4小时，用EtOH-HNO3(体积为200mL：100μL，其中，硝酸体积浓度为0.05％的)混合液洗涤4次，在-55℃冷冻干燥16h，得到WO3·0.33H2O。Under stirring conditions, mix 0.9896g of sodium tungstate dihydrate and 50mL of deionized water until completely dissolved, then add HNO 3 with a mass concentration of 20% dropwise to make the pH of the mixed system 1.5, and heat it at 180°C Reacted for 4 hours, washed 4 times with EtOH-HNO 3 (volume 200 mL: 100 μL, nitric acid volume concentration: 0.05%) mixture, and freeze-dried at -55°C for 16 hours to obtain WO 3 ·0.33H 2 O.
将0.62g WO3·0.33H2O和50mL去离子水混合至全部溶解后，滴加HNO3，使混合体系的pH值为1，在200℃水热反应8小时，用EtOH-HNO3混合液洗涤4次，在-55℃冷冻干燥16h，得到所述光催化剂，记为NWO-2，NWO-2中WO3·0.33H2O和m-WO3的质量比为81：19。Mix 0.62g WO 3 ·0.33H 2 O and 50mL deionized water until completely dissolved, then add HNO 3 dropwise to make the pH value of the mixed system 1, conduct a hydrothermal reaction at 200°C for 8 hours, and mix with EtOH-HNO 3 The photocatalyst was obtained by washing with liquid for 4 times and freeze-drying at -55°C for 16 hours, which was denoted as NWO-2. The mass ratio of WO 3 ·0.33H 2 O and m-WO 3 in NWO-2 was 81:19.
实施例3Example 3
在搅拌的条件下，将0.9896g二水合钨酸钠和50mL去离子水混合至全部溶解后，滴加质量浓度为20％的HNO3，使混合体系的pH值为1，在180℃水热反应4小时，用EtOH-HNO3(体积为200mL：100μL，其中，硝酸体积浓度为0.05％的)混合液洗涤4次，在-55℃冷冻干燥16h，得到WO3·0.33H2O。Under the condition of stirring, mix 0.9896g sodium tungstate dihydrate and 50mL deionized water until completely dissolved, then add HNO 3 with a mass concentration of 20% dropwise to make the pH of the mixed system 1, and heat it at 180°C Reacted for 4 hours, washed 4 times with EtOH-HNO 3 (volume 200 mL: 100 μL, nitric acid volume concentration: 0.05%) mixture, and freeze-dried at -55°C for 16 hours to obtain WO 3 ·0.33H 2 O.
将0.62g WO3·0.33H2O和50mL去离子水混合至全部溶解后，滴加HNO3，使混合体系的pH值为1，在200℃水热反应12小时，用EtOH-HNO3混合液洗涤4次，在-55℃冷冻干燥16h，得到所述光催化剂，记为NWO-3，NWO-3中WO3·0.33H2O和m-WO3的质量比为41：59。Mix 0.62g WO 3 ·0.33H 2 O and 50mL deionized water until completely dissolved, then add HNO 3 dropwise to make the pH of the mixed system 1, conduct a hydrothermal reaction at 200°C for 12 hours, and mix with EtOH-HNO 3 The photocatalyst was obtained by washing with liquid solution for 4 times and freeze-drying at -55°C for 16 hours, which was denoted as NWO-3. The mass ratio of WO 3 ·0.33H 2 O and m-WO 3 in NWO-3 was 41:59.
对比例1Comparative example 1
在搅拌的条件下，将0.9896g二水合钨酸钠和50mL去离子水混合至全部溶解后，滴加质量浓度为20％的HNO3，使混合体系的pH值为0.5，在180℃水热反应4小时，用EtOH-HNO3(体积为200mL：100μL，其中，硝酸体积浓度为0.05％的)混合液洗涤4次，在-55℃冷冻干燥16h，得到所述光催化剂，记为NWO-4，NWO-4中WO3·0.33H2O和m-WO3质量比为100：0。Under the condition of stirring, mix 0.9896g of sodium tungstate dihydrate and 50mL of deionized water until completely dissolved, then add HNO 3 with a mass concentration of 20% dropwise to make the pH of the mixed system 0.5. Reacted for 4 hours, washed 4 times with EtOH-HNO 3 (volume 200mL: 100μL, wherein the volume concentration of nitric acid is 0.05%) mixture, and freeze-dried at -55°C for 16h to obtain the photocatalyst, denoted as NWO- 4. The mass ratio of WO 3 ·0.33H 2 O and m-WO 3 in NWO-4 is 100:0.
对比例2Comparative example 2
在搅拌的条件下，将0.9896g二水合钨酸钠和50mL去离子水混合至全部溶解后，滴加质量浓度为20％的HNO3，使混合体系的pH值为0.5，在180℃水热反应4小时，用EtOH-HNO3(体积为200mL：100μL，其中，硝酸体积浓度为0.05％的)混合液洗涤4次，在-55℃冷冻干燥16h，得到WO3·0.33H2O。Under the condition of stirring, mix 0.9896g of sodium tungstate dihydrate and 50mL of deionized water until completely dissolved, then add HNO 3 with a mass concentration of 20% dropwise to make the pH of the mixed system 0.5. Reacted for 4 hours, washed 4 times with EtOH-HNO 3 (volume 200 mL: 100 μL, nitric acid volume concentration: 0.05%) mixture, and freeze-dried at -55°C for 16 hours to obtain WO 3 ·0.33H 2 O.
将0.62g WO3·0.33H2O和50mL去离子水混合至全部溶解后，滴加HNO3，使混合体系的pH值为1，在200℃水热反应48小时，用EtOH-HNO3混合液洗涤4次，在-55℃冷冻干燥16h，得到所述光催化剂，记为NWO-5，NWO-5中WO3·0.33H2O和m-WO3的质量比为0：100。Mix 0.62g WO 3 ·0.33H 2 O and 50mL deionized water until completely dissolved, then add HNO 3 dropwise to make the pH value of the mixed system 1, conduct a hydrothermal reaction at 200°C for 48 hours, and mix with EtOH-HNO 3 The photocatalyst was obtained by washing with liquid solution for 4 times and freeze-drying at -55°C for 16 hours, which was denoted as NWO-5. The mass ratio of WO 3 ·0.33H 2 O and m-WO 3 in NWO-5 was 0:100.
测试例1test case 1
将实施例3所述的光催化剂进行XRD测试，测试结果如图1所示。衍射角为14°、18°、27°、36°和49°处出现的峰为WO3·0.33H2O的特征峰，与WO3·0.33H2O标准卡片(PDF#72-0199)相一致；衍射角为23°、34°、39°和48°处出现的峰为m-WO3特征峰，与m-WO3标准卡片(PDF#71-2141)相一致，表明实施例3成功制备了WO3·0.33H2O和m-WO3的异相结光催化剂。所述WO3·0.33H2O导带位置为-0.53eV，价带位置为2.67eV；本发明提供的光催化剂包括m-WO3，所述m-WO3的导带位置为-0.03eV，价带位置为2.77eV。The photocatalyst described in Example 3 was tested by XRD, and the test results are shown in FIG. 1 . The peaks appearing at diffraction angles of 14°, 18°, 27°, 36° and 49° are the characteristic peaks of WO 3 ·0.33H 2 O, which are consistent with the WO 3 ·0.33H 2 O standard card (PDF#72-0199) Consistent; the peaks at 23°, 34°, 39° and 48° of diffraction angles are m-WO 3 characteristic peaks, which are consistent with the m-WO 3 standard card (PDF#71-2141), indicating that Example 3 A heterogeneous junction photocatalyst of WO 3 ·0.33H 2 O and m-WO 3 was successfully prepared. The conduction band position of the WO 3 ·0.33H 2 O is -0.53eV, and the valence band position is 2.67eV; the photocatalyst provided by the present invention includes m-WO 3 , and the conduction band position of the m-WO 3 is -0.03eV , the valence band position is 2.77eV.
应用例1Application example 1
将实施例1～3和对比例1～2制备得到的光催化剂进行催化活性测试：The photocatalysts prepared in Examples 1-3 and Comparative Examples 1-2 were tested for catalytic activity:
产氢活性测试：将0.1g光催化剂和90ml去离子水置于反应器中，在搅拌的条件下混合构成悬浮体系，依次加入50μL氯铂酸(浓度10mg/mL，以Pt计)和10ml甲醇。将反应器接入光催化测试系统，抽真空20min去除水中含有的溶解氧，开氙气灯进行照射，在300W的氙灯光源的照射下进行光催化分解水反应。开灯后前2个小时先进行光沉积反应，光沉积结束后移开光源，抽真空5min去除光催化测试循环系统中光沉积反应生成的气体，然后移回光源进行光催化分解水反应，并从此时开始计时，每1h取样1次，取样至开始计时后第4h。产氢活性由与光催化测试系统相接连的气相色谱仪进行展示。Hydrogen production activity test: put 0.1g of photocatalyst and 90ml of deionized water in the reactor, mix under stirring conditions to form a suspension system, add 50μL of chloroplatinic acid (concentration 10mg/mL, calculated as Pt) and 10ml of methanol in sequence . Connect the reactor to the photocatalytic test system, vacuumize for 20 minutes to remove the dissolved oxygen contained in the water, turn on the xenon lamp for irradiation, and carry out the photocatalytic water splitting reaction under the irradiation of the 300W xenon lamp light source. The first 2 hours after the light is turned on, the photodeposition reaction is carried out first. After the photodeposition is completed, the light source is removed, and the gas generated by the photodeposition reaction in the photocatalytic test cycle system is removed by vacuuming for 5 minutes. Then, the light source is moved back to the photocatalytic water splitting reaction, and Start timing from this moment, take a sample every 1h, and sample until the 4th hour after the start of timing. The hydrogen production activity was demonstrated by a gas chromatograph connected to a photocatalytic test system.
产氧活性测试：将0.1g光催化剂和100ml去离子水置于反应器中，在搅拌的条件下混合构成悬浮体系，加入0.1699g硝酸银。将反应器接入光催化测试系统，抽真空20min去除水中含有的溶解氧，开氙灯进行照射，在300W的氙灯光源的照射下进行光催化分解水反应。开灯后开始计时，每1h取样1次，取样至开始计时后第4h。产氧活性由与光催化测试系统相接连的气相色谱仪进行展示。Oxygen production activity test: 0.1g of photocatalyst and 100ml of deionized water were placed in a reactor, mixed under stirring conditions to form a suspension system, and 0.1699g of silver nitrate was added. Connect the reactor to the photocatalytic test system, vacuumize for 20 minutes to remove the dissolved oxygen contained in the water, turn on the xenon lamp for irradiation, and carry out the photocatalytic water splitting reaction under the irradiation of the 300W xenon lamp light source. Start timing after turning on the light, take a sample every 1h, and sample until the 4th hour after the start of timing. Oxygen production activity was demonstrated by a gas chromatograph connected to a photocatalytic test system.
测试结果如图3所示，由图3得出的数据现列于表1。由图3和表1得出，本发明提供的光催化剂由于形成了WO3·0.33H2O和m-WO3的界面异相结，极大地促进了催化剂光生电子和空穴的分离，从而提高了光催化剂的光催化活性，在光催化分解水时，产氢速率为0.3～0.7μmol/h，产氧速率为6.8～7.7μmol/h，而对比例1制备的催化剂仅为WO3·0.33H2O，产氢速率为0.02μmol/h，产氧速率为3.7μmol/h，对比例2制备的催化剂仅为m-WO3，产氢速率为0μmol/h，产氧速率为6.2μmol/h，均低于实施例1～3得到的催化剂产品。The test results are shown in Figure 3, and the data obtained from Figure 3 are listed in Table 1. As can be seen from Figure 3 and Table 1, the photocatalyst provided by the present invention greatly promotes the separation of catalyst photogenerated electrons and holes due to the formation of WO 3 ·0.33H 2 O and m-WO 3 interfacial heterogeneous junctions, thereby The photocatalytic activity of the photocatalyst is improved. When photocatalytically splitting water, the hydrogen production rate is 0.3-0.7 μmol/h, and the oxygen production rate is 6.8-7.7 μmol/h, while the catalyst prepared in Comparative Example 1 is only WO 3 · 0.33H 2 O, the hydrogen production rate is 0.02 μmol/h, the oxygen production rate is 3.7 μmol/h, the catalyst prepared in Comparative Example 2 is only m-WO 3 , the hydrogen production rate is 0 μmol/h, and the oxygen production rate is 6.2 μmol /h, are lower than the catalyst product that embodiment 1～3 obtains.
表1不同光催化剂产氢产氧活性Table 1 Hydrogen and oxygen production activities of different photocatalysts
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above is only a preferred embodiment of the present invention, it should be pointed out that, for those of ordinary skill in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, and these improvements and modifications can also be made. It should be regarded as the protection scope of the present invention.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010280551A (en) * | 2009-06-08 | 2010-12-16 | Kanto Denka Kogyo Co Ltd | Tungsten oxide fine particle and method for producing the same |
| JP2015100755A (en) * | 2013-11-26 | 2015-06-04 | 国立研究開発法人物質・材料研究機構 | Photocatalyst material and method for producing the same |
| CN106550613A (en) * | 2014-07-25 | 2017-03-29 | 苏州汉瀚储能科技有限公司 | A kind of purposes of tungstenic material |
| CN109364910A (en) * | 2018-12-14 | 2019-02-22 | 青岛大学 | A kind of heterogeneous tungsten trioxide nanobelt photocatalyst and its preparation method and application |
| CN109368703A (en) * | 2018-11-15 | 2019-02-22 | 厦门大学 | A kind of preparation method of tungsten trioxide sheet |
| JP2019037919A (en) * | 2017-08-23 | 2019-03-14 | シャープ株式会社 | Photocatalyst and method for producing photocatalyst |
| CN109731563A (en) * | 2019-02-25 | 2019-05-10 | 辽宁石油化工大学 | A kind of in-phase junction photocatalyst and its preparation method and application |
| CN112337458A (en) * | 2019-08-09 | 2021-02-09 | 辽宁石油化工大学 | Tungsten oxide hydrate heterogeneous photocatalyst and preparation method and application thereof |
-
2021
- 2021-04-01 CN CN202110353962.5A patent/CN113042032B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010280551A (en) * | 2009-06-08 | 2010-12-16 | Kanto Denka Kogyo Co Ltd | Tungsten oxide fine particle and method for producing the same |
| JP2015100755A (en) * | 2013-11-26 | 2015-06-04 | 国立研究開発法人物質・材料研究機構 | Photocatalyst material and method for producing the same |
| CN106550613A (en) * | 2014-07-25 | 2017-03-29 | 苏州汉瀚储能科技有限公司 | A kind of purposes of tungstenic material |
| JP2019037919A (en) * | 2017-08-23 | 2019-03-14 | シャープ株式会社 | Photocatalyst and method for producing photocatalyst |
| CN109368703A (en) * | 2018-11-15 | 2019-02-22 | 厦门大学 | A kind of preparation method of tungsten trioxide sheet |
| CN109364910A (en) * | 2018-12-14 | 2019-02-22 | 青岛大学 | A kind of heterogeneous tungsten trioxide nanobelt photocatalyst and its preparation method and application |
| CN109731563A (en) * | 2019-02-25 | 2019-05-10 | 辽宁石油化工大学 | A kind of in-phase junction photocatalyst and its preparation method and application |
| CN112337458A (en) * | 2019-08-09 | 2021-02-09 | 辽宁石油化工大学 | Tungsten oxide hydrate heterogeneous photocatalyst and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 不同晶型WO·30.33H_2O的结构及性能;胡栋虎等;《无机化学学报》;20110110(第01期);第22-29页 * |
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