CN105664929B - 一种含有贵金属的纳米片及其制备方法 - Google Patents
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- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 13
- 229910052737 gold Inorganic materials 0.000 claims abstract description 13
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 13
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 11
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 11
- 239000002114 nanocomposite Substances 0.000 claims abstract description 8
- 230000008021 deposition Effects 0.000 claims abstract description 5
- 230000009467 reduction Effects 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims description 3
- 229910004042 HAuCl4 Inorganic materials 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
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- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000003643 water by type Substances 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 2
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- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 235000013339 cereals Nutrition 0.000 claims 1
- 239000002243 precursor Substances 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 39
- 238000005805 hydroxylation reaction Methods 0.000 abstract description 10
- 239000001257 hydrogen Substances 0.000 abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 9
- 230000033444 hydroxylation Effects 0.000 abstract description 9
- 238000006303 photolysis reaction Methods 0.000 abstract description 7
- 230000015843 photosynthesis, light reaction Effects 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 5
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- 239000002356 single layer Substances 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
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- 238000011160 research Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
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- 230000001699 photocatalysis Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
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- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
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- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
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- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
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- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
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- 150000002989 phenols Chemical class 0.000 description 1
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- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
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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
- B01J23/48—Silver or gold
- B01J23/52—Gold
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- B01J35/39—
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- B01J35/40—
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/345—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of ultraviolet wave energy
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
- C07C45/512—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being a free hydroxyl group
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- C—CHEMISTRY; METALLURGY
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
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- C01B2203/107—Platinum catalysts
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
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- C01B2203/1041—Composition of the catalyst
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
本发明公开了一种含有贵金属的纳米片及其应用，属于催化材料的制备领域。M@H1.07Ti1.73O4•H2O纳米片是以H1.07Ti1.73O4•H2O纳米片为载体，通过光沉积还原法将Au、Pd、Pt等金属纳米颗粒负载于超薄的H1.07Ti1.73O4•H2O单分子层纳米片表面构成的纳米复合材料。该复合材料在光解水制氢方面表现出高效的性能，同时将其作为光催化剂用于光诱导下苯酚羟化反应制备环己酮，解决了高温高压下苯酚加氢制备环己酮的能耗大、选择性低、成本高等问题。本发明工艺简单，环保绿色，选择性高，能耗低，成本小，符合实际生产需要，具有较大的应用潜力。
Description
技术领域
本发明属于催化技术领域，具体涉及到一种贵金属@H1.07Ti1.73O4•H2O纳米片及其应用。
背景技术
环己酮是一种重要的有机化工产品，具有高溶解性和低挥发性，可以作为特种溶剂，对聚合物如硝化棉及纤维素等是一种理想的溶剂；也是重要的有机化工原料，是制备尼龙、己内酰胺和己二酸的主要中间体。随着社会现代化发展的需要环己酮的用途不断扩大，特别是作为一种高档的有机溶剂，在涂料、油墨、胶粘剂等行业被广泛应用，形成了较大的商品市场。目前常用于生产环己酮的方法有苯酚加氢法，环己烯水合法以及环己烷氧化法。然而这些制备环己酮的方法中存在着能耗高，成本大，副产物多，步骤繁杂，反应速率慢，污染大，效率低等问题。因此为了解决这些缺点以满足社会发展进步的需要和经济环境的要求，开发清洁、环保、高效的环己酮生产方法具有非常重大的意义。如何实现这一要求引起各国科研工作者们的广泛关注。到目前为止，很多苯酚液相和气相加氢条件下催化苯酚羟化反应制备环己酮的催化剂被开发出来，特别是负载金属纳米颗粒的无机材料，它们为促进苯酚的羟化制备环己酮提供了新思路和方法。然而这些催化剂大多都需要在加热，高压或者多相溶剂才能实现。此外，贵金属纳米粒子的均匀分散，以及粒径的大小对催化剂的催化活性都将产生影响。如果能使金属纳米粒子均匀分散在材料表面，并且催化剂能在常温常压等温和的条件下实现苯酚羟化制备环己酮的高效的转化，将有利于不可再生能源的节约和环境污染的降低。
而在近几十年来人们对于清洁能源的探索从未停止，光解水制氢作为一种利用太阳能制备清洁能源的方法一直是人们研究的热点，光催化剂的研究是最重要的研究热点之一，到目前为止已经有很多光催化剂被开发出来，其中二维材料由于其本身的独特结构成为今年研究的热点之一。
无机二维（2D）片状纳米材料是一类分子或原子厚度并具有各向异性的片状结构，是一种纳米级的特殊材料。同时也是重要的功能材料之一，其特殊的物理化学性质使之在催化，吸附，传导等方面有着重要的应用。贵金属Au，Pd，Pt具有较好的电学传导和催化性能，在基础研究和实际应用领域具有很大的价值，将贵金属纳米颗粒均匀地分散到纳米片表面形成复合材料不仅可以保持纳米片本身的优点，而且金属纳米颗粒与纳米片形成协同作用。用光沉积还原的方式制备高分散的纳米片已经得到很多研究者的认可，将金属纳米粒子以光沉积的方式负载到纳米片的表面形成的复合材料在多相催化反应中表现出优越的性能和诱人的前景。光催化是多相催化的一种，作为一种可利用清洁可再生的太阳能来实现化学反应的具有巨大潜力的技术，它具有绿色环保，无二次污染的特点，因此受到了国内外科学家的高度关注。如果能结合二维纳米材料的特点以及金属纳米颗粒的催化性能，将光沉积制备的金属纳米颗粒高分散于纳米片的表面制备的复合材料用于光催化反应生产清洁能源和苯酚的羟化反应制备环己酮，这将为清洁能源的开发以及生产低成本的环己酮带来新希望。
发明内容
本发明的目的在于提供一种M@H1.07Ti1.73O4•H2O(M=Au，Pd, Pt)纳米片及其制备方法和应用。本发明制得的M@H1.07Ti1.73O4•H2O纳米复合材料可作为催化剂用于光催化反应，该催化剂高效，无毒，制备方法简单，选择性高，操作简单，成本低廉，具有广阔的应用前景，并且可以扩展到其他两类或更多类贵金属的共沉积负载。
为实现上述目的，本发明采用如下技术方案：
一种贵金属@H1.07Ti1.73O4•H2O纳米片：以H1.07Ti1.73O4•H2O纳米片为载体，通过光沉积还原法将贵金属纳米颗粒负载于纳米片表面上而制备的纳米复合材料；所述的贵金属为Au、Pd或Pt，贵金属的负载量为0.5~10 wt%；贵金属纳米颗粒的粒径为2-5 nm。
一种制备如上所述的贵金属@H1.07Ti1.73O4•H2O纳米片的方法：将超薄的单分子层H1.07Ti1.73O4•H2O纳米片分散于20-25 mL去离子水中，超声搅拌直至其分散均匀，在搅拌下将金属前驱体溶液逐滴加入，并继续加入甲醇溶液，通氮气0.5 h，紫外灯照射3-5 h，过滤，洗涤和烘干后，即得到贵金属@ H1.07Ti1.73O4•H2O纳米片。
所述的金属前驱体溶液为HAuCl4•4H2O溶液、Pd(NO3)2•2H2O溶液或H2PtCl6•6H2O溶液中的一种。
所述的贵金属@H1.07Ti1.73O4•H2O纳米片作为光催化反应的催化剂的应用。
所述的光催化反应为光解水制氢的反应或光诱导下常温常压羟化苯酚制备环己酮的反应。
本发明的显著优点在于：
（1）本发明制得的M@H1.07Ti1.73O4•H2O纳米复合材料可作为催化剂用于光催化反应，该催化剂高效，无毒，制备方法简单，选择性高，操作简单，成本低廉，具有广阔的应用前景；
（2）本发明的纳米复合材料作为光解水制氢的催化剂，具有高效的光催化活性和反应稳定性；
（3）以本发明的纳米复合材料作为催化剂，在光诱导、水为溶剂以及常温常压的反应条件下，即可实现苯酚羟化制备环己酮；较传统的环己酮合成方法，本发明的方法节约能耗，降低环境污染，节约成本以及选择性更高；
（4）本发明的纳米复合材料作为催化剂时，实验操作方法简单，易于操作，有利于大规模的推广使用。
附图说明
图1是本发明的催化剂Pd@H1.07Ti1.73O4•H2O和H1.07Ti1.73O4•H2O纳米片的X射线衍射（XRD）图；
图2是本发明的催化剂Pd@H1.07Ti1.73O4•H2O的透射电子显微镜（TEM）图和高分辨透射电子显微镜（HRTEM）图；
图3是本发明的以Pd@H1.07Ti1.73O4•H2O纳米片为催化剂在光诱导下催化苯酚羟化生成环己酮的转化率-时间曲线：曲线（a, b）分别是有催化剂和光照的条件下苯酚羟化转化率和环己酮的产率情况；
图4是本发明的M@H1.07Ti1.73O4•H2O(Au,Pd,Pt)纳米片的紫外-可见漫反射图；
图5是本发明扩展的M@H1.07Ti1.73O4•H2O(Au,Pd,Pt)纳米片为催化剂光解水制氢活性图。
具体实施方式
为了使本发明所述的内容更加便于理解，下面结合具体实施方式对本发明所述的技术方案做进一步的说明，但是本发明不仅限于此。
实施例1
H1.07Ti1.73O4•H2O纳米片的制备
将摩尔比为2.4:0.8:10.4的K2CO3，Li2CO3和TiO2研磨均匀后，置于刚玉坩埚中，800℃煅烧2 h，冷却至室温，再次研磨，1000 ℃煅烧20 h，重复一次；得到层状K0.80Ti1.73Li0.67O4，取10 g所得K0.80Ti1.73Li0.67O4样品加入1000 ml，1 mol/L的盐酸溶液中搅拌，每24 h换一次酸，4天后，去离子水洗涤至中性，60 ℃干燥，即为层状H1.07Ti1.73O4•H2O；将上述层状H1.07Ti1.73O4•H2O与TBAOH（四丁基氢氧化铵）（40 wt%）溶液按照摩尔比1:1混合，磁力搅拌15天，3000 rpm离心，除去未剥离的层状物，得到H1.07Ti1.73O4•H2O纳米片的溶胶，在超声条件下滴加1 mol/L的盐酸，所得絮凝物用去离子水洗涤至离子浓度小于10 ppm；60℃干燥一晚上；即为H1.07Ti1.73O4•H2O纳米片。
取H1.07Ti1.73O4•H2O纳米片0.2 g置于玻璃瓶中，加入20 ml水，10 ml甲醇和388 μL的二水合硝酸钯溶液（10 mg/mL），超声30 min分散均匀，通0.5 h氮气以排进瓶子内部空气；用300 W氙灯照射3-5 h；所得灰黑色产物，过滤得到固体，洗涤烘干，即为Pd@H1.07Ti1.73O4•H2O纳米片。
图1展示了本发明的催化剂H1.07Ti1.73O4•H2O和Pd@H1.07Ti1.73O4•H2O纳米片的X射线衍射（XRD）图，从图中可以发现制备的H1.07Ti1.73O4•H2O纳米片为纯相，在负载Pd后H1.07Ti1.73O4•H2O纳米片结构没有改变；图2展示了本发明的催化剂Pd@H1.07Ti1.73O4•H2O的透射电子显微镜（TEM）图和高分辨透射电子显微镜（HRTEM）图，从图中可以看出Pd纳米颗粒均匀分散到H1.07Ti1.73O4•H2O纳米片表面，其平均颗粒尺寸在3-5 nm。
实施例2
Pd@H1.07Ti1.73O4•H2O纳米片在光诱导下催化苯酚的羟化制备环己酮。
将制备的Pd@H1.07Ti1.73O4•H2O纳米片用作催化剂在光诱导下实现苯酚的羟化制备环己酮，称取20 mg纳米片与100 mg硅钨酸，抽真空以排尽空气，加入2 mL纯净水、10 μL苯酚，在H2条件下搅拌，然后开启光源进行光催化反应，产物使用气相色谱检测；实验使用的光源为300 W氙灯；苯酚的转化及产物的生成情况如图3所示，从图上可以看出在有催化剂时，苯胺在光照15 h后转化率达到100 %（曲线a），环己酮的产率达到99 %以上（曲线b），而在没有加催化剂或不光照或以H1.07Ti1.73O4•H2O纳米片为催化剂的条件下，苯酚的转化率非常小，且没有环己酮的产生；因此，在光的诱导下，Pd@H1.07Ti1.73O4•H2O纳米片能高效地催化苯酚的羟化制备环己酮。
实施例3
M@H1.07Ti1.73O4•H2O(Au,Pd,Pt)纳米片制备并将其作为催化剂光解水制氢。
制备方法：将H1.07Ti1.73O4•H2O纳米片分散于22 mL去离子水中，超声搅拌直至其分散均匀；在搅拌下将HAuCl4•4H2O, H2PtCl6•6H2O或 Pd(NO3)2•2H2O溶液逐滴加入溶液中，并继续加入10 mL甲醇溶液，通氮气0.5 h，紫外灯照射3-5 h，过滤，洗涤和烘干，即得到M@H1.07Ti1.73O4•H2O(M=Au,Pd,Pt)中M的负载量按1wt%的最佳量进行换算。从图4可以看出合成的催化剂具有较强的SPR的特征吸收峰。
将制备的贵金属@H1.07Ti1.73O4•H2O(Au，Pt)纳米片为催化剂光解水制氢，取80 mg催化剂加入到72 mL水中加入8 mL三乙醇胺抽真空排尽空气，然后开启光源进行光催化反应，产物使用气相色谱检测。实验使用的光源为300 W氙灯。氢气的产生速率如图5所示，从图中可以看出M@H1.07Ti1.73O4•H2O(Au,Pd,Pt)纳米片表现出高效的产氢能力。
以上所述仅为本发明的较佳实施例，凡依本发明申请专利范围所做的均等变化与修饰，皆应属本发明的涵盖范围。
Claims (3)
1.一种贵金属@H1.07Ti1.73O4•H2O纳米片的应用，其特征在于：作为光催化反应的催化剂，所述的光催化反应为光诱导下常温常压羟化苯酚制备环己酮的反应;所述的纳米片是以H1.07Ti1.73O4•H2O纳米片为载体，通过光沉积还原法将贵金属纳米颗粒负载于纳米片表面上而制备的纳米复合材料；所述的贵金属为Au、Pd或Pt，贵金属的负载量为0.5~10 wt%；贵金属纳米颗粒的粒径为2-5 nm。
2.根据权利要求1所述的贵金属@H1.07Ti1.73O4•H2O纳米片的应用，其特征在于：所述的纳米片的制备方法为：将H1.07Ti1.73O4•H2O纳米片分散于20-25 mL去离子水中，超声搅拌直至其分散均匀，在搅拌下将金属前驱体溶液逐滴加入，并继续加入甲醇溶液，通氮气0.5 h，紫外灯照射3-5 h，过滤，洗涤和烘干后，即得到贵金属@ H1.07Ti1.73O4•H2O纳米片。
3.根据权利要求2所述的贵金属@H1.07Ti1.73O4•H2O纳米片的应用，其特征在于：所述的金属前驱体溶液为HAuCl4•4H2O溶液、Pd(NO3)2•2H2O溶液或H2PtCl6•6H2O溶液中的一种。
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