CN105944739A - 一种基于二氧化钛与硫化钼复合的半导体产氢催化剂及其制备方法和应用 - Google Patents
一种基于二氧化钛与硫化钼复合的半导体产氢催化剂及其制备方法和应用 Download PDFInfo
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 59
- 239000001257 hydrogen Substances 0.000 title claims abstract description 59
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 239000004065 semiconductor Substances 0.000 title claims abstract description 18
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000013329 compounding Methods 0.000 title abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000001699 photocatalysis Effects 0.000 claims abstract description 12
- 238000007146 photocatalysis Methods 0.000 claims abstract description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 10
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- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 claims description 11
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- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 9
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- -1 2-amino p-phthalic acid Chemical compound 0.000 claims description 7
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 6
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 6
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims description 6
- NASFKTWZWDYFER-UHFFFAOYSA-N sodium;hydrate Chemical compound O.[Na] NASFKTWZWDYFER-UHFFFAOYSA-N 0.000 claims description 6
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- 239000011684 sodium molybdate Substances 0.000 abstract description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 abstract description 2
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- YQGOJNYOYNNSMM-UHFFFAOYSA-N eosin Chemical compound [Na+].OC(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C(O)=C(Br)C=C21 YQGOJNYOYNNSMM-UHFFFAOYSA-N 0.000 description 3
- 229910052961 molybdenite Inorganic materials 0.000 description 3
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- 239000011148 porous material Substances 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- 230000003287 optical effect Effects 0.000 description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 2
- 229940043267 rhodamine b Drugs 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- WMVGVWZNSBHIBB-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol propan-2-one Chemical compound CC(C)=O.OCCN(CCO)CCO WMVGVWZNSBHIBB-UHFFFAOYSA-N 0.000 description 1
- KVYRCBOUKXJXDK-UHFFFAOYSA-N 3,4-dimethylphenazine-1,2-diamine hydrochloride Chemical compound Cl.C1=CC=CC2=NC3=C(C)C(C)=C(N)C(N)=C3N=C21 KVYRCBOUKXJXDK-UHFFFAOYSA-N 0.000 description 1
- 241000292525 Titanio Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
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- SEACYXSIPDVVMV-UHFFFAOYSA-L eosin Y Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C([O-])=C(Br)C=C21 SEACYXSIPDVVMV-UHFFFAOYSA-L 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- XTLNYNMNUCLWEZ-UHFFFAOYSA-N ethanol;propan-2-one Chemical compound CCO.CC(C)=O XTLNYNMNUCLWEZ-UHFFFAOYSA-N 0.000 description 1
- 229940031098 ethanolamine Drugs 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
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- 229910052741 iridium Inorganic materials 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
-
- B01J35/39—
-
- 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
-
- 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
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
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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
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1088—Non-supported 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
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
本发明公开了一种基于二氧化钛与硫化钼复合的半导体产氢催化剂及其制备方法和应用,涉及纳米催化剂和光催化技术领域。该复合催化剂以钛基MOF(NH2‑MIL‑125)为前驱体,在温和的水热反应中,与硫脲、二水合钼酸钠溶于水,封入反应釜,200‑220℃恒温反应,自然条件下降至室温得到纳米级复合材料。其产氢速率高达10046 μmol h‑1 g‑1,可经过离心分离回收再利用,提高了催化剂的利用率。
Description
技术领域
本发明涉及纳米催化剂和光催化技术领域,具体涉及一种基于二氧化钛与硫化钼复合的半导体产氢催化剂及其制备方法和其在光催化产氢方面的应用。
背景技术
由于全球工业化的发展,化石能源这一主要能源的过量使用导致了愈发严重的能源短缺危机以及严重的环境污染问题。因此,寻找更为清洁环保的替代能源是目前人们的研究热点。而作为一种取之不尽用之不竭的低成本能源,太阳能目前尚不能达到高效存储以及直接利用,于是科学工作者们致力于将其转化为其他可高效利用能源。
由于氢能源的燃烧产物清洁无污染、能量密度高,氢能源成为很有希望代替化石能源的新能源之一。日本Fujishima课题组于1972年首次报道了利用半导体TiO2电极在紫外光催化下分解水,得到氢气,实现了太阳能向氢能源的转化。这一发现引起了各地科学工作者的极大兴趣。水,作为一种大量存在且稳定的化合物,在自发状态下很难完成到氢气的转化。而通过能斯特方程计算,在电解池中将水分解的电压仅需1.23eV,在热力学角度上的可行性说明可以通过寻找合适的催化剂实现这一能量转化过程。
光催化分解水产氢体系基本的三个组分包括光敏剂、牺牲剂和催化剂。目前文献中大量报道的无机金属催化剂多为含有贵金属的催化剂,如Ru,Ir,Rh,Pd,Pt等。这些含贵金属催化剂虽然具有较高的光催化活性,但是昂贵的价格使其应用范围受到限制。因此非贵金属催化剂的制备是目前光催化分解水产氢的研究重点。
发明内容
本发明的目的在于提供一种可循环并回收利用的高效非贵金属产氢催化剂;另一目的在于提供其制备方法和应用。
为实现本发明的目的,本发明以传统的钛基MOF(NH2-MIL-125)为前驱体,在温和的水热反应中,与硫脲、二水合钼酸钠反应得到纳米级复合材料,用于可见光照射下催化水分解产氢。
所述高效可见光催化分解水产氢催化剂的制备方法如下:
(1)将2-氨基对苯二甲酸和钛酸四丁酯溶于无水的N,N-二甲基甲酰胺和无水乙醇的混合溶剂中,封入反应釜中,在水热法条件下,120-130℃恒温反应,自然条件下降至室温,得到悬浊液。
(2)将(1)中得到的悬浊液离心,洗涤,超声处理,离心得到固体。经干燥,研磨得到前驱体NH2-MIL-125固体粉末。
(3)将(2)中得到的前驱体和硫脲、二水合钼酸钠溶于去离子水,封入反应釜中,在水热法条件下,200-220℃恒温反应,自然条件下降至室温,得到悬浊液。
(4)将(3)中得到的悬浊液离心,洗涤,超声处理,离心得到固体。经干燥,研磨得到目标催化剂。
步骤(1)中2-氨基对苯二甲酸和钛酸四丁酯的摩尔比例是7-9:1。
步骤(1)中N,N-二甲基甲酰胺和无水乙醇体积比例是8-10:1。
步骤(3)中,前驱体和硫脲摩尔比是2-3:1;硫脲、二水合钼酸钠摩尔比例是2-4:1。
该复合材料作为催化剂应用于可见光分解水产氢系统,经优化条件后,与合适的光敏剂,牺牲剂在适当的pH条件下共同完成可见光照射下分解水产氢。在光催化产氢过程中优选的光敏剂是荧光素。优选的牺牲剂为三乙醇胺,三乙醇胺在丙酮/水溶液体系中体积百分比优选为7.5%。
本发明优点在于:经过二氧化钛与硫化钼复合得到的催化剂在可见光下的产氢速率高达10046μmol h-1 g-1,且可以循环利用。与传统催化剂相比具有合成方法简单,成本较低等优点。提供了一种解决能源危机潜在应用性的新途径,同时也为其他功能材料提供新的合成思路。
附图说明
图1为本发明催化剂合成用到的MOF前驱体的粉末X射线衍射(PXRD)图谱和单晶模拟PXRD图谱对比图;其中,1为本发明中用到的MOF,2为单晶模拟;可以看出制备的NH2-MIL-125纯度高,结晶性好。
图2为本发明催化剂的粉末X射线衍射(PXRD)表征图,其中1为本发明催化剂,2为MoS2,3为TiO2,从中可以看出,MoS2和TiO2均为纯相。
图3为本发明催化剂的放大不同倍数的透射电镜图,其中,(5)为(3)放大的高分辨透射电子显微镜图,从(5)中可以看出硫化钼与二氧化钛复合的很均匀,且连接紧密;
图4为本发明催化剂的元素面扫描(mapping)电镜图和隧道扫描电子显微镜图,其中,4-1,a、b为放大不同倍数的电镜图,4-2,c、d为放大不同倍数的隧道扫描电子显微镜图,可以看出此催化剂的形貌为花状纳米颗粒,直接显示了复合样品中Mo、Ti、S、O元素都存在并且分布情况也很清楚,从而进一步印证了是MoS2和TiO2的复合;
图5为本发明催化剂在光催化产氢过程中不同pH值对其产氢效果的影响对比图,从中可以看出最佳pH条件是11;
图6为本发明催化剂在光催化产氢过程中不同溶剂对产氢效果的影响对比图,其中1为丙酮与水,2为甲醇与水,3为乙腈与水,4为乙醇与水,从中可以看出最佳溶剂体系为丙酮和水;
图7为本发明催化剂在光催化产氢过程中不同光敏剂对产氢效果的影响对比图,其中1为荧光素,2为水溶曙红,3为醇溶曙红,4为罗丹明B,从中可以看到最佳光敏剂是荧光素;
图8为本发明催化剂在光催化产氢过程中不同牺牲剂对产氢效果的影响对比图,其中1为三乙醇胺,2为三乙胺,3为硫化钠与亚硫酸钠体系,4为乳酸,从中可以看到最佳牺牲剂是三乙醇胺;
图9为本发明催化剂的三组循环产氢效果图,从中可以看出,样品十分稳定,经过33小时循环测试,催化性能基本无衰减。
具体实施方式
下面通过实例对本发明做进一步的说明:
实施例1:合成基于二氧化钛与硫化钼复合的半导体产氢催化剂
(1)将2-氨基对苯二甲酸和钛酸四丁酯溶于无水的N,N-二甲基甲酰胺和无水乙醇的混合溶剂中,封入反应釜中,在水热法条件下,120℃恒温三天,自然条件下降至室温,得到悬浊液。2-氨基对苯二甲酸和钛酸四丁酯的摩尔比8:1。N,N-二甲基甲酰胺和无水乙醇体积比为9:1。
(2)将(1)中得到的悬浊液离心,用乙醇和纯水分别离心洗涤三次,并伴有超声处理,最后离心得到黄色固体。在75℃条件干燥12小时,取出研磨得到黄色固体粉末,即为制备催化剂的MOF前驱体NH2-MIL-125。
(3)将前驱体NH2-MIL-125(0.08mmol)和硫脲(0.04mmol)、二水合钼酸钠(0.02mmol)溶解在纯水(2mL)中,室温搅拌30分钟,然后封入在反应釜中,在水热条件下,220℃恒温24小时,自然条件下降至室温,得到黑色悬浊液离心,水和乙醇洗涤干燥,超声处理,离心得到黑色固体,经干燥,研磨得到目标催化剂。硫脲、二水合钼酸钠摩尔为3:1。
应用例1:将5mg实施例1制得的复合半导体催化剂和5mg荧光素加入到光催化反应器中,选用不同pH值的体积百分比为7.5%三乙醇胺的丙酮/水(3:1,v/v)溶液,在多孔道光催化反应系统(可见光)照射下进行光催化产氢,不同pH值的产氢效果如图5所示,最优pH值为11。
应用例2:将5mg实施例1制得的复合半导体催化剂和5mg荧光素加入到光催化反应器中,选用不同有机溶剂(有机溶剂和水的比例1:1,v/v),在pH值为11,体积百分比为7.5%的三乙醇胺,在多孔道光催化反应系统(可见光)照射下进行光催化产氢,不同有机溶剂的产氢量对比如图6所示,最优选有机溶剂为丙酮。
应用例3:将5mg实施例1制得的复合半导体催化剂加入到光催化反应器中,在pH值为11,体积百分比7.5%三乙醇胺的丙酮/水(3:1,v/v)溶液条件下,选用不同的光敏剂:曙红Y(醇溶)、曙红Y(水溶)、荧光素、罗丹明B和中性红,在多孔道光催化反应系统(可见光)照射下进行光催化产氢,不同光敏剂对产氢量的影响如图7所示,最优选光敏剂为荧光素。
应用例4:优化产氢条件后,将5mg实施例1制得的黑色固体粉末,倒入光催化反应器中,加入5mg荧光素,再注入15mL体积百分比为7.5%三乙醇胺的丙酮/水(3:1,v/v)溶液(pH=11),通氮气30分钟置换体系中的空气以保证无氧环境,用氙灯300W可见光(加420nm滤光片)进行照射,光源离反应器顶面的距离为10厘米。用安捷伦7820A型号的气相色谱检测,光照连续反应11小时,每隔一小时手动进样一次进行检测,11小时后氢气峰面积趋于稳定。产氢速率高达10046μmol h-1 g-1。
应用例5:将5mg实施例1制得的复合半导体催化剂和5mg荧光素加入到光催化反应器中,注入15mL体积百分比7.5%三乙醇胺的丙酮/水(3:1,v/v)溶液(pH=11)。在氙灯300W可见光(420nm滤光片)照射下进行第一组光催化产氢,用气相色谱测定产氢量,11小时后产氢量趋于不变。将催化剂经离心分离后回收,重新加入5mg荧光素和pH=11的体积百分比7.5%三乙醇胺的丙酮/水(3:1,v/v)溶液(15mL)。测量第二组光催化产氢量,第三组同第二组方法一样,最后将三组产氢量对比,得到如图9所示的催化剂的三组循环产氢效果图。如图9所示三组循环产氢量没有明显下降,说明该催化剂的重复利用效果较好,循环性高。
Claims (6)
1.一种基于二氧化钛与硫化钼复合的半导体产氢催化剂的制备方法,其特征在于,通过如下方法实现:
(1)将2-氨基对苯二甲酸和钛酸四丁酯溶于无水的N,N-二甲基甲酰胺和无水乙醇的混合溶剂中,封入反应釜中,在水热法条件下,120-130℃恒温反应,自然条件下降至室温,得到悬浊液;
(2)将(1)中得到的悬浊液离心,洗涤,超声处理,离心得到固体;经干燥,研磨得到前驱体NH2-MIL-125固体粉末;
(3)将(2)中得到的前驱体和硫脲、二水合钼酸钠溶于去离子水,封入反应釜中,在水热法条件下,200-220℃恒温反应,自然条件下降至室温,得到悬浊液;
(4)将(3)中得到的悬浊液离心,洗涤,超声处理,离心得到固体,经干燥,研磨得到目标催化剂。
2.如权利要求1所述的基于二氧化钛与硫化钼复合的半导体产氢催化剂的制备方法,其特征在于,步骤(1)中2-氨基对苯二甲酸和钛酸四丁酯的摩尔比例是7-9:1;
步骤(1)中N,N-二甲基甲酰胺和无水乙醇体积比例是8-10:1;
步骤(3)中,前驱体和硫脲摩尔比是2-3:1;硫脲、二水合钼酸钠摩尔比例是2-4:1。
3.一种基于二氧化钛与硫化钼复合的半导体产氢催化剂,其特征在于,采用权利要求1或2所述方法制备而成。
4.如权利要求3所述的基于二氧化钛与硫化钼复合的半导体产氢催化剂在光催化产氢中的应用,其特征在于,光催化反应器中,三乙醇胺的丙酮/水溶液中加入基于二氧化钛与硫化钼复合的半导体产氢催化剂及荧光素,pH值为11,在氙灯300W可见光照射下进行光催化产氢。
5.如权利要求4所述的基于二氧化钛与硫化钼复合的半导体产氢催化剂在光催化产氢中的应用,其特征在于,三乙醇胺在丙酮/水溶液体系中体积百分比选7.5%。
6.如权利要求4所述的基于二氧化钛与硫化钼复合的半导体产氢催化剂在光催化产氢中的应用,其特征在于,丙酮/水溶液体积比为3:1。
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