CN108452803B - 一种Nb-Rh共掺二氧化钛光催化剂及其制备方法和用途 - Google Patents
一种Nb-Rh共掺二氧化钛光催化剂及其制备方法和用途 Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000011941 photocatalyst Substances 0.000 title abstract description 7
- 239000004408 titanium dioxide Substances 0.000 title abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 230000001699 photocatalysis Effects 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 6
- 238000005336 cracking Methods 0.000 claims abstract description 4
- 239000010948 rhodium Substances 0.000 claims description 80
- 239000010955 niobium Substances 0.000 claims description 68
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 56
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 42
- 239000001257 hydrogen Substances 0.000 claims description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 27
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 21
- 238000004519 manufacturing process Methods 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 18
- 239000012153 distilled water Substances 0.000 claims description 16
- DASQFLOSJLGZBR-UHFFFAOYSA-K C(C)O.[Rh](Cl)(Cl)Cl Chemical compound C(C)O.[Rh](Cl)(Cl)Cl DASQFLOSJLGZBR-UHFFFAOYSA-K 0.000 claims description 12
- DSYGQOJJTJAWKY-UHFFFAOYSA-I [Nb+5].C(C)O.[Cl-].[Cl-].[Cl-].[Cl-].[Cl-] Chemical compound [Nb+5].C(C)O.[Cl-].[Cl-].[Cl-].[Cl-].[Cl-] DSYGQOJJTJAWKY-UHFFFAOYSA-I 0.000 claims description 12
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 claims description 10
- 238000006303 photolysis reaction Methods 0.000 claims description 10
- 230000015843 photosynthesis, light reaction Effects 0.000 claims description 10
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 10
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims description 9
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 239000002105 nanoparticle Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 238000004523 catalytic cracking Methods 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 2
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 2
- 229940012189 methyl orange Drugs 0.000 claims description 2
- 239000002086 nanomaterial Substances 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims 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 claims description 2
- 229940043267 rhodamine b Drugs 0.000 claims description 2
- 238000003980 solgel method Methods 0.000 claims description 2
- 239000010936 titanium Substances 0.000 abstract description 53
- 238000012986 modification Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 229910052758 niobium Inorganic materials 0.000 abstract description 3
- 229910052703 rhodium Inorganic materials 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 239000011858 nanopowder Substances 0.000 description 15
- 230000003197 catalytic effect Effects 0.000 description 7
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- 238000005516 engineering process Methods 0.000 description 6
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- 238000007146 photocatalysis Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000002238 attenuated effect Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- GGBGFOCTWZWAIO-UHFFFAOYSA-N ethanol rhodium Chemical compound C(C)O.[Rh] GGBGFOCTWZWAIO-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
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- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种多用途Nb‑Rh共掺二氧化钛光催化剂及其制备方法和用途,所述催化剂通过Nb和Rh对TiO2进行掺杂改性合成。掺杂改性合成的Ti1‑x‑yNbxRhyO2催化剂具有极好的光催化效应,主要是针对光催化裂解水和光催化裂解有机物。改性后的Ti1‑x‑yNbxRhyO2维持了TiO2原有的化学稳定性。根据这些特性,该催化剂在能源和环境领域具有较好的应用前景。
Description
技术领域
本发明涉及一种光催化裂解水制氢和光催化裂解有机物催化剂及其制备方法和应用,涉及半导体光催化技术领域,具体涉及二氧化钛光催化材料技术领域。
背景技术
随着石油、煤炭等传统化石能源的逐渐枯竭和环境问题的日益恶化,以化石能源为基础的传统能源结构体系正面临着前所未有的危机与挑战。氢气具有高的能量密度、优异的燃烧性能、清洁无污染等优点,是传统化石能源的最佳可替代绿色能源。然而,氢能的利用很大程度上取决于制氢技术工艺的发展,目前工业制氢工艺主要是石化催化裂化及天然气蒸汽重整制氢,该工艺从环境以及能量综合利用的角度来考虑并不符合“绿色可持续发展”的发展需求。近年来,随着新型技术和材料的不断发展和电网系统的不断优化与升级,光解水制氢技术的优势被不断放大,甚至被许多科学家与企业家们誉为“最理想的工业制氢方法”,而该技术的最核心问题是高效、稳定、廉洁的制氢光催化剂的开发。
二氧化钛成本低,化学性质稳定且无污染,被认为是较有前景的光催化剂。然而,二氧化钛的价带较宽对光的吸收利用较为有限,限制了其在光催化领域的应用。
发明内容
本发明的目的是针对目前光催化领域存在的催化剂催化效率低的问题,提供一种Nb-Rh共掺杂TiO2催化剂,其化学组成可表示为Ti1-x-yNbxRhyO2,其中,x的范围为0<x≤0.1,y的范围为0<y≤0.1。优选地,1×10-5≤x≤0.08,1×10-5≤y≤0.08;还优选地,1×10-4≤x≤0.06,1×10-4≤y≤0.06;进一步优选地,5×10-4≤x≤0.05,5×10-4≤y≤0.06。
作为示例性的实例,所述催化剂的化学组成可表示为:Ti0.998Nb0.001Rh0.001O2;Ti0.949Nb0.05Rh0.001O2;Ti0.949Nb0.001Rh0.05O2;Ti0.996Nb0.002Rh0.002O2;Ti0.98Nb0.01Rh0.01O2;Ti0.90Nb0.05Rh0.05O2;Ti0.97Nb0.02Rh0.01O2;Ti0.999Nb0.0005Rh0.0005O2;Ti0.97Nb0.015Rh0.015O2;Ti0.94Nb0.03Rh0.03O2;Ti0.99Nb0.005Rh0.005O2;Ti0.96Nb0.02Rh0.02O2。
根据本发明,当所述催化剂用于光解水产氢时,优选地,x、y为0.002≤x=y≤0.02,进一步优选地,x、y为0.01。
根据本发明,优选地,所述催化剂为掺杂型纳米材料,微结构为零维纳米颗粒。
根据本发明,所述纳米颗粒平均粒度可以为10-55nm,优选为30-50nm,进一步优选地,所述平均粒度为40nm。
根据本发明,优选地,所述催化剂为金红石相与锐钛矿相混合晶相,进一步优选地,以金红石相为主要晶相。
根据本发明,所述催化剂可循环使用15次以上,其催化活性没有衰减,具体的,所述催化剂可循环使用20次其活性没有衰减。
本发明所述催化剂具有较高的催化活性,作为实例,Ti0.98Nb0.01Rh0.01O2的光解水产氢率高达1.62mmol/g.h,为同等条件下制备的TiO2的产氢率(0.039mmol/g.h)的41倍。
本发明进一步提供上述Nb-Rh共掺杂TiO2催化剂的制备方法,通过溶胶-凝胶法制备。
根据本发明,所述方法包括以下步骤:
(1)将盐酸,五氯化铌乙醇溶液,氯化铑乙醇溶液和钛酸丁酯依次加入到乙醇中,搅拌形成透明溶液;
(2)然后加入水,继续搅拌形成溶胶,溶胶经过静置老化直至形成凝胶;
(3)将上述凝胶置于烘箱干燥,之后放入马弗炉中煅烧,获得所述催化剂。
根据本发明,步骤(1)中,所述盐酸的质量分数可以为20%-35%,优选质量分数为35%的浓盐酸;
所述五氯化铌乙醇溶液的浓度可以为0.001-0.2M,优选为0.01-0.1M,还优选0.02-0.08M,例如为0.05M;
所述氯化铑乙醇溶液的浓度可以为0.001-0.2M,优选为0.005-0.1M,还优选0.009-0.05M,例如为0.01M;
根据本发明,步骤(1)中,所述盐酸的体积与五氯化铌乙醇溶液中五氯化铌,氯化铑乙醇溶液中氯化铑,钛酸丁酯的摩尔比可以为(0.02-1.5mL):(1×10-7-0.001mol):(1×10-7-0.001mol):0.01mol,优选为(0.1-1.0mL):(1×10-6-0.001mol):(1×10-6-0.001mol):0.01mol,作为示例性的实例,为0.3mL:(5×10-6-5×10-4mol):(5×10-6-5×10-4mol):0.01mol;
根据本发明,步骤(1)中,所述乙醇优选为无水乙醇;
优选地,所述乙醇的体积与钛酸丁酯的摩尔量的比可以为(5-40mL):0.01mol,优选为(10-15mL):0.01mol。
根据本发明,步骤(2)中,所述水优选为蒸馏水。
根据本发明,步骤(3)中,所述干燥温度为60℃以上,作为示例性的实例,干燥温度为70℃;
优选地,所述干燥时间为15h以上,例如可以为20h;
优选地,所述煅烧的温度可以为400℃以上,例如可以为450℃,550℃,900℃或1200℃;
优选地,所述煅烧时间可以为1h以上,例如可以为2h,3h,4h或6h。
本发明还提供如上所述催化剂用于光解水产氢的用途。
本发明还提供如上所述催化剂用于光催化裂解有机物的用途,例如可催化裂解甲基橙、亚甲基蓝、罗丹明B,优选为用于催化亚甲基蓝分解。
本发明的有益效果:
1.本发明的催化剂与普通的光催化剂二氧化钛相比,具有较高的光催化产氢活性,且其制备方法简单,易于大规模生产。
2.本发明催化剂可重复利用,循环使用多次(如至少20次)未发现其催化效果有明显下降现象。
3.本发明的催化剂具有多种用途,一方面可以用作光解水产氢催化剂,另一方面可用作催化裂解有机物,例如亚甲基蓝。当本发明的催化剂用作光解水产氢催化剂时,其催化产氢率可高达1.62mmol/g.h,为同等条件下制备的TiO2的产氢率(0.039mmol/g.h)的41倍;
附图说明
图1为实施例1-12中不同煅烧条件下所得催化剂Ti1-x-yNbxRhyO2纳米颗粒的XRD图。其中各附图标记含义如下:(a)Ti0.998Nb0.001Rh0.001O2;(b)Ti0.949Nb0.05Rh0.001O2;(c)Ti0.949Nb0.001Rh0.05O2;(d)Ti0.996Nb0.002Rh0.002O2;(e)Ti0.98Nb0.01Rh0.01O2;(f)Ti0.90Nb0.05Rh0.05O2;(g)Ti0.97Nb0.02Rh0.01O2;(h)Ti0.999Nb0.0005Rh0.0005O2;(i)Ti0.97Nb0.015Rh0.015O2;(j)Ti0.99Nb0.005Rh0.005O2;(k)Ti0.94Nb0.03Rh0.03O2;(l)Ti0.96Nb0.02Rh0.02O2。
图2为实施例4中Ti0.996Nb0.002Rh0.002O2的TEM图谱。
图3为对比例1、实施例4、实施例5、实施例6、实施例8以及实施例11中催化剂Ti1-x- yNbxRhyO2的紫外-可见光吸收谱图。其中各附图标记含义如下:(s)TiO2;(d)Ti0.996Nb0.002Rh0.002O2;(e)Ti0.98Nb0.01Rh0.01O2;(f)Ti0.90Nb0.05Rh0.05O2;(h)Ti0.999Nb0.0005Rh0.0005O2;(j)Ti0.99Nb0.005Rh0.005O2。
图4为经550℃煅烧3h后的Ti1-x-yNbxRhyO2(0≤x=y≤0.05)纳米粉的产氢率随掺杂量(x)变化图。
图5为对比例1、实施例1、实施例5、实施例9、实施例10、实施例12中催化剂Ti1-x- yNbxRhyO2纳米粉光催化降解有机物亚甲基蓝的性能测试。其中,各附图标记含义如下:(s)TiO2;(a)Ti0.998Nb0.001Rh0.001O2;(e)Ti0.98Nb0.01Rh0.01O2;(i)Ti0.97Nb0.015Rh0.015O2;(k)Ti0.94Nb0.03Rh0.03O2;(l)Ti0.96Nb0.02Rh0.02O2。
具体实施方式
下面结合具体实施例,进一步阐述本发明。应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。此外,应理解,在阅读了本发明所记载的内容之后,本领域技术人员可以对本发明作各种改动或修改,这些等价形式同样落于本发明所限定的范围。
本发明通过下述实施例进行详细说明。但本领域技术人员了解,下述实施例不是对本发明保护范围的限制。任何在本发明基础上做出的改进和变化,都在本发明的保护范围之内。
除非另有说明,实施例中使用的原料和试剂均为市售物质。
实施例样品的XRD谱图是使用miniflex-600粉末衍射仪进行表征。
实施例样品的透射电镜是使用扫描透射电子显微镜Tecnai G2F20进行表征。
实施例样品的紫外可见吸收光谱是使用Lambda950紫外-可见分光光度计进行表征。
实施例样品的催化光解水产氢是使用北京中教金源的光催化系统进行测试。
对比例1
将0.3mL盐酸和3.4g钛酸丁酯依次加入到10mL无水乙醇溶液中,搅拌以形成透明溶液,然后慢慢滴加蒸馏水,同时继续搅拌直至形成凝胶。将凝胶于70℃烘箱干燥20h,之后放入马弗炉中于550℃煅烧2h,获得TiO2纳米粉。
实施例1
将0.3mL质量分数为35%的盐酸,0.2mL 0.05M五氯化铌乙醇溶液,1mL 0.01M氯化铑乙醇溶液和3.4g钛酸丁酯依次加入到10mL无水乙醇溶液中,搅拌以形成透明溶液,然后慢慢滴加蒸馏水,同时继续搅拌直至形成凝胶。将凝胶于70℃烘箱干燥20h,之后放入马弗炉中于450℃煅烧2h,获得Ti0.998Nb0.001Rh0.001O2纳米粉。
实施例2
将0.3mL质量分数为35%的盐酸,10.5mL 0.05M五氯化铌乙醇溶液,1.1mL 0.01M氯化铑乙醇溶液和3.4g钛酸丁酯依次加入到10mL无水乙醇溶液中,搅拌以形成透明溶液,然后慢慢滴加蒸馏水,同时继续搅拌直至形成凝胶。将凝胶于70℃烘箱干燥20h,之后放入马弗炉中于450℃煅烧2h,获得Ti0.949Nb0.05Rh0.001O2纳米粉。
实施例3
将0.3mL质量分数为35%的盐酸,0.2mL 0.05M五氯化铌乙醇溶液,53mL 0.01M氯化铑乙醇溶液和3.4g钛酸丁酯依次加入到10mL无水乙醇溶液中,搅拌以形成透明溶液,然后慢慢滴加蒸馏水,同时继续搅拌直至形成凝胶。将凝胶于70℃烘箱干燥20h,之后放入马弗炉中于450℃煅烧2h,获得Ti0.949Nb0.001Rh0.05O2纳米粉。
实施例4
将0.3mL质量分数为35%的盐酸,0.4mL 0.05M五氯化铌乙醇溶液,2mL 0.01M氯化铑乙醇溶液和3.4g钛酸丁酯依次加入到10mL无水乙醇溶液中,搅拌以形成透明溶液,然后慢慢滴加蒸馏水,同时继续搅拌直至形成凝胶。将凝胶于70℃烘箱干燥20h,之后放入马弗炉中于550℃煅烧3h,获得Ti0.996Nb0.002Rh0.002O2纳米粉。
实施例5
将0.3mL质量分数为35%的盐酸,2mL 0.05M五氯化铌乙醇溶液,10mL 0.01M氯化铑乙醇溶液和3.4g钛酸丁酯依次加入到10mL无水乙醇溶液中,搅拌以形成透明溶液,然后慢慢滴加蒸馏水,同时继续搅拌直至形成凝胶。将凝胶于70℃烘箱干燥20h,之后放入马弗炉中于550℃煅烧3h,获得Ti0.98Nb0.01Rh0.01O2纳米粉。
实施例6
将0.3mL质量分数为35%的盐酸,11mL 0.05M五氯化铌乙醇溶液,56mL 0.01M氯化铑乙醇溶液和3.4g钛酸丁酯依次加入到10mL无水乙醇溶液中,搅拌以形成透明溶液,然后慢慢滴加蒸馏水,同时继续搅拌直至形成凝胶。将凝胶于70℃烘箱干燥20h,之后放入马弗炉中于550℃煅烧3h,获得Ti0.90Nb0.05Rh0.05O2纳米粉。
实施例7
将0.3mL质量分数为35%的盐酸,4mL 0.05M五氯化铌乙醇溶液,10mL 0.01M氯化铑乙醇溶液和3.4g钛酸丁酯依次加入到10mL无水乙醇溶液中,搅拌以形成透明溶液,然后慢慢滴加蒸馏水,同时继续搅拌直至形成凝胶。将凝胶于70℃烘箱干燥20h,之后放入马弗炉中于900℃煅烧6h,获得Ti0.97Nb0.02Rh0.01O2纳米粉。
实施例8
将0.3mL质量分数为35%的盐酸,0.1mL 0.05M五氯化铌乙醇溶液,0.5mL 0.01M氯化铑乙醇溶液和3.4g钛酸丁酯依次加入到10mL无水乙醇溶液中,搅拌以形成透明溶液,然后慢慢滴加蒸馏水,同时继续搅拌直至形成凝胶。将凝胶于70℃烘箱干燥20h,之后放入马弗炉中于1200℃煅烧4h,获得Ti0.999Nb0.0005Rh0.0005O2纳米粉。
实施例9
将0.3mL质量分数为35%的盐酸,3mL 0.05M五氯化铌乙醇溶液,15mL 0.01M氯化铑乙醇溶液和3.4g钛酸丁酯依次加入到10mL无水乙醇溶液中,搅拌以形成透明溶液,然后慢慢滴加蒸馏水,同时继续搅拌直至形成凝胶。将凝胶于70℃烘箱干燥20h,之后放入马弗炉中于1200℃煅烧4h,获得Ti0.97Nb0.015Rh0.015O2纳米粉。
实施例10
将0.3mL质量分数为35%的盐酸,6mL 0.05M五氯化铌乙醇溶液,30mL 0.01M氯化铑乙醇溶液和3.4g钛酸丁酯依次加入到10mL无水乙醇溶液中,搅拌以形成透明溶液,然后慢慢滴加蒸馏水,同时继续搅拌直至形成凝胶。将凝胶于70℃烘箱干燥20h,之后放入马弗炉中于550℃煅烧3h,获得Ti0.94Nb0.03Rh0.03O2纳米粉。
实施例11
将0.3mL质量分数为35%的盐酸,1mL 0.05M五氯化铌乙醇溶液,5mL 0.01M氯化铑乙醇溶液和3.4g钛酸丁酯依次加入到10mL无水乙醇溶液中,搅拌以形成透明溶液,然后慢慢滴加蒸馏水,同时继续搅拌直至形成凝胶。将凝胶于70℃烘箱干燥20h,之后放入马弗炉中于550℃煅烧3h,获得Ti0.99Nb0.005Rh0.005O2纳米粉。
实施例12
将0.3mL质量分数为35%的盐酸,4mL 0.05M五氯化铌乙醇溶液,20mL 0.01M氯化铑乙醇溶液和3.4g钛酸丁酯依次加入到10mL无水乙醇溶液中,搅拌以形成透明溶液,然后慢慢滴加蒸馏水,同时继续搅拌直至形成凝胶。将凝胶于70℃烘箱干燥20h,之后放入马弗炉中于550℃煅烧3h,获得Ti0.96Nb0.02Rh0.02O2纳米粉。
实施例13催化剂催化光解水产氢测试
向石英反应容器中加入10mL甲醇、100mL蒸馏水,分别加入如上实施例1-12的催化剂0.1g,利用机械泵抽真空直至光催化系统真空度达到负的一个大气压并继续抽真空约2h,以除去光解水制氢系统中的空气,打开磁控玻璃气泵促进系统内气体流动使气体分布均匀,用300W氙灯垂直向下照射反应器,维持光催化反应10小时,每隔1h采样一次,通过气相色谱在线检测反应产物中的氢气组分的含量。
测试结果见图4。由图4可见随着Nb和Rh的掺杂量x的增加,催化剂的产氢率升高,当x达到一定值后,随着x的增加,催化剂的产氢率逐渐下降,当x数值在0.005-0.03之间时样品的产氢率较高。
实施例14催化剂催化裂解亚甲基蓝测试
向石英反应器中分别加入0.1g如上对比例1、实施例1、5、9、10、12中的一种催化剂和100mL 5×10-5M亚甲基蓝溶液,开始搅拌。将发射波长为254nm的低压汞灯至于反应器上方,汞灯距离液面约20cm。打开汞灯光源使得紫外光可以垂直照射在液体表面。每隔一段时间,取出5mL溶液,离心,取上层清液,用紫外分光光度计测试并和预测试的标准曲线对照以确定其浓度变化。
测试结果见图5。从图5可见图中对比例1和实施例中所述催化剂都有明显的降解亚甲基蓝的作用,且实施例所述Nb-Rh共掺杂的催化剂的降解效率远高于对比例1催化剂,其中Nb和Rh的掺杂量为0.01时降解效果最佳。
以上,对本发明的实施方式进行了说明。但是,本发明不限定于上述实施方式。凡在本发明的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (20)
1.一种Nb-Rh共掺杂TiO2催化剂,其特征在于,所述催化剂的化学组成表示为Ti1-x- yNbxRhyO2,其中,x的范围为0<x≤0.1,y的范围为0<y≤0.1;
所述催化剂为金红石相与锐钛矿相混合晶相;
所述催化剂为掺杂型纳米材料,微结构为零维纳米颗粒;
纳米颗粒平均粒度为10-55nm。
2.如权利要求1所述的Nb-Rh共掺杂TiO2催化剂,其特征在于,1×10-5≤x≤ 0.08,1×10-5≤y≤0.08。
3.如权利要求2所述的Nb-Rh共掺杂TiO2催化剂,其特征在于,1×10-4≤x≤0.06,1×10-4≤y≤0.06。
4.如权利要求3所述的Nb-Rh共掺杂TiO2催化剂,其特征在于,5×10-4≤x≤0.05,5×10-4≤y≤0.06。
5.如权利要求1所述的Nb-Rh共掺杂TiO2催化剂,其特征在于,所述催化剂的化学组成表示为:Ti0.998Nb0.001Rh0.001O2;Ti0.949Nb0.05Rh0.001O2;Ti0.949Nb0.001Rh0.05O2;Ti0.996Nb0.002Rh0.002O2;Ti0.98Nb0.01Rh0.01O2;Ti0.90Nb0.05Rh0.05O2;Ti0.97Nb0.02Rh0.01O2;Ti0.999Nb0.0005Rh0.0005O2;Ti0.97Nb0.015Rh0.015O2;Ti0.94Nb0.03Rh0.03O2;Ti0.99Nb0.005Rh0.005O2;Ti0.96Nb0.02Rh0.02O2。
6.如权利要求1所述的Nb-Rh共掺杂TiO2催化剂,其特征在于,当所述催化剂用于光解水产氢时,x、y为0.002≤ x=y ≤ 0.02。
7.如权利要求6所述的Nb-Rh共掺杂TiO2催化剂,其特征在于,纳米颗粒平均粒度为30-50nm。
8.如权利要求1-6任一项所述的Nb-Rh共掺杂TiO2催化剂,其特征在于,所述催化剂以金红石相为主要晶相。
9.一种如权利要求1-8任一项所述催化剂的制备方法,其特征在于,所述催化剂通过溶胶-凝胶法制备,包括以下步骤:
(1)将盐酸,五氯化铌乙醇溶液,氯化铑乙醇溶液和钛酸丁酯依次加入到乙醇中,搅拌形成透明溶液;
(2)然后加入水,继续搅拌形成溶胶,溶胶经过静置老化直至形成凝胶;
(3)将上述凝胶置于烘箱干燥,之后放入马弗炉中煅烧,获得所述催化剂。
10.如权利要求9所述的制备方法,其特征在于,步骤(1)中,所述盐酸的质量分数为20%-35%。
11.如权利要求9所述的制备方法,其特征在于,步骤(1)中,所述五氯化铌乙醇溶液的浓度为0.001-0.2M。
12.如权利要求9所述的制备方法,其特征在于,步骤(1)中,所述氯化铑乙醇溶液的浓度为0.001-0.2M。
13.如权利要求9所述的制备方法,其特征在于,步骤(1)中,所述盐酸的体积与五氯化铌乙醇溶液中五氯化铌,氯化铑乙醇溶液中氯化铑,钛酸丁酯的摩尔比为(0.02-1.5mL):(1×10-7-0.001mol):(1×10-7-0.001mol):0.01mol。
14.如权利要求9所述的制备方法,其特征在于,步骤(1)中,所述乙醇为无水乙醇;
所述乙醇的体积与钛酸丁酯的摩尔量的比为(5-40mL):0.01mol。
15.如权利要求9-14任一项所述的制备方法,其特征在于,步骤(1)中,所述氯化铑乙醇溶液的浓度为0.005-0.1M;
所述盐酸的体积与五氯化铌乙醇溶液中五氯化铌,氯化铑乙醇溶液中氯化铑,钛酸丁酯的摩尔比为(0.1-1.0mL):(1×10-6-0.001mol):(1×10-6-0.001mol):0.01mol;
乙醇的体积与钛酸丁酯的摩尔量的比为(10-15mL):0.01mol。
16.如权利要求9所述的制备方法,其特征在于,步骤(2)中,所述水为蒸馏水。
17.如权利要求9所述的制备方法,其特征在于,步骤(3)中,所述干燥温度为60oC以上;
所述煅烧的温度为400oC以上。
18.如权利要求1-8任一项所述的催化剂的用途,其特征在于,所述催化剂用于光解水产氢。
19.如权利要求1-8任一项所述的催化剂的用途,其特征在于,所述催化剂用于光催化裂解有机物。
20.根据权利要求19所述的用途,其特征在于,所述催化剂用于催化裂解甲基橙、亚甲基蓝、罗丹明B。
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CN101791562A (zh) * | 2010-03-25 | 2010-08-04 | 东华大学 | 铁、氟共掺杂的纳米二氧化钛可见光光催化剂的制备方法 |
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Photocatalytic O2 Evolution of Rhodium and Antimony-Codoped Rutile-Type TiO2 under Visible Light Irradiation;Ryo Niishiro等;《J. Phys. Chem. C》;20071030;第111卷;摘要、3.1 Characterization of Rhodium Species in TiO2:Rh and TiO2:Rh/M(M=Sb,Ta,and Nb) * |
Ryo Niishiro等.Photocatalytic O2 Evolution of Rhodium and Antimony-Codoped Rutile-Type TiO2 under Visible Light Irradiation.《J. Phys. Chem. C》.2007,第111卷摘要、3.1 Characterization of Rhodium Species in TiO2:Rh and TiO2:Rh/M(M=Sb,Ta,and Nb). * |
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