CN106693994A - 一种核壳结构硫化铋@硫化铜复合物微球的制备与应用 - Google Patents
一种核壳结构硫化铋@硫化铜复合物微球的制备与应用 Download PDFInfo
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- NNLOHLDVJGPUFR-UHFFFAOYSA-L calcium;3,4,5,6-tetrahydroxy-2-oxohexanoate Chemical compound [Ca+2].OCC(O)C(O)C(O)C(=O)C([O-])=O.OCC(O)C(O)C(O)C(=O)C([O-])=O NNLOHLDVJGPUFR-UHFFFAOYSA-L 0.000 title claims abstract description 53
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 239000011258 core-shell material Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000004005 microsphere Substances 0.000 title abstract 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000001699 photocatalysis Effects 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000007146 photocatalysis Methods 0.000 claims abstract description 12
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 238000005342 ion exchange Methods 0.000 claims abstract description 5
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 3
- 239000008367 deionised water Substances 0.000 claims abstract 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract 5
- 229910052802 copper Inorganic materials 0.000 claims description 21
- 239000010949 copper Substances 0.000 claims description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 238000004073 vulcanization Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 229910001431 copper ion Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 claims 2
- 239000000725 suspension Substances 0.000 claims 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 238000000354 decomposition reaction Methods 0.000 claims 1
- 239000006185 dispersion Substances 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000011859 microparticle Substances 0.000 claims 1
- 239000005416 organic matter Substances 0.000 claims 1
- 239000003643 water by type Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 17
- 238000000034 method Methods 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- -1 bismuth nitride Chemical class 0.000 abstract description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 abstract description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 9
- 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 7
- 229940043267 rhodamine b Drugs 0.000 description 7
- 241000289669 Erinaceus europaeus Species 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000356 contaminant Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000165940 Houjia Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000010748 Photoabsorption Effects 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000002872 contrast media Substances 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical group [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- DKUYEPUUXLQPPX-UHFFFAOYSA-N dibismuth;molybdenum;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mo].[Mo].[Bi+3].[Bi+3] DKUYEPUUXLQPPX-UHFFFAOYSA-N 0.000 description 1
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical class [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 238000001429 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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- 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
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Abstract
本发明提供了一种核壳结构硫化铋@硫化铜复合物微球及其制备方法,属于材料制备领域。该方法是先通过在乙二醇中加入硝酸铋和硫脲,然后采用溶剂热法制备硫化铋微球,再将硫化铋分散在一定量的去离子水中,接着与氯化铜溶液进行离子交换反应制备硫化铋@硫化铜复合材料。本发明制备的核壳结构硫化铋@硫化铜复合物微球具有形貌可控、操作简单、不使用添加剂、高产率、低成本、合成工艺简单等特点;且本发明制备的核壳结构硫化铋@硫化铜复合材料具有高的反应活性,在光电器件、光催化等领域具有潜在的应用前景。
Description
技术领域
本发明涉及材料制备领域,具体地说涉及一种核壳结构硫化铋@硫化铜复合物微球的制备及其在光催化降解有机污染物中的应用。
背景技术
近年来,能源危机与环境污染日趋严重,解决这两大问题是实现可持续发展的迫切需要。其中,环境污染物中的有机物污染已严重影响到人们的日常生活,因此如何有效的消除对人类有害的有机污染物,已成为科学家关注的焦点。一种新型高效实用的环保处理技术的研究极大地激发了人们对太阳能利用的研究兴趣。太阳能作为一种清洁,取之不尽用之不竭的能源,它的充分利用一直被认为是解决这两大问题的最有可能的途径之一。半导体光催化剂被公认为的新型高效绿色的催化剂,该技术可望应用于光解水、二氧化碳光催化还原和环境污染物的处理等领域。到目前为止,研究最多是传统的光催化材料二氧化钛仅仅停留在只能吸收太阳光中的紫外光,其太阳光的利用率低。近年来,硫化铋,钼酸铋和硫化铜等窄带隙非钛基可见光催化剂的开发引起了人们的广泛关注,但是由于其光致电子和空穴容易复合,光催化效率仍然很低。因此,对可见光材料的处理开发是光催化研究的重点。
作为一种二元直接带隙半导体,硫化铋的禁带宽度约为1.8eV,几乎能在整个太阳光区都有吸收,因此是一种很有潜力的可见光催化剂,然而由于其光致电子和空穴容易复合,其光催化效率不高。近年来,研究人员为改善硫化铋的光催化活性做出了很多努力,如:结构控制、掺杂、贵金属修饰和与其他半导体形成异质结等。其中与其他半导体进行复合不仅能够有效的抑制光生电子-空穴的复合、提高载流子的寿命,还能有效的利用两种半导体的优势,得到了广泛的应用。硫化铜是一种重要的过渡金属硫化物,具有独特的量子尺寸效应、表面效应和介电限制效应,表现出新奇的物理和化学性质,在发光、抗菌和光催化等领域具有广泛的应用前景。
迄今为止,尚未有报道在常温下通过简易的离子交换法制备核壳结构硫化铋@硫化铜的光催化复合材料。此方法制备的复合材料除具有形貌可控,未加任何添加剂等优势外,还能通过改变材料的组成来调控材料的光催化活性。更重要的,这种复合材料相对于单一的硫化铋和硫化铜有着更强的光催化性能。
发明内容
本发明针对传统光催化材料光吸收差和载流子复合率高等问题,以及制备硫化铋粒子方法的复杂化问题,提供了一种硫化铋@硫化铜复合光催化材料,该材料具有可见光吸收可调、高效的特点。同时提供了一种简单易行的制备材料的方法,该方法成本低廉,易于大规模生产,能够调控材料的光吸收,改善光生载流子的分离,显著提高复合材料的光催化性能。
本发明采用的技术方案为:离子交换法生长制备硫化铋/硫化铜复合光催化材料,其特征在于包括以下步骤:
(1)制备针状结构的硫化铋微米球:将硝酸铋和硫代硫酸钠分别溶解在乙二醇中,磁力搅拌一段时间使其完全溶解,然后将两种溶液混合并且继续搅拌,保证硝酸铋浓度为0.03-0.04mol/L、硫代硫酸钠0.09-0.11mol/L,且硝酸铋和硫代硫酸钠的摩尔比为1:(2-4)。最后转移到密闭的高压釜中,置于120-160℃下反应4-14小时,待冷却至室温后,将产物收集、洗涤、真空干燥,得到均一的硫化铋微米球。
(2)制备核壳结构硫化铋@硫化铜复合材料:将硫化铋微米球加入到含有铜源的水溶液中,60-100℃下磁力搅拌2-8小时,铜源分解产生的铜离子与硫化铋发生离子交换反应,生产核壳结构硫化铋@硫化铜复合材料,所述的铜源为硫酸铜、氯化铜或硝酸铜。
(3)步骤(1)所述的硝酸铋与硫脲的摩尔比为:1:3,乙二醇的体积为:75毫升。
(4)步骤(1)所述的硫化铋微米球、铜源的摩尔比为4:1,2:1,2:3,2:5,2:7;铜源与水的摩尔比优选1:3333。
本发明的方法成本低,设备简单易操作,且可大规模生产,在工业方面具有重要的潜在应用。制备的硫化铋/硫化铜复合光催化材料具有良好的可见光吸收(图1)看出,硫化铋@硫化铜复合材料在可见光区域(400-800nm)具有可调的光吸收;通过可见光降解罗丹明B(RhB)(图2)可以看出,单独的硫化铋或硫化铜在75分钟可见光照射下可以降解24.5%和7.5%的RhB,而同样条件下硫化铋@硫化铜复合材料的光催化效率达到92.2%,本发明材料比单独的硫化铋和单独的硫化铜效果更好。
附图说明
图1为本发明的核壳结构硫化铋@硫化铜复合材料不同比例的光吸收图,其中a,b,c,d,e,f。
图2为本发明的核壳结构硫化铋@硫化铜复合材料不同比例的SEM对比图,从图中明显看出硫化铋由刺猬状结构变为片状与棒状相互依附的结构。
图3为本发明的核壳结构硫化铋@硫化铜复合材料不同比例的XRD图,从图中可以看出随着铜源的比例增大,硫化铜的峰(箭头所指)越来越强。
图4为本发明单一硫化铋,单一硫化铜和硫化铋@硫化铜复合材料以及对比材料的可见光降解RhB性能对比图a,b,c,d。从图中很明显的看出复合材料相对于单一材料有更好的的光催化性能。
具体实施方式
下面结合实施例对本专利进一步说明。
实施例1
按照反应混合物中五水硝酸铋:硫脲:乙二醇的摩尔比为2.5:7.5:1348,称取1.2克五水硝酸铋和0.57克硫脲溶于75毫升的乙二醇中,然后转移至100毫升聚四氟乙烯高压反应釜,160℃下反应6小时。按常规方法过滤、洗涤、干燥得黑色粉末。经X-射线粉末衍射仪,扫描电子显微镜等对材料进行表征,所得产物为刺猬状硫化铋微米球。
称取上述刺猬状硫化铋0.1克,分散在30毫升的二次水中,然后加入定量的二水氯化铜,最后将混合液转移至100毫升的圆底烧瓶中,95℃下反应5小时。按常规方法过滤、二次水和乙醇洗涤、干燥得硫化铋@硫化铜复合物微球。
利用Rint-2000型X射线衍射仪(XRD)、ESCALAB 250Xi型X射线光电子能谱仪(XPS)、Nova Nano SEM 230型扫描电子显微镜(SEM)、TU-1901spectrophotometer型紫外-可见光谱(UV-vis)仪等仪器表征所得目标产物的结构、组成、形貌与吸光性能。
以降解RhB为模型反应考察所制备复合物微球的光催化活性:取50毫克所制备的复合光催化材料,分散于50毫升RhB溶液中(10毫克/升),黑暗下搅拌30分钟,然后打开光源(500瓦的氙灯),同时打开冷凝水控制反应液温度为25℃。光照一段时间后取样5毫升,离心,分离出催化剂然后用紫外可见光谱测定反应液中染料的浓度。光照75分钟,RhB的降解率为92.9%。
实施例2
以硝酸铜为铜源
称取上述相同方法制备的刺猬状硫化铋0.1克,分散在30毫升的二次水中,然后加入定量的三水硝酸铜,最后将混合液转移至100毫升的圆底烧瓶中,95℃下反应5小时。按常规方法过滤、二次水和乙醇洗涤、干燥得硫化铋@硫化铜复合物微球。
Claims (5)
1.一种核壳结构硫化铋@硫化铜异质结光催化复合材料的制备方法,其特征在于包括以下步骤:
(1)制备硫化铋微米球:取一定量的五水硝酸铋溶于定量的乙二醇中,在搅拌状态下加入一定比例的硫脲;混合均匀后将溶液倒入反应釜内120-160℃下反应4-14小时;待反应结束,冷却至室温,用去离子水和乙醇反复洗涤;干燥即得硫化铋微米粒子;
(2)制备硫化铋微米球的悬浊液:将硫化铋微米球以一定的比例分散到去离子水中,搅拌均匀;
(3)将一定比例的二水氯化铜加入到上述悬浊液中,并搅拌30-60分钟,然后将所得溶液转移至三颈烧瓶中,并在60-100℃温度下磁力搅拌,铜源在溶液中电离产生的铜离子与硫化铋发生离子交换反应,生成核壳结构硫化铋@硫化铜复合材料;
(4)反应结束后,自然冷却,用去离子水、乙醇对反应产物进行多次离心洗涤后,最后将产物干燥得到核壳结构硫化铋@硫化铜复合材料。
2.根据权利要求1所述核壳结构硫化铋@硫化铜光催化复合材料的制备方法,其特征在于:所述铋源为硝酸铋及其水合物,所述铜源为氯化铜及其水合物。
3.根据权利要求1所述的核壳结构硫化铋@硫化铜光催化复合材料的制备方法,其特征在于:所述硫化铋与去离子水的分散比例为:0.1克硫化铋分散于10-50毫升去离子水中。
4.根据权利要求1所述的核壳结构硫化铋@硫化铜光催化复合材料的制备方法,其特征在于:所述步骤(3)所述的温度为95℃,磁力搅拌5小时。
5.权利要求1所制备的核壳结构硫化铋@硫化铜光催化复合材料作为光催化剂在可见光催化降解有机染料、光催化分解有机物、电催化制氢中的应用。
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