CN106111181A - 多孔石墨烯‑沸石‑卤氧化铋光催化材料及制备与应用 - Google Patents
多孔石墨烯‑沸石‑卤氧化铋光催化材料及制备与应用 Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 58
- 239000010457 zeolite Substances 0.000 title claims abstract description 58
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 56
- 239000000463 material Substances 0.000 title claims abstract description 43
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 35
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000002131 composite material Substances 0.000 claims abstract description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
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- 150000001336 alkenes Chemical class 0.000 claims description 7
- 229910052797 bismuth Inorganic materials 0.000 claims description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 6
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- 238000007146 photocatalysis Methods 0.000 description 15
- 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 14
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 13
- 230000015556 catabolic process Effects 0.000 description 12
- 238000006731 degradation reaction Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
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- 229940043267 rhodamine b Drugs 0.000 description 8
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- -1 and in tube furnace Chemical compound 0.000 description 6
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 229940073609 bismuth oxychloride Drugs 0.000 description 4
- PIJVDJTXPKJZHD-UHFFFAOYSA-M bismuth;oxygen(2-);bromide Chemical compound [O-2].[Br-].[Bi+3] PIJVDJTXPKJZHD-UHFFFAOYSA-M 0.000 description 4
- ORZGULPODBRYCV-UHFFFAOYSA-M bismuth;oxygen(2-);iodide Chemical compound [O-2].[I-].[Bi+3] ORZGULPODBRYCV-UHFFFAOYSA-M 0.000 description 4
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- 240000005373 Panax quinquefolius Species 0.000 description 3
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- 238000002835 absorbance Methods 0.000 description 3
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- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 3
- 235000013339 cereals Nutrition 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
- CQPFMGBJSMSXLP-UHFFFAOYSA-M acid orange 7 Chemical compound [Na+].OC1=CC=C2C=CC=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 CQPFMGBJSMSXLP-UHFFFAOYSA-M 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- FQMZOWUZJQNWBB-UHFFFAOYSA-K [Bi](Cl)(Cl)Cl.[I] Chemical compound [Bi](Cl)(Cl)Cl.[I] FQMZOWUZJQNWBB-UHFFFAOYSA-K 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
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- 239000002055 nanoplate Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
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- 235000009566 rice Nutrition 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
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- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/39—Photocatalytic properties
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Abstract
本发明属于光催化材料技术领域,公开了一种多孔石墨烯‑沸石‑卤氧化铋光催化材料及制备与应用。所述光催化材料由9~50质量份的多孔石墨烯、50~91质量份的沸石和10~100质量份的卤氧化铋复合而成。所述制备方法为:将多孔石墨烯和沸石在乙醇溶液中反应,得到多孔石墨烯‑沸石复合材料,然后将其与卤氧化铋在乙醇溶液中反应,冷冻干燥,得到多孔石墨烯‑沸石‑卤氧化铋光催化材料。本发明方法采用多孔石墨烯‑沸石作为载体,可以更好地负载卤氧化铋,增大卤氧化铋的比表面积,减小卤氧化铋晶粒尺寸,显著提高催化剂活性。
Description
技术领域
本发明属于光催化材料技术领域,具体涉及一种多孔石墨烯-沸石-卤氧化铋光催化材料及制备与应用。
背景技术
随着全球环境问题的日益突出,利用半导体材料的光催化氧化进行污染物治理已成为污染治理技术领域的研究热点。同时,在能源日益短缺的今天,太阳能的利用自然会成为人们关注的焦点。到目前为止,TiO2被证实为最优秀的半导体光催化剂,其氧化能力强,催化活性高,生物、化学、光化学稳定性等优势一直处于光催化研究中的核心地位(Xu Bai-Huan,Lin Bi-Zhou,Wang Qin-Qin,Pian Xue-Tao,Zhang Ou,Fu Li-Mei.Anatase TiO2-pillared hexaniobate mesoporous nanocomposite with enhanced photocatalyticactivity[J].Microporous and Mesoporous Materials,2012,147(1):79-85.)。然而,TiO2的带隙能为3.2ev,只有波长小于387nm的紫外光才能激发它产生电子—空穴对。在太阳光谱中紫外光(400nm以下)不到5%,而波长为400~800nm的可见光占到43%,因此,寻求具有高性能的可见光光催化材料已是必然趋势(Surajit Kumar,Andrei G.Fedorova,James L.Gole.Photodegradation of ethylene using visible light responsivesurfaces prepared from titania nanoparticle slurries[J].Applied Catalysis B:Environmental,2005,57(2):93-107.)。
卤氧化铋(BiOX,X=F,Cl,Br,I)以其独特的电子结构,良好的光催化性能和高的化学稳定性,吸引了研究者的广泛关注,并成为光催化研究领域中的一颗新星(魏平玉,杨青林,郭林.卤氧化铋化合物光催化剂[J].化学进展.2009,21(9):1734-1741.)。但是,卤氧化铋光催化性能的发挥强烈依赖于其自身的粒径,只有将卤氧化铋颗粒的粒径控制在微纳米范围,才能有效缩短电子与空穴的激发路程,提高可见光催化效率(AR Liu,SM Wanga,YRZhao,Z Zheng.Low temperature preparation of nanocrystalline TiO2photocatalyst with a very large specific surface area[J].Materials Chemistryand Physics,2006,99(1):131-134.)。另外,卤氧化铋很容易产生团聚,降低了光催化效率(魏平玉,杨青林,郭林.卤氧化铋化合物光催化剂[J].化学进展.2009,21(9):1734-1741.)。为了避免上述缺陷,目前常用的解决方法是制备可固定化的卤氧化铋光催化剂。
Wang等(Changhua Wang,Changlu Shao,Yichun Liu,LinaZhang.Photocatalytic properties BiOCl and Bi2O3 nanofibers prepared byelectrospinning[J].Scripta Materialia,2008,59(3):332-335.)采用电纺丝的方法,以PAN为载体制备出粒径为80~140nm,长度达几个微米的BiOCl纤维。以BiOCl纤维作为光催化剂时,在紫外-可见光下,60min内将罗丹明B(RB)几乎全部降解完全;相同条件下,其催化性能是Bi2O3纳米纤维光催化剂的三倍。此外,对BiOCl纤维反应后沉降性能的研究表明,长度为微米级的BiOCl纤维在光催化完成后,1h之内从水悬浮液中沉降完全。BiOCl纤维具有可重复利用性,能够避免二次污染,降低成本,在工业化应用中具有广阔的前景。Yu等(Changlin Yu,Jimmy C.Yu,Caifeng Fan,Herui Wen,Shengjie Hu.Synthesis andcharacterization of Pt/BiOI nanoplate catalyst with enhanced activity undervisible light irradiation[J].Materials Science and Engineering:B,AdvancedFunctional Solid-State Materials,2010,166(3):213-219.)合成了一系列Pt/BiOI纳米片,铂纳米粒可以充当电子捕获剂,促进电子和空穴的分离,降低再复合率,增加量子效率。通过在可见光照射下降解酸性橙II以测定其活性。结果表明,照射1h,Pt(0.2%wt)/BiOI催化活性最高,对酸性橙II的降解率为90%,能明显克服卤氧化铋很容易产生团聚的问题。专利(CN101653732)“一种分子筛负载卤氧化铋光催化剂、制备方法及其应用”提供了一种分子筛负载卤氧化铋光催化剂、制备方法及其应用,该发明的催化剂是以SBA-15、ZSM-5、HY中的一种或几种为载体,卤氧化铋为活性组分构成的负载型催化剂。该催化剂用于气相有机物的去除。该催化剂中引入分子筛为载体,增大了催化剂的比表面积,减小了晶粒尺寸,显著提高催化剂降解苯的活性。
从以上分析可以看出,现有技术仍然存在功能单一的问题,不能全面解决卤氧化铋很容易产生团聚和光催化效率受粒径影响的问题。
发明内容
为了解决以上现有技术的缺点和不足之处,本发明的首要目的在于提供一种多孔石墨烯-沸石-卤氧化铋光催化材料。所得材料的卤氧化铋粒径可控、不易团聚、有机物吸附能力强、可见光催化活性增强。
本发明的另一目的在于提供上述多孔石墨烯-沸石-卤氧化铋光催化材料的制备方法。
本发明的再一目的在于提供上述多孔石墨烯-沸石-卤氧化铋光催化材料在可见光催化降解水中有机污染物的应用。
本发明目的通过以下技术方案实现:
一种多孔石墨烯-沸石-卤氧化铋光催化材料,所述光催化材料由9~50质量份的多孔石墨烯、50~91质量份的沸石和10~100质量份的卤氧化铋复合而成。其组成可表示为[多孔石墨烯]a[沸石]b[BiOX]c,其中a、b、c表示多孔石墨烯、沸石和卤氧化铋(BiOX)的质量比。
优选地,所述多孔石墨烯的比表面积为350~450m2/g,电导率为20~60S·m-1,900℃内的失重为4~6wt%;所述沸石的粒径为0.3~0.5nm,比表面积为100~400m2/g。
上述多孔石墨烯-沸石-卤氧化铋光催化材料的制备方法,包括如下制备步骤:
(1)多孔石墨烯的制备:将石墨粉加入浓硫酸中,冰盐浴冷却下加入KMnO4,室温搅拌反应,反应完成后加水稀释,再加入双氧水,离心去除杂质后,所得上清液依次经超声和微波处理,得到氧化石墨烯溶液,然后加入NaOH,于700~800℃及氮气保护下烧结,得到多孔石墨烯;
(2)多孔石墨烯-沸石复合材料的制备:步骤(1)所得多孔石墨烯加入到乙醇中,超声处理后加入沸石搅拌混合均匀,加热去除乙醇后于700~800℃烧结,得到多孔石墨烯-沸石复合材料;
(3)多孔石墨烯-沸石-卤氧化铋的制备:将BiOX加入到乙醇中,然后加入步骤(2)所得多孔石墨烯-沸石复合材料,超声分散均匀后冷冻干燥,得到所述多孔石墨烯-沸石-卤氧化铋光催化材料。
优选地,步骤(1)中所述KMnO4的用量为石墨粉质量的2.5~3倍;所述双氧水的用量与石墨粉的质量体积比为(2~3)-:1mL/g;所述NaOH的用量为石墨粉质量的3~5倍。
优选地,步骤(2)中所述沸石的用量为多孔石墨烯质量的1~10倍。
优选地,步骤(3)中所述BiOX与多孔石墨烯-沸石复合材料加入的质量比为(10~100):(100~110)。
上述多孔石墨烯-沸石-卤氧化铋光催化材料在可见光催化降解水中有机污染物的应用。
相对于现有技术,本发明具有如下优点及有益效果:
(1)本发明方法采用多孔石墨烯-沸石作为载体,可以更好地负载卤氧化铋,增大卤氧化铋的比表面积,减小卤氧化铋晶粒尺寸,显著提高催化剂活性。
(2)多孔石墨烯可以充当电子捕获剂,促进电子和空穴的分离,降低再复合率,增加卤氧化铋的量子效率。
(3)采用冷冻干燥法处理多孔石墨烯-沸石-卤氧化铋,在增大了催化剂的比表面积的同时减小了晶粒的尺寸,可以提高卤氧化铋的催化活性。
(4)多孔石墨烯-沸石-卤氧化铋具有可重复利用性,能够避免二次污染,降低成本,在工业化应用中具有广阔的前景。
具体实施方式
下面结合实施例对本发明作进一步详细的描述,但本发明的实施方式不限于此。
以下实施例所得产物的理化性能通过如下方法测定:
比表面积:采用Micromeritics ASAP 2010测定氧化石墨烯比表面积;
多孔石墨烯的电阻率和电导率:利用RTS-8型四探针仪器测试多孔石墨烯的电阻率和电导率;
多孔石墨烯的热失重:使用美国TA公司的SDT-Q600型热重分析仪进行热重测试,升温速率10℃/min,在N2气氛中进行;
实施例1
(1)100g石墨粉加入2.5L浓硫酸中,冰盐浴冷却到0℃,缓慢加入250g的KMnO4,然后升温至30℃,60rpm搅拌2h,加入20L水,再加入200mL双氧水,600rpm离心去除杂质后,超声(400W,50Hz)处理上层液1h,继而微波(800W,2450Hz)处理上层液1h,得到氧化石墨烯溶液,然后加入300g NaOH,在管式炉中氮气保护700℃加热1h,得到50g多孔石墨烯;多孔石墨烯的比表面积为350m2/g;其电导率为60S·m-1;900℃内的失重为4wt%。
(2)将50g多孔石墨烯加入到50L乙醇中,超声(400W,50Hz)处理1h,然后加入50g粒径为3A沸石,20rpm搅拌1h,80℃加热1h去除乙醇,700℃加热1h得到100g固体多孔石墨烯-沸石复合材料。
(3)10g的BiOCl加入到100mL乙醇中,然后加入100g的多孔石墨烯-沸石复合材料,超声(400W,50Hz)处理1h,冷冻干燥,得到多孔石墨烯-沸石-卤氧化铋光催化材料。其组成为[多孔石墨烯]50[沸石]50[BiOCl]10。
实施例2
(1)100g石墨粉加入2.5L浓硫酸中,冰盐浴冷却到0℃,缓慢加入260g的KMnO4,然后升温至30℃,60rpm搅拌2h,加入20L水,再加入300mL双氧水,600rpm离心去除杂质后,超声(400W,50Hz)处理上层液1h,继而微波(800W,2450Hz)处理上层液1h,得到氧化石墨烯溶液,然后加入300g NaOH,在管式炉中氮气保护760℃加热1h,得到33g多孔石墨烯;多孔石墨烯的比表面积为370m2/g;其电导率为50S·m-1;900℃内的失重为4.5wt%。
(2)将33g多孔石墨烯加入到33L乙醇中,超声(400W,50Hz)处理1h,然后加入67g粒径为4A沸石,20rpm搅拌1h,80℃加热1h去除乙醇,760℃加热1h得到100g固体多孔石墨烯-沸石复合材料;
(3)20g的BiOBr加入到100mL乙醇中,然后加入100g的多孔石墨烯-沸石复合材料,超声(400W,50Hz)处理1h,冷冻干燥,得到多孔石墨烯-沸石-卤氧化铋光催化材料。其组成为[多孔石墨烯]33[沸石]67[BiOBr]20。
实施例3
(1)100g石墨粉加入2.5L浓硫酸中,冰盐浴冷却到0℃,缓慢加入270g的KMnO4,然后升温至30℃,60rpm搅拌2h,加入20L水,再加入200mL双氧水,600rpm离心去除杂质后,超声(400W,50Hz)处理上层液1h,继而微波(800W,2450Hz)处理上层液1h,得到氧化石墨烯溶液,然后加入400g NaOH,在管式炉中氮气保护800℃加热1h,得到20g多孔石墨烯;多孔石墨烯的比表面积为390m2/g;其电导率为40S·m-1;900℃内的失重为5wt%。
(2)将20g多孔石墨烯加入到100mL乙醇中,超声(400W,50Hz)处理1h,然后加入80g粒径为5A沸石,20rpm搅拌1h,80℃加热1h去除乙醇,800℃加热1h得到100g固体多孔石墨烯-沸石复合材料。
(3)40g的BiOI加入到100mL乙醇中,然后加入100g的多孔石墨烯-沸石复合材料,超声(400W,50Hz)处理1h,冷冻干燥,得到多孔石墨烯-沸石-卤氧化铋光催化材料。其组成为[多孔石墨烯]20[沸石]80[BiOI]40。
实施例4
(1)100g石墨粉加入2.5L浓硫酸中,冰盐浴冷却到0℃,缓慢加入280g的KMnO4,然后升温至30℃,60rpm搅拌2h,加入20L水,再加入300mL双氧水,600rpm离心去除杂质后,超声(400W,50Hz)处理上层液1h,继而微波(800W,2450Hz)处理上层液1h,得到氧化石墨烯溶液,然后加入300g NaOH,在管式炉中氮气保护760℃加热1h,得到14g多孔石墨烯;多孔石墨烯的比表面积为410m2/g;其电导率为30S·m-1;900℃内的失重为5.5wt%。
(2)将14g多孔石墨烯加入到100mL乙醇中,超声(400W,50Hz)处理1h,然后加入86g粒径为3A沸石,20rpm搅拌1h,80℃加热1h去除乙醇,760℃加热1h得到100g固体多孔石墨烯-沸石复合材料。
(3)60g的BiOCl加入到100mL乙醇中,然后加入100g的多孔石墨烯-沸石复合材料,超声(400W,50Hz)处理1h,冷冻干燥,得到多孔石墨烯-沸石-卤氧化铋光催化材料。其组成为[多孔石墨烯]14[沸石]86[BiOCl]60。
实施例5
(1)100g石墨粉加入2.5L浓硫酸中,冰盐浴冷却到0℃,缓慢加入290g的KMnO4,然后升温至30℃,60rpm搅拌2h,加入20L水,再加入200mL双氧水,600rpm离心去除杂质后,超声(400W,50Hz)处理上层液1h,继而微波(800W,2450Hz)处理上层液1h,得到氧化石墨烯溶液,然后加入400g NaOH,在管式炉中氮气保护700℃加热1h,得到11g多孔石墨烯;多孔石墨烯的比表面积为430m2/g;其电导率为25S·m-1;900℃内的失重为5.5wt%。
(2)将11g多孔石墨烯加入到100mL乙醇中,超声(400W,50Hz)处理1h,然后加入89g粒径为4A沸石,20rpm搅拌1h,80℃加热1h去除乙醇,700℃加热1h得到100g固体多孔石墨烯-沸石复合材料。
(3)80g的BiOBr加入到100mL乙醇中,然后加入100g的多孔石墨烯-沸石复合材料,超声(400W,50Hz)处理1h,冷冻干燥,得到多孔石墨烯-沸石-卤氧化铋光催化材料。其组成为[多孔石墨烯]11[沸石]89[BiOBr]80。
实施例6
(1)100g石墨粉加入2.5L浓硫酸中,冰盐浴冷却到0℃,缓慢加入300g的KMnO4,然后升温至30℃,60rpm搅拌2h,加入20L水,再加入300mL双氧水,600rpm离心去除杂质后,超声(400W,50Hz)处理上层液1h,继而微波(800W,2450Hz)处理上层液1h,得到氧化石墨烯溶液,然后加入500g NaOH,在管式炉中氮气保护800℃加热1h,得到9g多孔石墨烯;多孔石墨烯的比表面积为450m2/g;其电导率为20S·m-1;900℃内的失重为6wt%。
(2)将9g多孔石墨烯加入到100mL乙醇中,超声(400W,50Hz)处理1h,然后加入91g粒径为5A沸石,20rpm搅拌1h,800℃加热1h,得到100g固体多孔石墨烯-沸石复合材料。
(3)100g的BiOI加入到100mL乙醇中,然后加入100g的多孔石墨烯-沸石复合材料,超声(400W,50Hz)处理1h,冷冻干燥,得到多孔石墨烯-沸石-卤氧化铋光催化材料。其组成为[多孔石墨烯]9[沸石]91[BiOI]100。
从实施例1~6可以看出,通过改变多孔石墨烯-沸石-卤氧化铋的加入量,分别制得多孔石墨烯-沸石-卤氧化铋比例不同的可见光催化剂。
本发明所得多孔石墨烯-沸石-卤氧化铋可见光催化剂的性能评价:
(1)取实施例6制备的多孔石墨烯-沸石-碘氧化铋0.05g,加入到50mL的罗丹明(10mg/L)水溶液中,调节pH=3.0,混合混合均匀后转入玻璃瓶中,在黑暗的环境中暗反应60min后做光催化测试,可见光灯为氙灯(300W,>420nm)。2h后取样,在551nm处测量溶液的吸光度(Lambda25紫外-可见光分光光度计),测试罗丹明的降解效果(王昭,毛峰,黄祥平,黄应平,冯笙琴,易佳,张昌远,刘栓.TiO2/石墨烯复合材料的制备及其光催化性能[J].材料科学与工程学报,2011,29(2):267-232.)。结果如表1所示。
表1多孔石墨烯-沸石-碘氧化铋可见光催化剂降解罗丹明B的活性效果
活性测试结果表明,采用多孔石墨烯-沸石作为载体,可以更好地负载碘氧化铋,增大碘氧化铋的比表面积,减小碘氧化铋晶粒尺寸,经过多孔石墨烯-沸石负载后,碘氧化铋降解罗丹明B的活性得到显著提高,说明多孔石墨烯-沸石可显著提高碘氧化铋催化剂活性,具有广阔的前景。
(2)取实施例5制备的多孔石墨烯-沸石-溴氧化铋0.05g,加入到50mL的罗丹明(10mg/L)水溶液中,调节pH=3.0,混合混合均匀后转入玻璃瓶中,在黑暗的环境中暗反应60min后做光催化测试,可见光灯为氙灯(300W,>420nm)。2h后取样,在551nm处测量溶液的吸光度(Lambda25紫外-可见光分光光度计),测试罗丹明的降解效果(王昭,毛峰,黄祥平,黄应平,冯笙琴,易佳,张昌远,刘栓.TiO2/石墨烯复合材料的制备及其光催化性能[J].材料科学与工程学报,2011,29(2):267-232.)。结果如表2所示。
表2多孔石墨烯-沸石-溴氧化铋可见光催化剂降解罗丹明B的活性效果
活性测试结果表明,采用多孔石墨烯-沸石作为载体,可以更好地负载溴氧化铋,增大溴氧化铋的比表面积,减小溴氧化铋晶粒尺寸,经过多孔石墨烯-沸石负载后,溴氧化铋降解罗丹明B的活性得到显著提高,说明多孔石墨烯-沸石可显著提高溴氧化铋催化剂活性,具有广阔的前景。
(3)取实施例4制备的多孔石墨烯-沸石-氯氧化铋0.05g,加入到50mL的罗丹明(10mg/L)水溶液中,调节pH=3.0,混合混合均匀后转入玻璃瓶中,在黑暗的环境中暗反应60min后做光催化测试,可见光灯为氙灯(300W,>420nm)。2h后取样,在551nm处测量溶液的吸光度(Lambda25紫外-可见光分光光度计),测试罗丹明的降解效果(王昭,毛峰,黄祥平,黄应平,冯笙琴,易佳,张昌远,刘栓.TiO2/石墨烯复合材料的制备及其光催化性能[J].材料科学与工程学报,2011,29(2):267-232.)。结果如表3所示。
表3多孔石墨烯-沸石-卤氧化铋可见光催化剂降解罗丹明B的活性效果
活性测试结果表明,采用多孔石墨烯-沸石作为载体,可以更好地负载氯氧化铋,增大氯氧化铋的比表面积,减小碘氯化铋晶粒尺寸,经过多孔石墨烯-沸石负载后,氯氧化铋降解罗丹明B的活性得到显著提高,说明多孔石墨烯-沸石可显著提高氯氧化铋催化剂活性,具有广阔的前景。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其它的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (7)
1.一种多孔石墨烯-沸石-卤氧化铋光催化材料,其特征在于:所述光催化材料由9~50质量份的多孔石墨烯、50~91质量份的沸石和10~100质量份的卤氧化铋复合而成。
2.根据权利要求1所述的一种多孔石墨烯-沸石-卤氧化铋光催化材料,其特征在于:所述多孔石墨烯的比表面积为350~450m2/g,电导率为20~60S·m-1,900℃内的失重为4~6wt%;所述沸石的粒径为0.3~0.5nm,比表面积为100~400m2/g。
3.权利要求1或2所述的多孔石墨烯-沸石-卤氧化铋光催化材料的制备方法,其特征在于包括如下制备步骤:
(1)多孔石墨烯的制备:将石墨粉加入浓硫酸中,冰盐浴冷却下加入KMnO4,室温搅拌反应,反应完成后加水稀释,再加入双氧水,离心去除杂质后,所得上清液依次经超声和微波处理,得到氧化石墨烯溶液,然后加入NaOH,于700~800℃及氮气保护下烧结,得到多孔石墨烯;
(2)多孔石墨烯-沸石复合材料的制备:步骤(1)所得多孔石墨烯加入到乙醇中,超声处理后加入沸石搅拌混合均匀,加热去除乙醇后于700~800℃烧结,得到多孔石墨烯-沸石复合材料;
(3)多孔石墨烯-沸石-卤氧化铋的制备:将BiOX加入到乙醇中,然后加入步骤(2)所得多孔石墨烯-沸石复合材料,超声分散均匀后冷冻干燥,得到所述多孔石墨烯-沸石-卤氧化铋光催化材料。
4.根据权利要求3所述的多孔石墨烯-沸石-卤氧化铋光催化材料的制备方法,其特征在于:步骤(1)中所述KMnO4的用量为石墨粉质量的2.5~3倍;所述双氧水的用量与石墨粉的体积质量比为(2~3):1mL/g;所述NaOH的用量为石墨粉质量的3~5倍。
5.根据权利要求3所述的多孔石墨烯-沸石-卤氧化铋光催化材料的制备方法,其特征在于:步骤(2)中所述沸石的用量为多孔石墨烯质量的1~10倍。
6.根据权利要求3所述的多孔石墨烯-沸石-卤氧化铋光催化材料的制备方法,其特征在于:步骤(3)中所述BiOX与多孔石墨烯-沸石复合材料加入的质量比为(10~100):(100~110)。
7.权利要求1或2所述的多孔石墨烯-沸石-卤氧化铋光催化材料在可见光催化降解水中有机污染物的应用。
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107051587A (zh) * | 2017-06-01 | 2017-08-18 | 上海师范大学 | 漂浮型半导体光催化材料及其制备方法和应用 |
CN109364999A (zh) * | 2018-11-23 | 2019-02-22 | 淮北师范大学 | 一种超薄多孔2d石墨烯/硫化镉-有机胺复合光催化剂及其制备方法 |
CN111097393A (zh) * | 2018-10-25 | 2020-05-05 | 中国科学院上海硅酸盐研究所 | 一种基于二维多孔石墨烯的光催化材料及其制备方法和应用 |
CN113019401A (zh) * | 2021-03-11 | 2021-06-25 | 黑龙江工业学院 | 一种石墨烯基光催化复合材料的制备方法和应用及应用方法 |
CN113117728A (zh) * | 2021-03-07 | 2021-07-16 | 桂林理工大学 | 一种ZSM-5/Bi4O5Br2复合光催化材料的制备方法 |
CN117399059A (zh) * | 2023-10-19 | 2024-01-16 | 北京道思克能源设备有限公司 | 一种氢氰酸的制备方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101653732A (zh) * | 2009-09-29 | 2010-02-24 | 福州大学 | 一种分子筛负载卤氧化铋光催化剂、制备方法及其应用 |
CN103111286A (zh) * | 2013-01-22 | 2013-05-22 | 湖南元素密码石墨烯研究院(有限合伙) | 一种新型纳米复合可见光催化剂及其制备方法 |
CN103877971A (zh) * | 2014-03-07 | 2014-06-25 | 中国科学院东北地理与农业生态研究所 | 高效可见光催化剂及其制备方法 |
CN104353472A (zh) * | 2014-11-26 | 2015-02-18 | 安徽工业大学 | 一种BiOBr/RGO纳米复合材料的制备方法及其在降解罗丹明反应中的应用 |
-
2016
- 2016-06-22 CN CN201610471976.6A patent/CN106111181B/zh active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101653732A (zh) * | 2009-09-29 | 2010-02-24 | 福州大学 | 一种分子筛负载卤氧化铋光催化剂、制备方法及其应用 |
CN103111286A (zh) * | 2013-01-22 | 2013-05-22 | 湖南元素密码石墨烯研究院(有限合伙) | 一种新型纳米复合可见光催化剂及其制备方法 |
CN103877971A (zh) * | 2014-03-07 | 2014-06-25 | 中国科学院东北地理与农业生态研究所 | 高效可见光催化剂及其制备方法 |
CN104353472A (zh) * | 2014-11-26 | 2015-02-18 | 安徽工业大学 | 一种BiOBr/RGO纳米复合材料的制备方法及其在降解罗丹明反应中的应用 |
Non-Patent Citations (5)
Title |
---|
KOVTYUKHOVA, NI等: "Layer-by-layer assembly of ultrathin composite films from micron-sized graphite oxide sheets and polycations", 《CHEMISTRY OF MATERIALS》 * |
于爱丽: "石墨烯/沸石复合材料的制备及对水中污染物的吸附性能研究", 《中国优秀硕士学位论文全文数据库工程科技I辑》 * |
于爱丽: "石墨烯/沸石复合材料的制备及对水中污染物的吸附性能研究", 《暨南大学硕士学位论文》 * |
林立等: "卤氧化铋异质结型可见光光催化的新进展", 《材料导报A:综述篇》 * |
郑昌琼等: "《简明材料词典》", 30 April 2002 * |
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