WO2017219793A1 - 一种短孔道有序介孔碳负载硫铟钴和硫铟镍三元复合光催化剂及其制备方法和应用 - Google Patents

一种短孔道有序介孔碳负载硫铟钴和硫铟镍三元复合光催化剂及其制备方法和应用 Download PDF

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WO2017219793A1
WO2017219793A1 PCT/CN2017/084504 CN2017084504W WO2017219793A1 WO 2017219793 A1 WO2017219793 A1 WO 2017219793A1 CN 2017084504 W CN2017084504 W CN 2017084504W WO 2017219793 A1 WO2017219793 A1 WO 2017219793A1
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indium
short
ordered mesoporous
cobalt
preparation
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PCT/CN2017/084504
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English (en)
French (fr)
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安太成
陈江耀
刘宏利
李桂英
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广东工业大学
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Priority to US16/099,554 priority Critical patent/US10661255B2/en
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Definitions

  • the invention belongs to the technical field of adsorption type catalytic materials, and particularly relates to a short-channel ordered mesoporous carbon-loaded sulfur indium cobalt and sulfur indium nickel ternary composite photocatalyst and a preparation method thereof, and the application in the field of atmospheric environmental protection.
  • VOCs volatile organic compounds
  • ordered mesoporous materials are commonly used, which are a class of important materials with ordered pore structures obtained by self-assembly methods, such as ordered mesoporous carbon.
  • ordered mesoporous carbon Such materials have a series of properties such as large specific surface area and pore volume, narrow pore size distribution, uniform uniformity in the nanometer range, regular pore structure, controllability, easy surface modification and good thermal stability.
  • the traditional ordered mesoporous carbon is rod-shaped or fibrous, the pores are long, and the particles tend to aggregate, which is not conducive to the expansion of VOCs in the pores. Dispersion and transmission.
  • the primary object of the present invention is to provide a method for preparing a short-hole ordered mesoporous carbon-loaded sulfur indium cobalt and a sulfur indium nickel ternary composite photocatalyst.
  • Another object of the present invention is to provide a short-hole ordered mesoporous carbon-loaded sulfur indium cobalt and sulfur indium nickel ternary composite photocatalyst prepared by the above method.
  • the short-hole ordered mesoporous carbon-loaded indium-cobalt-sulfur and sulfur-indium-nickel ternary composite photocatalysts not only have strong adsorption properties for typical VOCs, but also have strong photocatalytic activity.
  • a preparation method of short-channel ordered mesoporous carbon-loaded sulfur indium cobalt and sulfur indium nickel ternary composite photocatalyst comprises the following steps:
  • the mixed solution B obtained in the step S2 is charged into a 25-200 mL polytetrafluoroethylene tank, and hydrothermally reacted at 60 to 250 ° C for 2 to 72 hours. After cooling in the polytetrafluoroethylene tank, the lower layer precipitate is collected and 300 Calcined at ⁇ 800 ° C for 1 ⁇ 24h, to obtain short-channel ordered mesoporous silica;
  • the short-channel ordered mesoporous silica, the carbon source and the water obtained in the step S3 are charged into the crucible at a mass ratio of 1: (10 to 30): (10 to 30), and reacted at 50 to 100 ° C for 1 to 24 hours. Then, it is calcined under nitrogen at 300-1000 ° C for 1-24 hours to obtain ordered mesoporous carbon in short pores;
  • step S6 The 50-200 mg pretreated short-channel ordered mesoporous carbon obtained in step S5 and 20-100 mg cobalt salt, 50-500 mg nickel salt, 60-300 mg indium salt and 30-300 mg reducing agent are sequentially added to 30-100 mL alcohol solution. In the ultrasonic dispersion for 10 to 60 minutes, it is charged into a 50-200 mL polytetrafluoroethylene tank, and hydrothermally reacted at 60-250 ° C for 2 to 72 h.
  • the precipitate After cooling in a polytetrafluoroethylene tank, the precipitate is washed with water at 40 After drying at ⁇ 80 °C for 3 ⁇ 12h, the ordered mesoporous carbon-loaded sulfur indium cobalt and sulfur indium-nickel ternary composite photocatalyst were obtained.
  • the surfactant in the step S1 is a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, polyethylene glycol or cetyltrimethylammonium bromide.
  • the alkane in step S2 is octane, decane or decane.
  • the carbon source in step S4 is phenol or sucrose.
  • the cobalt salt in step S6 is cobalt chloride, cobalt nitrate or cobalt sulfate;
  • the nickel salt is nickel chloride nickel nitrate or nickel sulfate;
  • the indium salt is indium chloride, indium nitrate or indium sulfate;
  • the reducing agent is thiourea, urea or thioacetamide.
  • the alcohol solution described in step S6 is one of ethanol or methanol dissolved in an organic solvent, and the organic solvent is one of glycerin or t-butanol.
  • the volume ratio of the ethanol or methanol to the organic solvent is from 1 to 10:1.
  • the water in steps S1, S5 and S6 is deionized water.
  • the short-hole ordered mesoporous carbon-loaded sulfur indium cobalt and sulfur indium-nickel ternary composite photocatalyst prepared by the above method and its application as a selective adsorbent or photocatalyst for VOCs in the environmental protection field are also in the present invention.
  • the short-hole ordered mesoporous carbon-loaded sulfur indium cobalt and sulfur indium-nickel ternary composite photocatalyst prepared by the above method and its application as a selective adsorbent or photocatalyst for VOCs in the environmental protection field are also in the present invention.
  • the short-hole ordered mesoporous carbon-loaded indium-cobalt-sulfur and sulfur-indium-nickel ternary composite photocatalyst has better adsorption and photocatalytic effects on xylene.
  • the present application provides a method for preparing a short-hole ordered mesoporous carbon-loaded sulfur indium cobalt and sulfur indium nickel ternary composite photocatalyst, comprising the following steps:
  • the mixed solution B is hydrothermally reacted in a polytetrafluoroethylene tank, and after cooling, the precipitate is collected and Calcination to obtain a short-channel ordered mesoporous silica;
  • the ratio of the solution of the water and the concentrated hydrochloric acid to the surfactant is (10-120) mL: (0.1-10) g, and the volume ratio of the water to the concentrated hydrochloric acid (1 to 20): 1.
  • the mixing is carried out in a stirring manner, the stirring temperature is 30 to 90 ° C, and the stirring time is 0.5 to 24 h.
  • the process of obtaining the mixed solution B is specifically:
  • Ammonium fluoride was mixed with the mixed solution A, and after stirring, a mixed solution of an alkane and an orthosilicate was added, and the mixture was stirred again to obtain a mixed solution B.
  • the ratio of the ammonium fluoride to the mixed solution is (0.01 to 0.1) g: (5 to 50) mL; and the volume ratio of the alkane to the tetraethyl orthosilicate is (1 to 10).
  • the stirring time is 0.5 to 60 min, the re-stirring temperature is 30 to 90 ° C, and the re-stirring time is 2 to 72 h.
  • the hydrothermal reaction temperature is 60 to 250 ° C, and the time is 2 to 72 h; the calcination temperature is 300 to 800 ° C, and the time is 1 to 2 h.
  • the mass ratio of the ordered mesoporous carbon, carbon source and water in the short-channel is 1: (10-30): (10-30); the temperature of the reaction is 50-100 °C, The reaction time is from 1 to 24 h; the calcination is carried out under a protective atmosphere, and the calcination temperature is from 300 to 1000 ° C for a period of from 1 to 24 h.
  • the mass ratio of the ordered mesoporous carbon, water, concentrated sulfuric acid and ammonium persulfate in the short-channel is 1: (10-30): (2-10): (1-10);
  • the mixing is carried out in a stirring manner, the stirring temperature is 40 to 90 ° C, the stirring time is 1 to 24 hours, the drying temperature is 50 to 180 ° C, and the time is 1 to 36 hours.
  • the pretreated short-hole ordered mesoporous carbon, cobalt salt, nickel salt, indium salt is (50 to 200) mg: (20 to 100) mg: (50 to 500) mg: (60 to 300) mg: (30 to 300) mg: (30 to 100) mL.
  • the mixing time is 10 to 60 minutes, and the hydrothermal reaction temperature is 60 to 250 ° C, and the time is 2 to 72 hours.
  • the surfactant in the step S1 is a polyethylene oxide-polyglycidyl-polyethylene oxide triblock copolymer, polyethylene glycol or cetyltrimethylammonium bromide.
  • the alkane in step S2 is octane, decane or decane.
  • the carbon source in step S4 is phenol or sucrose.
  • the cobalt salt in step S6 is cobalt chloride, cobalt nitrate or cobalt sulfate: the nickel salt is nickel chloride nickel nitrate or nickel sulfate; the indium salt is indium chloride, indium nitrate or indium sulfate;
  • the reducing agent is thiourea, urea or thioacetamide.
  • the alcohol solution described in step S6 is one of ethanol or methanol dissolved in an organic solvent, and the organic solvent is one of glycerin or t-butanol.
  • the volume ratio of the ethanol or methanol to the organic solvent is from 1 to 10:1.
  • the water in steps S1, S5 and S6 is deionized water.
  • the present application also provides a short-hole ordered mesoporous carbon-loaded sulfur indium cobalt and sulfur indium nickel ternary composite photocatalyst prepared by the preparation method described in the above scheme.
  • the application also provides the application of the short-hole ordered mesoporous carbon-loaded sulfur indium cobalt and sulfur indium nickel ternary composite photocatalysts in the environmental protection field described in the above scheme.
  • a novel high-efficiency adsorption-photocatalytic composite material is prepared by compounding sulfurized indium cobalt and sulfur indium nickel as catalysts with ordered mesoporous carbon materials. Under the sunlight, it can effectively adsorb volatile organic compounds, enhance the absorption and utilization of light by the catalyst, and further improve the stability of the catalyst. This is because the sulfur indium cobalt and the sulfur indium nickel have a narrow band gap energy, can effectively absorb visible light, and generate photogenerated electron-hole pairs, wherein the photogenerated electrons have a reduction effect on the indium sulfide and the sulfur indium nickel to generate light. Corrosion phenomenon.
  • sulfur indium cobalt and sulfur indium nickel have different conduction band and valence band positions, the mutual contact between them facilitates the transmission of photogenerated electrons, thereby separating photogenerated electrons and holes, and effectively suppressing photogenerated electrons to sulfur indium.
  • the reduction of cobalt and sulfur indium nickel improves its photo-corrosion resistance and thus improves the stability of the catalyst.
  • a short-hole ordered mesoporous carbon material is used as an adsorbent for volatile organic substances, because of the pores thereof. Shorter than the traditional ordered mesoporous carbon, it is rod-like or fibrous, which is easier to mass transfer and diffuse VOCs in the pores, so that VOCs can rapidly diffuse on the surface of the indium sulfide and sulfur-indium-nickel catalysts, and quickly reach the activity of the catalyst. The site enhances the adsorption of VOCs.
  • the ordered mesoporous carbon in the short-pores can increase the transmission rate of photogenerated electrons, and the photogenerated electrons are transferred from the indium sulfide and the indium-sulfur-indium to the mesoporous carbon, which can further inhibit the photo-etching of the indium-cobalt-sulfide and the indium-sulfur-indium-nickel. Improve catalyst stability and photocatalytic performance.
  • the ordered mesoporous carbon-loaded indium-cobalt-sulfur and sulfur-indium-nickel ternary composite photocatalysts can not only enhance the adsorption and enrichment of volatile organic compounds by indium-cobalt-sulfide and sulfur-indium-nickel, but also further improve the solar stability of the catalyst. And photocatalytic properties, thus achieving the integration of adsorption and photocatalytic oxidation of VOCs.
  • the present invention has the following beneficial effects:
  • the invention combines the adsorption and enrichment action of short-hole ordered mesoporous carbon on VOCs and the photocatalytic degradation of sulfur-indium-zinc photocatalyst, and prepares a novel high-efficiency adsorption-photocatalytic integrated material--a short hole has
  • the mesoporous carbon-loaded sulfur indium cobalt and sulfur indium-nickel ternary composite photocatalysts have higher light utilization efficiency, electron transport performance and light stability than the binary composite photocatalyst.
  • the short-channel ordered mesoporous carbon-loaded sulfur indium cobalt and sulfur indium-nickel ternary composite photocatalyst prepared by the invention exhibits good adsorption and photocatalytic activity for gas chromatography of typical VOCs, and the adsorption rate of p-xylene reaches within 40 min. With 20.3%, the degradation rate of gas-phase xylene is as high as 93.9% within 60min, which can integrate the adsorption of xylene with photocatalytic oxidation of typical VOCs, so that the hydroxyl radical generated on the catalyst surface can be effectively in situ.
  • Degradation of adsorbed and enriched VOCs greatly enhances the reaction rate and efficiency of photocatalytic degradation of organic pollutants, and solves the problem of regeneration of adsorbents in situ, avoiding post-treatment and secondary pollution of adsorbents.
  • Figure 1 shows the adsorption kinetics and photocatalytic degradation kinetics of gas phase xylene in a short-channel ordered mesoporous carbon-loaded indium-cobalt-sulfur and sulfur-indium-nickel ternary composite photocatalyst.
  • step S2 Add 0.01g of ammonium fluoride to the clear solution obtained in step S1, stir for 0.5min, then add 5mL of a mixture of octane and tetraethyl orthosilicate in a volume ratio of 1:1, and stir at 30 ° C for 2h to obtain a white turbid solution;
  • step S3 The white turbid solution obtained in step S2 is charged into a 25 mL polytetrafluoroethylene tank, and hydrothermally reacted at 60 ° C for 72 h. After cooling in a polytetrafluoroethylene tank, the lower layer precipitate is collected and calcined at 300 ° C for 24 h to obtain Short-hole ordered mesoporous silica;
  • step S4 The short-hole ordered mesoporous silica, phenol and water obtained in step S3 are charged into the crucible at a mass ratio of 1:10:10, reacted at 50 ° C for 1 h, and then calcined at 300 ° C for 24 h under nitrogen to obtain a short-channel.
  • step S5 The short-channel ordered mesoporous carbon obtained in step S4 is stirred with water, concentrated sulfuric acid and ammonium persulfate at a mass ratio of 1:10:10:10 at 40 ° C for 24 hours, and the precipitate is collected and washed at 50 ° C after washing. 36h, the pretreated short-channel ordered mesoporous carbon was obtained;
  • Figure 1 shows the adsorption kinetics and photocatalytic degradation kinetics of gas phase xylene in a short-channel ordered mesoporous carbon-loaded indium-cobalt-sulfur and sulfur-indium-nickel ternary composite photocatalyst. It can be seen from Fig. 1 that the photocatalyst exhibits good adsorption and photocatalytic activity, the adsorption rate of p-xylene reaches 20.3% within 40 min, and the degradation rate of p-xylene reaches 93.9% within 60 min.
  • step S2 Add 0.01g of ammonium fluoride to the clear solution obtained in step S1, stir for 60 minutes, then add 5mL of a mixed solution of decane and tetraethyl orthosilicate in a volume ratio of 10:1, and stir at 30 ° C for 2h to obtain a white turbid solution;
  • step S3 The white turbid solution obtained in step S2 is charged into a 200 mL polytetrafluoroethylene tank, and hydrothermally reacted at 250 ° C for 2 h. After cooling in a polytetrafluoroethylene tank, the lower layer precipitate is collected and calcined at 800 ° C for 1 h to obtain Short-hole ordered mesoporous silica;
  • step S4 The short-hole ordered mesoporous silica, sucrose and water obtained in step S3 are charged into the crucible at a mass ratio of 1:30:30, reacted at 100 ° C for 24 h, and then calcined at 1000 ° C for 1 h under nitrogen gas to obtain a short pore channel.
  • step S5 The short-cell ordered mesoporous carbon obtained in step S4 is stirred with water, concentrated sulfuric acid and ammonium persulfate at a mass ratio of 1:30:2:1 at 90 ° C for 1 h, and the precipitate is collected and washed at 180 ° C. 1h, the pretreated short-hole ordered mesoporous carbon is obtained;
  • step S2 Add 0.05g of ammonium fluoride to the clear solution obtained in step S1, stir for 30min, then add 10mL of a mixed solution of decane and tetraethyl orthosilicate in a volume ratio of 4:1, and stir at 4 ° C for 12h to obtain a white turbid solution;
  • step S3 The white turbid solution obtained in step S2 is charged into a 100 mL polytetrafluoroethylene tank, and hydrothermally reacted at 100 ° C for 48 h. After cooling in a polytetrafluoroethylene tank, the lower layer precipitate is collected and calcined at 540 ° C for 5 h to obtain Short-hole ordered mesoporous silica;
  • step S4 The short-channel ordered mesoporous silica, sucrose and water obtained in step S3 are charged into the crucible at a mass ratio of 1:20:20, reacted at 45 ° C for 12 h, and then calcined at 900 ° C for 4 h under nitrogen gas to obtain a short pore channel.
  • step S5 The short-cell ordered mesoporous carbon obtained in step S4 is stirred with water, concentrated sulfuric acid and ammonium persulfate at a mass ratio of 1:15:5:5 at 50 ° C for 8 hours, and the precipitate is collected and washed at 100 ° C after washing. 12h, the pretreated short-channel ordered mesoporous carbon was obtained;
  • step S2 0.02 g of ammonium fluoride was added to the clear solution obtained in step S1, and after stirring for 10 min, 25 mL of a mixed solution of decane and tetraethyl orthosilicate having a volume ratio of 6:1 was added, and stirred at 35 ° C for 24 hours to obtain a white turbid solution;
  • step S3 The white turbid solution obtained in step S2 is charged into a 150 mL polytetrafluoroethylene tank, and hydrothermally reacted at 90 ° C for 24 h. After cooling in a polytetrafluoroethylene tank, the lower layer precipitate is collected and calcined at 600 ° C for 6 h to obtain Short-hole ordered mesoporous silica;
  • step S4 The short-channel ordered mesoporous silica, phenol and water obtained in step S3 are charged into the crucible at a mass ratio of 1:15:15, reacted at 45 ° C for 12 h, and then calcined at 850 ° C for 10 h under nitrogen atmosphere to obtain a short pore channel.
  • step S5 The short-channel ordered mesoporous carbon obtained in step S4 is stirred with water, concentrated sulfuric acid and ammonium persulfate at a mass ratio of 1:12:4:2 at 60 ° C for 4 hours, and the precipitate is collected and washed at 100 ° C. 6h, the pretreated short-channel ordered mesoporous carbon was obtained;

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Abstract

一种短孔道有序介孔碳负载硫铟钴和硫铟镍三元复合光催化剂及其制备方法和应用。所述短孔道有序介孔碳负载硫铟钴和硫铟镍三元复合光催化剂是将经预处理的短孔道介孔碳与钴盐、镍盐、铟盐和还原剂混合，经水热反应制得。所述短孔道有序介孔碳是将短孔道有序介孔氧化硅与碳源在氮气保护下锻烧获得，所述短孔道有序介孔氧化硅是由表面活性剂、盐酸溶液、氟化铵和正硅酸乙酯的混合物经溶胶-凝胶-水热-锻烧依次反应后获得。该光催化剂对VOCs具有较强的吸附性和可见光催化活性，在催化剂表面原位就能有效地吸附和降解所富集的VOCs，大大增强光催化降解有机污染物的反应速率和效率，在环保领域可作为吸附剂或光催化剂应用。

Description

一种短孔道有序介孔碳负载硫铟钴和硫铟镍三元复合光催化剂及其制备方法和应用
本申请要求于2016年06月20日提交中国专利局、申请号为201610451136.3、发明名称为“一种短孔道有序介孔碳负载硫铟钴和硫铟镍三元复合光催化剂及其制备方法和应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明属于吸附型催化材料技术领域，特别涉及一种短孔道有序介孔碳负载硫铟钴和硫铟镍三元复合光催化剂及其制备方法，以及在大气环境保护领域中的应用。
背景技术
挥发性有机物(Volatile organic compounds,VOCs)引起的污染正逐渐破坏人类生存环境和危害人体健康。如何经济有效地消除VOCs对人类生存环境和人体健康的威胁是当前所要解决的重大难题。由于光催化氧化技术能在光的照射和催化剂的存在下，将VOCs最终降解成CO2和H2O，而受到广泛的关注。目前，大多数已报道的半导体光催化剂仅在紫外光激发下才表现出活性，决定了其只能利用太阳光中的紫外光部分(紫外光只占太阳光总能量的约5％)，这极大地限制了它们的实际应用。为此，大量的科研人员开始致力于研发具有可见光响应的光催化剂，并且已经开发出了大量的可见光活性催化剂，但其催化效率却低于紫外光响应的催化剂，也限制了它们的实际应用。而且由于太阳光中的紫外光会导致可见光响应的催化剂出现严重的光腐蚀，使可见光催化剂在太阳光照射下很不稳定。
为了更好地吸附挥发性有机物，通常采用有序介孔材料，它是利用自组装方法得到的一类重要具有有序孔道结构的材料，如有序介孔碳。这类材料具有比表面积和孔体积大、孔径分布窄、且在纳米范围内均匀可调，孔道结构规则、可控，表面易于修饰以及热稳定性好等一系列特性。然而，传统有序介孔碳呈棒状或纤维状，孔道较长，且颗粒往往呈聚集状，不利于VOCs在孔道内的扩 散和传输。那么，如何有效地吸附挥发性有机物并提高对其光催化效率，制备出在太阳光下具有稳定、高效的太阳光催化剂，能够增强催化剂对光的吸收和利用的同时，进一步提高催化剂的稳定性是亟待解决的技术问题。
目前，还没有关于短孔道有序介孔碳负载硫铟钴和硫铟镍三元复合光催化剂的制备及其在VOCs降解方面应用相关研究和报道。
发明内容
为了解决上述现有技术中存在的不足之处，本发明的首要目的是提供一种短孔道有序介孔碳负载硫铟钴和硫铟镍三元复合光催化剂的制备方法。
本发明的另一目的是提供上述方法制备得到的短孔道有序介孔碳负载硫铟钴和硫铟镍三元复合光催化剂。该短孔道有序介孔碳负载硫铟钴和硫铟镍三元复合光催化剂对典型VOCs不但具有较强的吸附性能，而且具有较强的光催化活性。
本发明的再一目的是提供上述短孔道有序介孔碳负载硫铟钴和硫铟镍三元复合光催化剂的应用。
本发明上述目的通过以下技术方案予以实现：
一种短孔道有序介孔碳负载硫铟钴和硫铟镍三元复合光催化剂的制备方法，包括如下步骤：
Sl.将0.1～10g表面活性剂加入到10～120mL体积比为1～20:1的水和浓盐酸溶液中，在30～90℃下搅拌0.5～24h，得到混合溶液A；
S2.将0.01～0.lg氟化铵加入步骤Sl所得混合溶液A，搅拌0.5～60min后加入5～50mL体积比为1～10:1的烷烃和正硅酸乙酯混合溶液，在30～90℃下搅拌2～72h，得到混合溶液B；
S3.将步骤S2所得混合溶液B装入25～200mL聚四氟乙烯罐中，在60～250℃下水热反应2～72h，待聚四氟乙烯罐中冷却后，收集下层沉淀物并在300～800℃下煅烧1～24h，得到短孔道有序介孔氧化硅；
S4.将步骤S3所得短孔道有序介孔氧化硅、碳源和水以质量比1：(10～30):(10～30)装入坩埚中，在50～100℃反应1～24h，然后在300～1000℃下氮气保护煅烧1～24h，得到短孔道有序介孔碳；
S5.将步骤S4所得短孔道有序介孔碳与水、浓硫酸和过硫酸铵以质量比1: (10～30):(2～10)：(1～10)在40～90℃搅拌1～24h，收集沉淀物经过水洗后在50～180℃下烘干1～36h，得到预处理短孔道有序介孔碳；
S6.将步骤S5所得50～200mg预处理短孔道有序介孔碳与20～l00mg钴盐、50～500mg镍盐、60～300mg铟盐和30～300mg还原剂依次添加到30～l00mL醇溶液中，超声分散10～60min后装入50～200mL聚四氟乙烯罐中，在60～250℃下水热反应2～72h，待聚四氟乙烯罐中冷却后，将沉淀物经水洗后在40～80℃下烘干3～12h后，即得短孔道有序介孔碳负载硫铟钴和硫铟镍三元复合光催化剂。
优选的，步骤S1所述表面活性剂为聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物、聚乙二醇或十六烷基三甲基溴化铵。
优选的，步骤S2所述烷烃为辛烷、癸烷或壬烷。
优选的，步骤S4所述碳源为苯酚或蔗糖。
优选的，步骤S6所述钴盐为氯化钴、硝酸钴或硫酸钴；所述镍盐为氯化镍硝酸镍或硫酸镍；所述铟盐为氯化铟、硝酸铟或硫酸铟；所述还原剂为硫脲、尿素或硫代乙酰胺。
优选的，步骤S6所述的醇溶液为乙醇或甲醇中的一种溶于有机溶剂，所述有机溶剂为甘油或叔丁醇中的一种。
优选的，所述的乙醇或甲醇与有机溶剂的体积比为1～10:1。
优选的，步骤Sl、S5和S6中所述水为去离子水。
另外，上述方法制备的短孔道有序介孔碳负载硫铟钴和硫铟镍三元复合光催化剂及其在环保领域作为VOCs的选择性吸附剂或光催化剂中的应用，也在本发明的保护范围之内。
优选的，该短孔道有序介孔碳负载硫铟钴和硫铟镍三元复合光催化剂尤其对二甲苯的吸附和光催化效果更优。
本申请提供了一种短孔道有序介孔碳负载硫铟钴和硫铟镍三元复合光催化剂的制备方法，包括如下步骤：
S1、将表面活性剂、水与浓盐酸混合，得到混合溶液A；
S2、将氟化铵、混合溶液A、烷烃和正硅酸乙酯混合，得到混合溶液B；
S3、将混合溶液B在聚四氟乙烯罐中进行水热反应，冷却后收集沉淀物并 煅烧，得到短孔道有序介孔氧化硅；
S4、将所述短孔道有序介孔氧化硅、碳源与水混合后反应，将得到的产物进行煅烧，得到短孔道有序介孔碳；
S5、将所述短孔道有序介孔碳、水、浓硫酸与过硫酸铵混合，收集沉淀物水洗后烘干，得到预处理短孔道有序介孔碳；
S6、将所述预处理短孔道有序介孔碳、钴盐、镍盐、铟盐、还原剂与醇溶液混合后置于聚四氟乙烯罐中进行水热反应，得到短孔道有序介孔碳负载硫铟钴和硫铟镍三元复合光催化剂。
优选的，S1步骤中，所述水与浓盐酸得到的溶液与所述表面活性剂的比例为(10～120)mL：(0.1～10)g，所述水与所述浓盐酸的体积比为(1～20)：1。
优选的，S1步骤中，所述混合以搅拌的方式进行，所述搅拌的温度为30～90℃，所述搅拌的时间为0.5～24h。
优选的，S2步骤中，所述得到混合溶液B的过程具体为：
将氟化铵与混合溶液A混合，搅拌后再加入烷烃和正硅酸乙酯的混合溶液，再次搅拌后，得到混合溶液B。
优选的，所述氟化铵与所述混合溶液的比例为(0.01～0.1)g：(5～50)mL；所述烷烃与所述正硅酸乙酯的体积比为(1～10)：1；所述搅拌的时间为0.5～60min，所述再次搅拌的温度为30～90℃，所述再次搅拌的时间为2～72h。
优选的，S3步骤中，所述水热反应的温度为60～250℃，时间为2～72h；所述煅烧的温度为300～800℃，时间为1～2h。
优选的，S4步骤中，所述短孔道有序介孔碳、碳源与水的质量比为1：(10～30):(10～30)；所述反应的温度为50～100℃，所述反应的时间为1～24h；所述煅烧在保护性气氛下进行，所述煅烧的温度为300～1000℃，时间为1～24h。
优选的，S5步骤中，所述短孔道有序介孔碳、水、浓硫酸与过硫酸铵的质量比为1：(10～30)：(2～10)：(1～10)；所述混合以搅拌的方式进行，所述搅拌的温度为40～90℃，所述搅拌的时间为1～24h；所述烘干的温度为50～180℃，时间为1～36h。
优选的，S6步骤中，所述预处理短孔道有序介孔碳、钴盐、镍盐、铟盐、 还原剂与醇溶液的比例为(50～200)mg：(20～100)mg：(50～500)mg：(60～300)mg：(30～300)mg：(30～100)mL。
优选的，S6步骤中，所述混合的时间为10～60min，所述水热反应的温度为60～250℃，时间为2～72h。
优选的，步骤Sl所述表面活性剂为聚环氧乙烷-聚环氧丙烧-聚环氧乙烷三嵌段共聚物、聚乙二醇或十六烷基三甲基溴化铵。
优选的，步骤S2所述烷烃为辛烷、癸烷或壬烷。
优选的，步骤S4所述碳源为苯酚或蔗糖。
优选的，步骤S6所述钴盐为氯化钴、硝酸钴或硫酸钴：所述镍盐为氯化镍硝酸镍或硫酸镍；所述铟盐为氯化铟、硝酸铟或硫酸铟；所述还原剂为硫脲、尿素或硫代乙酰胺。
优选的，步骤S6所述的醇溶液为乙醇或甲醇中的一种溶于有机溶剂，所述有机溶剂为甘油或叔丁醇中的一种。
优选的，所述的乙醇或甲醇与有机溶剂的体积比为1～10:1。
优选的，步骤Sl、S5和S6中所述水为去离子水。
本申请还提供了一种上述方案所述的制备方法所制备的短孔道有序介孔碳负载硫铟钴和硫铟镍三元复合光催化剂。
本申请还提供了上述方案所述的短孔道有序介孔碳负载硫铟钴和硫铟镍三元复合光催化剂在环保领域中的应用。
本发明中以硫铟钴和硫铟镍作为催化剂与有序介孔碳材料进行复合，制备出一种新型高效的吸附-光催化复合材料。在太阳光下既能有效地吸附挥发性有机物，又能增强催化剂对光的吸收和利用，进一步提高催化剂的稳定性。这是由于硫铟钴和硫铟镍具有较窄的带隙能，可以有效吸收可见光，产生光生电子-空穴对，其中光生电子对硫铟钴和硫铟镍具有还原作用，使其产生光腐蚀现象。但由于硫铟钴和硫铟镍具有不同的导带和价带位置，使得它们之间相互接触有利于光生电子的传输，从而使光生电子和空穴分离，有效地抑制了光生电子对硫铟钴和硫铟镍的还原作用，提高其抗光腐蚀性能，进而提高了催化剂的稳定性。
本发明中采用短孔道有序介孔碳材料作为挥发有机物的吸附剂，因其孔道 较短，比传统的有序介孔碳呈棒状或纤维状，更易于VOCs在孔道内的传质与扩散，使VOCs在硫铟钴和硫铟镍催化剂表面能够快速扩散，迅速达到催化剂的活性位点，提高了对VOCs的吸附。同时短孔道有序介孔碳可以提高光生电子的传输速率，使光生电子从硫铟钴和硫铟镍传递到介孔碳上，这样可以进一步抑制对硫铟钴和硫铟镍的光腐蚀，提高催化剂的稳定性和光催化性能。因此，短孔道有序介孔碳负载硫铟钴和硫铟镍三元复合光催化剂不仅可以提高硫铟钴和硫铟镍对挥发有机物的吸附富集，还能进一步提高催化剂的太阳光稳定性和光催化性能，从而实现了吸附与光催化氧化VOCs的一体化。
与现有技术相比，本发明具有以下有益效果：
本发明将短孔道有序介孔碳对VOCs的吸附富集作用与硫铟锌光催化剂的光催化降解作用相结合，制备出一种新型高效的吸附-光催化一体化材料——短孔道有序介孔碳负载硫铟钴和硫铟镍三元复合光催化剂，相比二元复合光催化剂，本发明提供的三元复合光催化剂具有更高的光利用效率、电子传输性能和光稳定性。
本发明制备出的短孔道有序介孔碳负载硫铟钴和硫铟镍三元复合光催化剂对典型VOCs气相二甲苯展现出良好的吸附和光催化活性，对二甲苯的吸附率在40min内达到了20.3％，对气相二甲苯的降解率在60min内高达93.9％，从而可以实典型VOCs二甲苯的吸附与光催化氧化的一体化，使得催化剂表面产生的羟基自由基在原位就可以有效地降解吸附和富集的VOCs，大大增强光催化降解有机污染物的反应速率和效率，同时原位解决了吸附剂的再生难题，避免了吸附剂的后处置和二次污染问题。
附图说明
图1为短孔道有序介孔碳负载硫铟钴和硫铟镍三元复合光催化剂对气相二甲苯的吸附动力学曲线和光催化降解动力学曲线。
具体实施方式
下面结合说明书附图和具体实施例进一步说明本发明的内容，但不应理解为对本发明的限制。若未特别指明，实施例中所用的技术手段为本领域技术人员所熟知的常规手段。除非特别说明，本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
实施例1
1.制备：
Sl.将0.lg聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物加入到l0mL体积比为20:1的水和浓盐酸溶液中，在90℃下搅拌0.5h，得到澄清溶液；
S2.将0.01g氟化铵加入步骤Sl所得澄清溶液，搅拌0.5min后加入5mL体积比为1:1的辛烷和正硅酸乙酯混合溶液，在30℃下搅拌2h，得到白色浑浊溶液；
S3.将步骤S2所得白色浑浊溶液装入25mL聚四氟乙烯罐中，在60℃下水热反应72h，待聚四氟乙烯罐中冷却后，收集下层沉淀物并在300℃下煅烧24h，得到短孔道有序介孔氧化硅；
S4.将步骤S3所得短孔道有序介孔氧化硅、苯酚和水以质量比1:10:10装入坩埚中，在50℃反应1h后，在300℃下氮气保护煅烧24h，得到短孔道有序介孔碳：
S5.将步骤S4所得短孔道有序介孔碳与水、浓硫酸和过硫酸铵以质量比1:10:10:10在40℃搅拌24h，收集沉淀物经过水洗后在50℃下烘干36h，得到预处理短孔道有序介孔碳；
S6.将步骤S5所得50mg预处理短孔道有序介孔碳与20mg氯化钴、50mg氯化镍、60mg氯化铟和30mg硫脲依次缓慢添加到30mL醇溶液(乙醇和甘油体积比1:1)中，超声分散10min后装入50mL聚四氟乙烯罐中，在60℃下水热反应72h，待聚四氟乙烯罐中冷却后，将沉淀物经水洗后在40℃下烘干12h后，即得短孔道有序介孔碳负载硫铟钴和硫铟镍三元复合光催化剂。
2.性能测试：
图1为短孔道有序介孔碳负载硫铟钴和硫铟镍三元复合光催化剂对气相二甲苯的吸附动力学曲线和光催化降解动力学曲线。由图1中可以看出，该光催化剂展现出良好的吸附和光催化活性，对二甲苯的吸附率在40min内达到了20.3％，对二甲苯的降解率在60min内可达93.9％。结果显示，本发明制备的短孔道有序介孔碳负载硫铟钴和硫铟镍三元复合光催化剂是一种高吸附和光催化活性的新型材料。
实施例2
Sl.将l0g聚乙二醇加入到120mL体积比为1:1的水和浓盐酸溶液中，在 30℃下搅拌24h，得到澄清溶液；
S2.将0.01g氟化铵加入步骤Sl所得澄清溶液，搅拌60分钟后加入5mL体积比为10:1的癸烷和正硅酸乙酯混合溶液，在30℃下搅拌2h，得到白色浑浊溶液；
S3.将步骤S2所得白色浑浊溶液装入200mL聚四氟乙烯罐中，在250℃下水热反应2h，待聚四氟乙烯罐中冷却后，收集下层沉淀物并在800℃下煅烧lh，得到短孔道有序介孔氧化硅；
S4.将步骤S3所得短孔道有序介孔氧化硅、蔗糖和水以质量比1:30:30装入坩埚中，在100℃反应24h后在1000℃下氮气保护煅烧lh，得到短孔道有序介孔碳；
S5.将步骤S4所得短孔道有序介孔碳与水、浓硫酸和过硫酸铵以质量比1:30:2:1在90℃搅拌lh，收集沉淀物经过水洗后在180℃下烘干1h，得到预处理短孔道有序介孔碳；
S6.将步骤S5所得200mg预处理短孔道有序介孔碳与100mg硝酸钴、500mg硝酸镍、300mg硝酸铟和300mg尿素依次缓慢添加到100mL醇溶液(甲醇和叔丁醇体积比10:1)中，超声分散60min后装入200mL聚四氟乙烯罐中，在250℃下水热反应2h，待聚四氟乙烯罐中冷却后，将沉淀物经水洗后在80℃下烘干3h后，即得短孔道有序介孔碳负载硫铟钴和硫铟镍三元复合光催化剂。
实施例3
Sl.将2g十六烷基三甲基溴化铵加入到50mL体积比为5:1的水和浓盐酸溶液中，在45℃下搅拌4h，得到澄清溶液；
S2.将0.05g氟化铵加入步骤Sl所得澄清溶液，搅拌30min后加入10mL体积比为4:1的壬烷和正硅酸乙酯混合溶液，在4℃下搅拌12h，得到白色浑浊溶液；
S3.将步骤S2所得白色浑浊溶液装入100mL聚四氟乙烯罐中，在100℃下水热反应48h，待聚四氟乙烯罐中冷却后，收集下层沉淀物并在540℃下煅烧5h，得到短孔道有序介孔氧化硅；
S4.将步骤S3所得短孔道有序介孔氧化硅、蔗糖和水以质量比1:20:20装入坩埚中，在45℃反应12h后在900℃下氮气保护煅烧4h，得到短孔道有序介孔碳；
S5.将步骤S4所得短孔道有序介孔碳与水、浓硫酸和过硫酸铵以质量比1:15:5:5在50℃搅拌8h，收集沉淀物经过水洗后在100℃下烘干12h，得到预处理短孔道有序介孔碳；
S6.将步骤S5所得100mg预处理短孔道有序介孔碳与50mg硫酸钴、200mg硫酸镍、250mg硫酸铟和250mg硫代乙酰胺依次缓慢添加到40mL醇溶液(乙醇和叔丁醇体积比5:1)中，超声分散20min后装入100mL聚四氟乙烯罐中，在150℃下水热反应9h，待聚四氟乙烯罐中冷却后，将沉淀物经水洗后在60℃下烘干8h后，即得短孔道有序介孔碳负载硫铟钴和硫铟镍三元复合光催化剂。
实施例4
Sl.将6g聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物加入到85mL体积比为8:1的水和浓盐酸溶液中，在35℃下搅拌3h，得到澄清溶液；
S2.将0.02g氟化铵加入步骤Sl所得澄清溶液，搅拌10min后加入25mL体积比为6:1的癸烷和正硅酸乙酯混合溶液，在35℃下搅拌24h，得到白色浑浊溶液；
S3.将步骤S2所得白色浑浊溶液装入150mL聚四氟乙烯罐中，在90℃下水热反应24h，待聚四氟乙烯罐中冷却后，收集下层沉淀物并在600℃下煅烧6h，得到短孔道有序介孔氧化硅；
S4.将步骤S3所得短孔道有序介孔氧化硅、苯酚和水以质量比1:15:15装入坩埚中，在45℃反应12h后在850℃下氮气保护煅烧10h，得到短孔道有序介孔碳；
S5.将步骤S4所得短孔道有序介孔碳与水、浓硫酸和过硫酸铵以质量比1:12:4:2在60℃搅拌4h，收集沉淀物经过水洗后在100℃下烘干6h，得到预处理短孔道有序介孔碳；
S6.将步骤S5所得150mg预处理短孔道有序介孔碳与80mg氯化钴、145mg氯化镍、145mg硝酸铟和155mg尿素依次缓慢添加到45mL醇溶液(甲醇和甘油体积比3:1)中，超声分散15min后装入100mL聚四氟乙烯罐中，在180℃下水热反应10h，待聚四氟乙烯罐中冷却后，将沉淀物经水洗后在50℃下烘干12h后，即得短孔道有序介孔碳负载硫铟钴和硫铟镍三元复合光催化剂。
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，其他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 (29)

  1. 一种短孔道有序介孔碳负载硫铟钴和硫铟镍三元复合光催化剂的制备方法，其特征在于，包括如下步骤：
    Sl.将0.1～10g表面活性剂加入到10～120mL体积比为1～20:1的水和浓盐酸溶液中，在30～90℃下搅拌0.5～24h，得到混合溶液A；
    S2.将0.01～0.lg氟化铵加入步骤Sl所得混合溶液A，搅拌0.5～60min后加入5～50mL体积比为1～10:1的烷烃和正硅酸乙酯混合溶液，在30～90℃下搅拌2～72h，得到混合溶液B；
    S3.将步骤S2所得混合溶液B装入25～200mL聚四氟乙烯罐中，在60～250℃下水热反应2～72h，待聚四氟乙烯罐中冷却后，收集下层沉淀物并在300～800℃下煅烧1～2h，得到短孔道有序介孔氧化硅；
    S4.将步骤S3所得短孔道有序介孔氧化硅、碳源和水以质量比1：(10～30):(10～30)装入坩埚中，在50～100℃反应1～24h，然后在300～1000℃下氮气保护煅烧1～24h，得到短孔道有序介孔碳；
    S5.将步骤S4所得短孔道有序介孔碳与水、浓硫酸和过硫酸铵以质量比1:(10～30):(2～10)：(1～10)在40～90℃搅拌1～24h，收集沉淀物经过水洗后在50～180℃下烘干1～36h，得到预处理短孔道有序介孔碳；
    S6.将步骤S5所得50～200mg预处理短孔道有序介孔碳与20～l00mg钴盐、50～500mg镍盐、60～300mg铟盐和30～300mg还原剂依次添加到30～l00mL醇溶液中，超声分散10～60min后装入50～200mL聚四氟乙烯罐中，在60～250℃下水热反应2～72h，待聚四氟乙烯罐中冷却后，将沉淀物经水洗后在40～80℃下烘干3～12h后，即得短孔道有序介孔碳负载硫铟钴和硫铟镍三元复合光催化剂。
  2. 根据权利要求1所述的制备方法，其特征在于，步骤Sl所述表面活性剂为聚环氧乙烷-聚环氧丙烧-聚环氧乙烷三嵌段共聚物、聚乙二醇或十六烷基三甲基溴化铵。
  3. 根据权利要求1所述的制备方法，其特征在于，步骤S2所述烷烃为辛烷、癸烷或壬烷。
  4. 根据权利要求1所述的制备方法，其特征在于，步骤S4所述碳源为苯酚或蔗糖。
  5. 根据权利要求1所述的制备方法，其特征在子，步骤S6所述钴盐为氯化钴、硝酸钴或硫酸钴；所述镍盐为氯化镍硝酸镍或硫酸镍；所述铟盐为氯化铟、硝酸铟或硫酸铟；所述还原剂为硫脲、尿素或硫代乙酰胺。
  6. 根据权利要求1所述的制备方法，其特征在于，步骤S6所述的醇溶液为乙醇或甲醇中的一种溶于有机溶剂，所述有机溶剂为甘油或叔丁醇中的一种。
  7. 根据权利要求6所述的制备方法，其特征在于，所述的乙醇或甲醇与有机溶剂的体积比为1～10:1。
  8. 根据权利要求1所述的制备方法，其特征在于，步骤Sl、S5和S6中所述水为去离子水。
  9. 一种由权利要求1～8任一项所述的制备方法所制备的短孔道有序介孔碳负载硫铟钴和硫铟镍三元复合光催化剂。
  10. 权利要求9所述的短孔道有序介孔碳负载硫铟钴和硫铟镍三元复合光催化剂在环保领域中的应用。
  11. 一种短孔道有序介孔碳负载硫铟钴和硫铟镍三元复合光催化剂的制备方法，其特征在于，包括如下步骤：
    S1、将表面活性剂、水与浓盐酸混合，得到混合溶液A；
    S2、将氟化铵、混合溶液A、烷烃和正硅酸乙酯混合，得到混合溶液B；
    S3、将混合溶液B在聚四氟乙烯罐中进行水热反应，冷却后收集沉淀物并煅烧，得到短孔道有序介孔氧化硅；
    S4、将所述短孔道有序介孔氧化硅、碳源与水混合后反应，将得到的产物进行煅烧，得到短孔道有序介孔碳；
    S5、将所述短孔道有序介孔碳、水、浓硫酸与过硫酸铵混合，收集沉淀物水洗后烘干，得到预处理短孔道有序介孔碳；
    S6、将所述预处理短孔道有序介孔碳、钴盐、镍盐、铟盐、还原剂与醇溶液混合后置于聚四氟乙烯罐中进行水热反应，得到短孔道有序介孔碳负载硫铟钴和硫铟镍三元复合光催化剂。
  12. 根据权利要求11所述的制备方法，其特征在于，S1步骤中，所述水与浓盐酸得到的溶液与所述表面活性剂的比例为(10～120)mL：(0.1～10)g，所述水与所述浓盐酸的体积比为(1～20)：1。
  13. 根据权利要求11所述的制备方法，其特征在于，S1步骤中，所述混合以搅拌的方式进行，所述搅拌的温度为30～90℃，所述搅拌的时间为0.5～24h。
  14. 根据权利要求11所述的制备方法，其特征在于，S2步骤中，所述得到混合溶液B的过程具体为：
    将氟化铵与混合溶液A混合，搅拌后再加入烷烃和正硅酸乙酯的混合溶液，再次搅拌后，得到混合溶液B。
  15. 根据权利要求14所述的制备方法，其特征在于，所述氟化铵与所述混合溶液的比例为(0.01～0.1)g：(5～50)mL；所述烷烃与所述正硅酸乙酯的体积比为(1～10)：1；所述搅拌的时间为0.5～60min，所述再次搅拌的温度为30～90℃，所述再次搅拌的时间为2～72h。
  16. 根据权利要求11所述的制备方法，其特征在于，S3步骤中，所述水热反应的温度为60～250℃，时间为2～72h；所述煅烧的温度为300～800℃，时间为1～2h。
  17. 根据权利要求11所述的制备方法，其特征在于，S4步骤中，所述短孔道有序介孔碳、碳源与水的质量比为1：(10～30):(10～30)；所述反应的温度为50～100℃，所述反应的时间为1～24h；所述煅烧在保护性气氛下进行，所述煅烧的温度为300～1000℃，时间为1～24h。
  18. 根据权利要求11所述的制备方法，其特征在于，S5步骤中，所述短孔道有序介孔碳、水、浓硫酸与过硫酸铵的质量比为1：(10～30)：(2～10)：(1～10)；所述混合以搅拌的方式进行，所述搅拌的温度为40～90℃，所述搅拌的时间为1～24h；所述烘干的温度为50～180℃，时间为1～36h。
  19. 根据权利要求11所述的制备方法，其特征在于，S6步骤中，所述预处理短孔道有序介孔碳、钴盐、镍盐、铟盐、还原剂与醇溶液的比例为(50～200)mg：(20～100)mg：(50～500)mg：(60～300)mg：(30～300)mg：(30～100)mL。
  20. 根据权利要求11所述的制备方法，其特征在于，S6步骤中，所述混合 的时间为10～60min，所述水热反应的温度为60～250℃，时间为2～72h。
  21. 根据权利要求11所述的制备方法，其特征在于，步骤Sl所述表面活性剂为聚环氧乙烷-聚环氧丙烧-聚环氧乙烷三嵌段共聚物、聚乙二醇或十六烷基三甲基溴化铵。
  22. 根据权利要求11所述的制备方法，其特征在于，步骤S2所述烷烃为辛烷、癸烷或壬烷。
  23. 根据权利要求11所述的制备方法，其特征在于，步骤S4所述碳源为苯酚或蔗糖。
  24. 根据权利要求11所述的制备方法，其特征在子，步骤S6所述钴盐为氯化钴、硝酸钴或硫酸钴；所述镍盐为氯化镍硝酸镍或硫酸镍；所述铟盐为氯化铟、硝酸铟或硫酸铟；所述还原剂为硫脲、尿素或硫代乙酰胺。
  25. 根据权利要求11所述的制备方法，其特征在于，步骤S6所述的醇溶液为乙醇或甲醇中的一种溶于有机溶剂，所述有机溶剂为甘油或叔丁醇中的一种。
  26. 根据权利要求25所述的制备方法，其特征在于，所述的乙醇或甲醇与有机溶剂的体积比为1～10:1。
  27. 根据权利要求11所述的制备方法，其特征在于，步骤Sl、S5和S6中所述水为去离子水。
  28. 一种权利要求11～27任一项所述的制备方法所制备的短孔道有序介孔碳负载硫铟钴和硫铟镍三元复合光催化剂。
  29. 权利要求28所述的短孔道有序介孔碳负载硫铟钴和硫铟镍三元复合光催化剂在环保领域中的应用。
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