CN101811044B - Potassium niobate nanotube photocatalyst and preparation method and application thereof - Google Patents
Potassium niobate nanotube photocatalyst and preparation method and application thereof Download PDFInfo
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Abstract
本发明公开了一种铌酸钾纳米管光催化剂的制备方法和应用，将铌酸钾纳米粒子粉末分散在稀酸溶液中，持续搅拌3～4天后过滤、水洗至中性，得到酸化的铌酸钾；然后将酸化的铌酸钾分散在去离子水中，滴加烷基胺水溶液至pH为9～10，搅拌2～3天后将溶液静置分级，得到铌酸钾纳米管光催化剂，且可进一步负载金属、氧化物或染料，在紫外或可见光条件下催化还原水溶液制氢、降解有机污染物。本发明的制备方法条件温和、周期短、绿色环保，可以得到形貌均一、管径分布窄、催化效率高的铌酸钾纳米管催化剂。The invention discloses a preparation method and application of a potassium niobate nanotube photocatalyst. Potassium niobate nanoparticle powder is dispersed in a dilute acid solution, stirred continuously for 3 to 4 days, filtered and washed to neutrality to obtain acidified niobium Potassium niobate; then the acidified potassium niobate is dispersed in deionized water, and an aqueous alkylamine solution is added dropwise to a pH of 9 to 10. After stirring for 2 to 3 days, the solution is left to stand and graded to obtain a potassium niobate nanotube photocatalyst, and It can further support metals, oxides or dyes, and catalytically reduce aqueous solution to produce hydrogen and degrade organic pollutants under ultraviolet or visible light conditions. The preparation method of the invention has mild conditions, short period, and is environmentally friendly, and can obtain a potassium niobate nanotube catalyst with uniform appearance, narrow pipe diameter distribution and high catalytic efficiency.
Description
技术领域 technical field
本发明属于能源技术领域，具体的，涉及一种铌酸钾纳米管光催化剂及其制备方法和应用。The invention belongs to the field of energy technology, and in particular relates to a potassium niobate nanotube photocatalyst and a preparation method and application thereof.
背景技术 Background technique
随着化石能源的逐渐枯竭和环境污染问题的加剧，人类急需寻找新型的可替代能源。太阳能取之不尽，用之不竭，把太阳能转化为氢能，不仅可以缓解能源危机，还可以从根本上解决环境问题。With the gradual depletion of fossil energy and the aggravation of environmental pollution, human beings urgently need to find new alternative energy sources. Solar energy is inexhaustible and inexhaustible. Converting solar energy into hydrogen energy can not only alleviate the energy crisis, but also fundamentally solve environmental problems.
经过30余年的研究，以半导体光催化分解水制氢的多相光催化技术取得了飞速进展。目前，光解水制氢所用的催化剂体系主要有氧化物、硫化物、氮化物及其固溶体、层状金属氧化物及其柱撑改性产物等。目前一种新的催化剂体系-某些铌酸盐化合物如Cu掺杂的K2Nb4O11，Sr2Ta1-xNbxO7，KNb3O8和柱撑的HCa2Nb3O10，相对于TiO2体系具有更高的催化效果，从而引起了研究者的注意(Journal of Solid State Chemistry，2005，178：1968)。After more than 30 years of research, the heterogeneous photocatalytic technology of semiconductor photocatalytic water splitting to produce hydrogen has made rapid progress. At present, the catalyst systems used for photolysis of water to produce hydrogen mainly include oxides, sulfides, nitrides and their solid solutions, layered metal oxides and their pillared modified products, etc. Presently a new catalyst system - certain niobate compounds such as Cu-doped K 2 Nb 4 O 11 , Sr 2 Ta 1-x Nb x O 7 , KNb 3 O 8 and pillared HCa 2 Nb 3 O 10 , has a higher catalytic effect than the TiO 2 system, which has attracted the attention of researchers (Journal of Solid State Chemistry, 2005, 178: 1968).
铌酸钾纳米管因具有如下特点而在制氢性能方面具有优势：①比表面积大，表面的活性位点多，吸附能力强；②一维管状结构有利于光生电子和空穴的分离，有利于提高催化剂的光催化反应产率；③易于***客体分子，对主体结构进行有机、无机改性，提高其对太阳光的利用率及制氢效率。Geoffrey B.Saupe等人虽已对铌酸钾纳米管的制备进行了研究(Chemistry Materials，2000，12：1556-1562)，但问题是酸化铌酸钾纳米粒子须在40℃的条件下进行，其间更新盐酸4次，剥落后的溶液中须加入NaCl或KCl进行盐析，最后加入过量盐酸沉淀才能得到铌酸钾纳米管。Michael C.Sarahan等人在Geoffrey B.Saupe制备铌酸钾纳米管的基础上进一步研究了铌酸钾纳米管的光催化还原水制氢的性能(Journal of Solid StateChemistry，2008，181：1678-1683)，但在铌酸钾纳米管制备过程中酸化时间(五天)及剥落时间(六天)都较长，且没有做分级处理，在还原水选用甲醇作牺牲剂时，甲醇(20％)及催化剂(100mg)的用量大，管的产氢速率仅有0.25mmol·h-1·g-1。Potassium niobate nanotubes have advantages in hydrogen production performance due to the following characteristics: ① large specific surface area, many active sites on the surface, and strong adsorption capacity; ② one-dimensional tubular structure is conducive to the separation of photogenerated electrons and holes, and has It is beneficial to improve the photocatalytic reaction yield of the catalyst; ③ it is easy to insert guest molecules, carry out organic and inorganic modification to the main structure, and improve its utilization rate of sunlight and hydrogen production efficiency. Although Geoffrey B. Saupe and others have studied the preparation of potassium niobate nanotubes (Chemistry Materials, 2000, 12: 1556-1562), the problem is that the acidification of potassium niobate nanoparticles must be carried out at 40°C. During this period, the hydrochloric acid was renewed 4 times, and NaCl or KCl must be added to the peeled solution for salting out, and finally, excess hydrochloric acid was added for precipitation to obtain potassium niobate nanotubes. Michael C.Sarahan et al further studied the photocatalytic hydrogen production performance of potassium niobate nanotubes based on the preparation of potassium niobate nanotubes by Geoffrey B.Saupe (Journal of Solid State Chemistry, 2008, 181: 1678-1683 ), but the acidification time (five days) and exfoliation time (six days) are all longer in the preparation process of potassium niobate nanotubes, and there is no classification treatment. When methanol is used as sacrificial agent in reducing water, methanol (20%) And the amount of catalyst (100mg) is large, the hydrogen production rate of the tube is only 0.25mmol·h -1 ·g -1 .
层状的K4Nb6O17在紫外光辐射下能够分解水产生氢气(Journal ofPhotochemistry and Photobiology A：Chemistry，2004，166：115-122)。但是由于光生电子/空穴对的重组以及不能利用可见光等原因，使得它的太阳能光催化裂解水的能量转化效率很低。国内杨亚辉等(材料导报，2005，19：117-124)将高温固相合成的铌酸钾进行了一些过渡金属离子掺杂和贵金属负载，以提高铌酸钾纳米粒子对可见光的利用和铌酸钾纳米粒子光催化还原水制氢的效率，并取得了一定的结果。The layered K 4 Nb 6 O 17 can decompose water to generate hydrogen under ultraviolet radiation (Journal of Photochemistry and Photobiology A: Chemistry, 2004, 166: 115-122). However, due to the recombination of photogenerated electron/hole pairs and the inability to utilize visible light, the energy conversion efficiency of its solar photocatalytic water splitting is very low. In China, Yang Yahui et al. (Materials Herald, 2005, 19:117-124) carried out some transition metal ion doping and noble metal loading on potassium niobate synthesized in high temperature solid phase to improve the utilization of visible light and niobate Potassium nanoparticles photocatalytically reduce the efficiency of hydrogen production from water, and achieved certain results.
从文献和现有专利的结果看，现有铌酸钾催化剂大多负载量小，且结合力不牢固，稳定性差，在还原水过程中所用甲醇量大，在利用太阳能进行光催化方面还受到很大限制，所以在太阳能光催化研究中如何制备催化性能高的铌酸钾光催化剂并实现其对可见光的利用成为目前的研究热点之一。From the results of literature and existing patents, most of the existing potassium niobate catalysts have small loading capacity, weak binding force and poor stability. The amount of methanol used in the process of reducing water is large, and there are still many problems in the use of solar energy for photocatalysis. Therefore, how to prepare potassium niobate photocatalyst with high catalytic performance and realize its utilization of visible light has become one of the current research hotspots in the research of solar photocatalysis.
发明内容 Contents of the invention
本发明的第一个目的在于提供一种铌酸钾纳米管光催化剂的制备方法。The first object of the present invention is to provide a preparation method of potassium niobate nanotube photocatalyst.
本发明的第二个目的在于提供一种由该方法制备的铌酸钾纳米管光催化剂。The second object of the present invention is to provide a potassium niobate nanotube photocatalyst prepared by the method.
本发明的第三个目的在于提供铌酸钾纳米管光催化剂的应用。The third object of the present invention is to provide the application of potassium niobate nanotube photocatalyst.
本发明的制备方法，包括以下步骤：The preparation method of the present invention comprises the following steps:
A)、酸化：将铌酸钾纳米粒子粉末，分散于稀酸溶液中，持续搅拌3～4天后将溶液过滤、水洗至中性，得到酸化的铌酸钾；A), acidification: the potassium niobate nanoparticle powder is dispersed in the dilute acid solution, and after 3-4 days of continuous stirring, the solution is filtered and washed to neutrality to obtain acidified potassium niobate;
B)、剥落：将所述酸化的铌酸钾分散在去离子水中，滴加剥落剂至pH为9～10，持续搅拌2～3天，离心分离得到铌酸钾纳米管光催化剂。B) Exfoliation: disperse the acidified potassium niobate in deionized water, add an exfoliation agent dropwise until the pH is 9-10, keep stirring for 2-3 days, and centrifuge to obtain a potassium niobate nanotube photocatalyst.
优选的，所述步骤A中持续搅拌4天；所述步骤B中滴加剥落剂至pH为10，持续搅拌3天。Preferably, in the step A, the stirring is continued for 4 days; in the step B, the peeling agent is added dropwise until the pH is 10, and the stirring is continued for 3 days.
进一步的，本发明的制备方法还包括步骤C)、分级：将所述步骤B得到的溶液静置分级，离心分离得到铌酸钾纳米管光催化剂。Further, the preparation method of the present invention also includes step C), classification: the solution obtained in step B is statically classified, and centrifuged to obtain the potassium niobate nanotube photocatalyst.
本发明的制备方法，所述步骤A中的铌酸钾纳米粒子是以摩尔比为2∶3混合的碳酸钾与五氧化二铌为原料通过高温固相法制备得到，或者以五氧化二铌和KOH为原料，通过水热法制得。所述步骤B中的剥落剂为烷基胺水溶液或四丁基氢氧化铵水溶液，所述烷基胺为CnH2n+1NH2，n＝1，3，4，5，6，7，8，12，16。In the preparation method of the present invention, the potassium niobate nanoparticles in the step A are prepared by a high-temperature solid-phase method using potassium carbonate and niobium pentoxide mixed in a molar ratio of 2:3, or the And KOH as raw materials, prepared by hydrothermal method. The exfoliating agent in the step B is an aqueous solution of alkylamine or aqueous solution of tetrabutylammonium hydroxide, and the alkylamine is C n H2 n+1 NH 2 , n=1, 3, 4, 5, 6, 7, 8 , 12, 16.
进一步的，本发明的制备方法还包括将步骤C得到的铌酸钾纳米管负载金属、氧化物的步骤。所述金属来源于氯化铜、氯铂酸、氯金酸、氯钯酸中的一种或几种的组合，相应的，所述负载金属为铜、铂、金、钯中的一种或几种的组合；所述金属氧化物来源于硝酸铜、氢氧化铜、硝酸镍中的一种或几种的组合，相应的，所述负载金属氧化物为氧化铜、氧化镍或氧化铜与氧化镍的组合。优选的，本发明的制备方法得到的铌酸钾纳米管光催化剂负载Pt。Further, the preparation method of the present invention also includes the step of loading the potassium niobate nanotubes obtained in step C with metals and oxides. The metal is derived from one or more of copper chloride, chloroplatinic acid, chloroauric acid, and chloropalladic acid, and correspondingly, the supported metal is one or more of copper, platinum, gold, and palladium. Several combinations; the metal oxide is derived from one or more combinations of copper nitrate, copper hydroxide, nickel nitrate, correspondingly, the supported metal oxide is copper oxide, nickel oxide or copper oxide and A combination of nickel oxides. Preferably, the potassium niobate nanotube photocatalyst obtained by the preparation method of the present invention is loaded with Pt.
采用本发明的制备方法制备的铌酸钾纳米管光催化剂可单独或负载在金属、ITO、FTO、活性炭或玻璃上使用，其管径为20-90nm，管长度为500nm-4μ，长径比高，可用于在紫外光条件下催化还原水制氢，在紫外光照射下还原水、甲醇、乙醇、三乙醇胺、罗丹明B，甲基橙、维生素C或葡萄糖的水溶液获得氢气，紫外光下的产氢速率为0.2-5mmol·h-1·g-1；在紫外光及可见光下降解有机污染物，所述有机污染物为对硝基苯酚、甲基橙或罗丹明B。The potassium niobate nanotube photocatalyst prepared by the preparation method of the present invention can be used alone or supported on metal, ITO, FTO, activated carbon or glass. Its tube diameter is 20-90nm, tube length is 500nm-4μ, aspect ratio High, can be used to catalyze the reduction of water to produce hydrogen under ultraviolet light, reduce water, methanol, ethanol, triethanolamine, rhodamine B, methyl orange, vitamin C or glucose in aqueous solution to obtain hydrogen under ultraviolet light The hydrogen production rate is 0.2-5mmol·h -1 ·g -1 ; it degrades organic pollutants under ultraviolet light and visible light, and the organic pollutants are p-nitrophenol, methyl orange or rhodamine B.
本发明的铌酸钾纳米管光催化剂的制备方法，包括酸化、剥落，分级等步骤，在室温条件下，水溶液中，在较短的酸化时间和剥落时间内制备得到铌酸钾纳米管，制备条件温和、周期短、绿色环保，通过对催化剂进行分级筛选，避免了由于剥落不彻底造成催化剂整体光催化性能低的缺点，得到的光催化剂比表面积大，活性位点多，性能稳定，金属、氧化物或染料的负载量高，金属或氧化物的负载量为0.1％-50％，不仅能被紫外光激发，还能被可见光激发，提高了铌酸钾纳米管对可见光的响应和光催化还原水制氢和光催化降解的性能，铌酸钾纳米管在紫外光下的光催化还原水制氢的性能是铌酸钾纳米粒子的4-6倍，负载后铌酸钾纳米管光催化剂较纯铌酸钾纳米管在紫外光下的催化活性提高20-30倍，是商品级P25TiO2光催化剂的10-15倍。The preparation method of the potassium niobate nanotube photocatalyst of the present invention comprises the steps of acidification, exfoliation, classification, etc., at room temperature, in an aqueous solution, the potassium niobate nanotube is prepared in a shorter acidification time and exfoliation time, and the preparation The conditions are mild, the cycle is short, and the environment is green. By classifying and screening the catalyst, the shortcoming of the overall photocatalytic performance of the catalyst due to incomplete exfoliation is avoided. The obtained photocatalyst has a large specific surface area, many active sites, and stable performance. Metal, The load of oxide or dye is high, and the load of metal or oxide is 0.1%-50%. It can be excited not only by ultraviolet light, but also by visible light, which improves the response of potassium niobate nanotubes to visible light and photocatalytic reduction. The performance of water hydrogen production and photocatalytic degradation, the performance of photocatalytic reduction of water hydrogen production by potassium niobate nanotubes under ultraviolet light is 4-6 times that of potassium niobate nanoparticles, and the photocatalyst of potassium niobate nanotubes is relatively pure after loading The catalytic activity of potassium niobate nanotubes under ultraviolet light is increased by 20-30 times, which is 10-15 times that of commercial grade P25TiO2 photocatalyst.
附图说明 Description of drawings
图1为铌酸钾纳米管的TEM照片，其中a为分级得到的上层铌酸钾纳米管；b为分级得到的下层铌酸钾纳米管。Figure 1 is a TEM photo of potassium niobate nanotubes, wherein a is the upper layer potassium niobate nanotubes obtained by classification; b is the lower layer potassium niobate nanotubes obtained by classification.
图2为铌酸钾纳米粒子，上、下层铌酸钾纳米管及1.5％Pt负载的上层铌酸钾纳米管在紫外光下催化还原水制氢性能，其中牺牲剂为10％的三乙醇胺水溶液。Figure 2 shows the hydrogen production performance of potassium niobate nanoparticles, upper and lower layers of potassium niobate nanotubes and 1.5% Pt-loaded upper layer of potassium niobate nanotubes under ultraviolet light, where the sacrificial agent is 10% triethanolamine aqueous solution .
具体实施方式 Detailed ways
以下结合具体实施例，对本发明做进一步说明。应理解，以下实施例仅用于说明本发明而非用于限制本发明的范围。The present invention will be further described below in conjunction with specific embodiments. It should be understood that the following examples are only used to illustrate the present invention but not to limit the scope of the present invention.
在本发明的上下文中，术语“牺牲剂”是指在光催化还原水制氢过程中为了保证催化剂复原而加入的、主要起还原剂作用的试剂。本发明中所用的牺牲剂包括：甲醇、乙醇、三乙醇胺、罗丹明B，甲基橙、维生素C、葡萄糖。“剥落剂”是指能进入到铌酸钾粒子的层间进而将层状铌酸钾撑开变成片状进一步卷曲成管的试剂。(正确)In the context of the present invention, the term "sacrificial agent" refers to a reagent that is added to ensure catalyst recovery during the photocatalytic reduction of water to hydrogen production and mainly functions as a reducing agent. The sacrificial agents used in the present invention include: methanol, ethanol, triethanolamine, rhodamine B, methyl orange, vitamin C, and glucose. "Exfoliating agent" refers to an agent that can enter into the interlayer of potassium niobate particles and then expand the layered potassium niobate into a sheet shape and then curl it into a tube. (correct)
实施例1铌酸钾纳米粒子的制备The preparation of embodiment 1 potassium niobate nanoparticles
1.1高温固相法1.1 High temperature solid phase method
以摩尔比为2∶3混合的碳酸钾与五氧化二铌为原料将其研磨、混合均匀后在1100℃下煅烧24小时，冷却至室温后即得到铌酸钾纳米粒子。Potassium carbonate and niobium pentoxide mixed at a molar ratio of 2:3 were used as raw materials, ground and mixed uniformly, calcined at 1100°C for 24 hours, and cooled to room temperature to obtain potassium niobate nanoparticles.
1.2水热法1.2 Hydrothermal method
将0.86g五氧化二铌分散于30mL 1mol·L-1KOH溶液中，于250℃水热反应8小时，反应结束自然冷却至室温，然后过滤、洗涤后即得到铌酸钾纳米粒子。Disperse 0.86g of niobium pentoxide in 30mL of 1mol·L -1 KOH solution, conduct a hydrothermal reaction at 250°C for 8 hours, cool naturally to room temperature after the reaction, filter and wash to obtain potassium niobate nanoparticles.
实施例2铌酸钾纳米管光催化剂的制备Preparation of Example 2 Potassium Niobate Nanotube Photocatalyst
将铌酸钾纳米粒子粉末分散于稀酸溶液中，持续搅拌3～4天后过滤，水洗至中性，得到酸化的铌酸钾；然后将酸化的铌酸钾颗粒分散于去离子水中，滴加剥落剂四丁基氢氧化铵水溶液至pH为9～10，持续搅拌2～3天，离心分离即得到产物铌酸钾纳米管。Disperse the potassium niobate nanoparticle powder in dilute acid solution, keep stirring for 3 to 4 days, filter, wash with water until neutral, and obtain acidified potassium niobate; then disperse the acidified potassium niobate particles in deionized water, add dropwise The stripping agent tetrabutylammonium hydroxide aqueous solution is adjusted to a pH of 9-10, continuously stirred for 2-3 days, and centrifuged to obtain the product potassium niobate nanotube.
此外，将加入剥落剂持续搅拌后得到的溶液静置分级，然后离心分离可得到分级后的铌酸钾纳米管。用透射电镜观察所得铌酸钾纳米管光催化剂的形貌，如图1所示，a为分级得到的上层铌酸钾纳米管，b为分级得到的下层铌酸钾纳米管。由透射电镜结果可见，上层产物都具有管状形貌，管形完整，管径分布窄，平均为20nm，管长度为800-1000nm，长径比大；下层则由于剥落不充分既存在长且粗的管状结构，又存在片和大块状物质，成管率较上层低。In addition, the solution obtained after adding the exfoliating agent and continuously stirring is statically classified, and then centrifuged to obtain classified potassium niobate nanotubes. The morphology of the obtained potassium niobate nanotube photocatalyst was observed with a transmission electron microscope, as shown in Figure 1, a is the upper layer potassium niobate nanotube obtained by classification, and b is the lower layer potassium niobate nanotube obtained by classification. It can be seen from the results of transmission electron microscopy that the upper layer of the product has a tubular shape, the tube shape is complete, the tube diameter distribution is narrow, the average is 20nm, the tube length is 800-1000nm, and the aspect ratio is large; the lower layer has both long and thick tubes due to insufficient exfoliation. The tubular structure, and there are sheets and large blocks, the tube forming rate is lower than that of the upper layer.
实施例3负载金属/金属氧化物的铌酸钾纳米管光催化剂的制备The preparation of the potassium niobate nanotube photocatalyst of embodiment 3 loaded metal/metal oxide
3.1负载Pt的铌酸钾纳米管光催化剂的制备3.1 Preparation of Pt-loaded potassium niobate nanotube photocatalyst
称量一定量的实施例2中分级得到的上层铌酸钾纳米管，分散于甲醇溶液中，滴加氯铂酸溶液，使氯铂酸所含铂质量与铌酸钾纳米管的质量比为1.5％，通N2半小时，然后在紫外光下照射半小时，干燥，即得到负载Pt的铌酸钾纳米管。Weigh a certain amount of the upper layer potassium niobate nanotube obtained by grading in embodiment 2, be dispersed in methanol solution, add dropwise chloroplatinic acid solution, make the mass ratio of platinum mass contained in chloroplatinic acid and potassium niobate nanotube be 1.5%, pass N2 for half an hour, then irradiate under ultraviolet light for half an hour, and dry to obtain Pt-loaded potassium niobate nanotubes.
3.2～3.7重复实施例3.1中的制备过程，不同点在于：采用氯化铜、氯金酸、氯钯酸代替氯铂酸，得到负载金属铜、金、钯的催化剂；采用硝酸铜、硝酸镍、氢氧化铜代替氯铂酸，通过金属硝酸盐或氢氧化物热分解法得到负载金属氧化物氧化铜、氧化镍的催化剂；金属或金属氧化物与铌酸钾纳米管的质量比为0.01％-50％。具体的，如表1所示。3.2～3.7 Repeat the preparation process in embodiment 3.1, difference is: adopt cupric chloride, chloroauric acid, chloropalladium acid to replace chloroplatinic acid, obtain the catalyst of supporting metal copper, gold, palladium; Adopt copper nitrate, nickel nitrate 1. Copper hydroxide replaces chloroplatinic acid, and a metal oxide catalyst supporting metal oxide copper oxide and nickel oxide is obtained by thermal decomposition of metal nitrate or hydroxide; the mass ratio of metal or metal oxide to potassium niobate nanotube is 0.01% -50%. Specifically, as shown in Table 1.
表1实施例3.2～3.7的实验条件The experimental conditions of table 1 embodiment 3.2～3.7
3.11～3.13重复实施例3.1中的制备过程，不同点仅在于：铂质量与铌酸钾纳米管的质量比为0.5-2％，具体的，如表2所示。3.11-3.13 Repeat the preparation process in Example 3.1, the only difference is that the mass ratio of platinum to potassium niobate nanotubes is 0.5-2%, specifically, as shown in Table 2.
表2实施例3.11～3.13的实验条件The experimental conditions of table 2 embodiment 3.11～3.13
实施例3.2～3.13的实验结果表明，采用实施例3.2～3.13的实验条件，经分级后上层均可得到管状形貌完整，平均管径为20～90nm，管径分布窄，长径比大，管长度为500nm～4μm，比表面积大的铌酸钾纳米管/负载金属或金属氧化物的铌酸钾纳米管。The experimental results of Examples 3.2 to 3.13 show that, using the experimental conditions of Examples 3.2 to 3.13, the upper layer can have a complete tubular shape after classification, with an average diameter of 20 to 90 nm, a narrow distribution of pipe diameters, and a large aspect ratio. Potassium niobate nanotubes with a tube length of 500 nm to 4 μm and a large specific surface area/potassium niobate nanotubes loaded with metal or metal oxide.
实施例4负载染料的铌酸钾纳米管光催化剂的制备The preparation of the potassium niobate nanotube photocatalyst of embodiment 4 loading dyes
将铌酸钾纳米管分散于曙红的乙醇溶液中，搅拌6小时，离心、干燥，即得到染料曙红负载的铌酸钾纳米管。Potassium niobate nanotubes are dispersed in eosin ethanol solution, stirred for 6 hours, centrifuged and dried to obtain potassium niobate nanotubes loaded with dye eosin.
采用卟啉、酞菁或芘代替曙红，重复上述制备过程，即得到不同染料负载的铌酸钾纳米管。Using porphyrin, phthalocyanine or pyrene instead of eosin, and repeating the above preparation process, potassium niobate nanotubes loaded with different dyes can be obtained.
实施例5光催化剂在降解对硝基苯酚，罗丹明B，甲基橙中的应用Example 5 Application of photocatalyst in degrading p-nitrophenol, rhodamine B, methyl orange
以石英容器作为紫外光下降解的反应容器，高压汞灯和碘钨灯分别作为紫外和可见光的光源，附以磁力搅拌***。A quartz container is used as a reaction vessel for degradation under ultraviolet light, a high-pressure mercury lamp and an iodine-tungsten lamp are used as light sources of ultraviolet and visible light respectively, and a magnetic stirring system is attached.
测试时，将60mg催化剂和60mL 15mg·L-1的待降解溶液加入到反应容器中，避光磁力搅拌半小时以达到吸附-脱附平衡。开启300W的高压汞灯或1000W碘钨灯照射下反应，每隔10分钟取样，经高速离心机离心分离，取上清液于紫外-可见分光光度计上测试其在313nm处的吸光度，采用如下公式计算：During the test, 60 mg of catalyst and 60 mL of 15 mg·L -1 solution to be degraded were added to the reaction vessel, and magnetically stirred for half an hour in the dark to achieve adsorption-desorption equilibrium. Turn on a 300W high-pressure mercury lamp or a 1000W iodine-tungsten lamp to react, take samples every 10 minutes, and centrifuge them in a high-speed centrifuge. Take the supernatant and test its absorbance at 313nm on a UV-visible spectrophotometer. The following method is used: Formula calculation:
其中，η为降解效率，A0为暗吸附之后对硝基苯酚溶液在最大吸收313nm处的吸光度，A为光催化降解后对硝基苯酚溶液在313nm处的吸光度。Wherein, η is the degradation efficiency, A 0 is the absorbance of the p-nitrophenol solution at the maximum absorption 313nm after the dark adsorption, and A is the absorbance of the p-nitrophenol solution at 313nm after the photocatalytic degradation.
光照1h后的降解结果如表3所示。The degradation results after 1 h of light are shown in Table 3.
结果表明：在可见光条件下曙红敏化的铌酸钾纳米管对甲基橙、罗丹明B、对硝基苯酚等有明显的降解效果；在可见光条件下CuO负载的铌酸钾纳米管对对硝基苯酚有明显的降解效果。The results show that under visible light conditions, eosin-sensitized potassium niobate nanotubes have obvious degradation effects on methyl orange, rhodamine B, p-nitrophenol, etc.; under visible light conditions, CuO-loaded potassium niobate nanotubes p-Nitrophenol has obvious degradation effect.
表3光催化剂在降解对硝基苯酚，罗丹明B，甲基橙中的应用效果Table 3 Photocatalysts in the degradation of p-nitrophenol, rhodamine B, the application effect of methyl orange
实施例6光催化剂在催化还原水制氢中的应用Example 6 Application of Photocatalyst in Hydrogen Production by Catalytic Reduction of Water
以石英容器作为主反应器，300W的高压汞灯、1000W碘钨灯分别作为紫外和可见光的光源，附以磁力搅拌及冷凝***。A quartz vessel is used as the main reactor, a 300W high-pressure mercury lamp and a 1000W iodine-tungsten lamp are used as light sources for ultraviolet and visible light respectively, and a magnetic stirring and condensation system is attached.
测试时，将40mg催化剂和50mL牺牲剂溶液加入到石英反应器中，磁力搅拌，通氮气40min以除去溶液中的溶解氧，在300W的高压汞灯照射下反应一定的时间。光照一定时间后，用GC112A(上海精密科学仪器有限公司)气相色谱测试产生氢气的百分含量并计算产氢的速率。During the test, 40mg of catalyst and 50mL of sacrificial agent solution were added to the quartz reactor, magnetically stirred, and nitrogen gas was passed for 40 minutes to remove dissolved oxygen in the solution, and reacted for a certain period of time under the irradiation of a 300W high-pressure mercury lamp. After irradiating for a certain period of time, use GC112A (Shanghai Precision Scientific Instrument Co., Ltd.) gas chromatograph to test the percentage of hydrogen produced and calculate the rate of hydrogen production.
图2为以1mol·L-1三乙醇胺溶液作为牺牲剂，40mg光催化剂，具体的，光催化剂分别为铌酸钾纳米粒子，上、下层铌酸钾纳米管及1.5％Pt负载的上层铌酸钾纳米管在紫外光光照2h条件下催化还原水制氢的性能。由图中结果可知，上、下层铌酸钾纳米管在紫外光催化还原水制氢性能上差异明显，其中上层铌酸钾纳米管的产氢速率(82.04μmol·g-1·h-1)是下层(36.64μmol·g-1·h-1)的2.2倍，是铌酸钾纳米粒子(22.38μmol·g-1·h-1)的3.5倍多。该催化剂稳定性高，循环使用产氢效率没有任何降低。对上层的铌酸钾纳米管进一步负载Pt后，紫外光催化还原水制氢的性能有了明显的提高，其中1.5％Pt负载的铌酸钾纳米管的产氢速率(2296.875μmol·g-1·h-1)是负载前的28.1倍，是铌酸钾纳米粒子的102.6倍。Figure 2 shows the use of 1mol L -1 triethanolamine solution as a sacrificial agent, 40 mg of photocatalyst, specifically, the photocatalysts are potassium niobate nanoparticles, upper and lower layers of potassium niobate nanotubes and upper layer of niobate loaded with 1.5% Pt Catalytic reduction of water to hydrogen production by potassium nanotubes under the condition of ultraviolet light for 2 h. From the results in the figure, it can be seen that the hydrogen production performance of the upper and lower potassium niobate nanotubes is significantly different in the ultraviolet photocatalytic reduction of water, and the hydrogen production rate of the upper potassium niobate nanotubes (82.04μmol·g -1 ·h -1 ) It is 2.2 times that of the lower layer (36.64 μmol·g -1 ·h -1 ), and more than 3.5 times that of potassium niobate nanoparticles (22.38 μmol·g -1 ·h -1 ). The catalyst has high stability, and the efficiency of hydrogen production is not reduced in recycling. After the potassium niobate nanotubes on the upper layer were further loaded with Pt, the hydrogen production performance of the ultraviolet photocatalytic reduction of water was significantly improved, and the hydrogen production rate of the potassium niobate nanotubes loaded with 1.5% Pt (2296.875 μmol·g -1 · h -1 ) is 28.1 times that before loading, and 102.6 times that of potassium niobate nanoparticles.
表4Pt负载量不同的铌酸钾纳米管光催化剂的产氢速率Table 4 Hydrogen production rate of potassium niobate nanotube photocatalysts with different loadings of Pt
以1mol·L-1三乙醇胺溶液作为牺牲剂，其他实验条件相同，得到Pt负载量不同的铌酸钾纳米管产氢速率的结果，如表4所示。Using 1 mol L -1 triethanolamine solution as the sacrificial agent, the other experimental conditions were the same, and the results of hydrogen production rate of potassium niobate nanotubes with different Pt loading were obtained, as shown in Table 4.
可知，负载后铌酸钾纳米管光催化剂较纯铌酸钾纳米管在紫外光下的催化活性提高12.6-28.1倍，是商品级P25TiO2光催化剂(产氢速率为0.245mmol·g-1·h-1)的4.2-9.5倍。It can be seen that the catalytic activity of the loaded potassium niobate nanotube photocatalyst is 12.6-28.1 times higher than that of the pure potassium niobate nanotube under ultraviolet light, which is the commercial grade P25TiO 2 photocatalyst (the hydrogen production rate is 0.245mmol·g -1 · 4.2-9.5 times of h -1 ).
以10％甲醇溶液作为牺牲剂，其他实验条件相同，得到的产氢速率的结果如表5所示。文献Journal of Solid State Chemistry 181(2008)：1678-1683报导了以20％甲醇作为牺牲剂时，铌酸钾颗粒的产氢速率为339.33μmol·g-1·h-1，铌酸钾纳米管的产氢速率为246μmol·g-1·h-1。可知本申请制备的上层铌酸钾纳米管、0.5％Pt负载的铌酸钾纳米管的产氢速率显著提高。Using 10% methanol solution as the sacrificial agent, the other experimental conditions are the same, and the results of the hydrogen production rate are shown in Table 5. The literature Journal of Solid State Chemistry 181(2008): 1678-1683 reported that when 20% methanol was used as a sacrificial agent, the hydrogen production rate of potassium niobate particles was 339.33μmol·g -1 ·h -1 , and potassium niobate nanotubes The hydrogen production rate is 246μmol·g -1 ·h -1 . It can be seen that the hydrogen production rate of the upper-layer potassium niobate nanotubes and 0.5% Pt-loaded potassium niobate nanotubes prepared by the present application is significantly improved.
表5铌酸钾纳米管光催化剂的产氢速率Table 5 The hydrogen production rate of potassium niobate nanotube photocatalyst
此外，采用负载后铌酸钾纳米管光催化剂或纯铌酸钾纳米管以乙醇、维生素C、罗丹明B等水溶液作为牺牲剂制氢获得氢气的速率为：0.2-5mmol·g-1·h-1。In addition, the rate of hydrogen production by using loaded potassium niobate nanotube photocatalysts or pure potassium niobate nanotubes with ethanol, vitamin C, rhodamine B and other aqueous solutions as sacrificial agents to obtain hydrogen is: 0.2-5mmol·g -1 ·h -1 .
本发明的铌酸钾纳米管光催化剂的制备方法，可在室温条件下，水溶液中，在较短的酸化时间和剥落时间内制备得到铌酸钾纳米管，制备条件温和、周期短、绿色环保，得到的光催化剂比表面积大，活性位点多，性能稳定，金属、氧化物或染料的负载量高，金属或氧化物的负载量为0.1％-50％，不仅能被紫外光激发，还能被可见光激发，提高了铌酸钾纳米管对可见光的响应和光催化还原水制氢和光催化降解的性能，铌酸钾纳米管在紫外光下的光催化还原水制氢的性能是铌酸钾纳米粒子的4-6倍，负载后铌酸钾纳米管光催化剂较纯铌酸钾纳米管在紫外光下的催化活性提高20-30倍，是商品级P25TiO2光催化剂的10-15倍。The preparation method of the potassium niobate nanotube photocatalyst of the present invention can prepare potassium niobate nanotubes in an aqueous solution at room temperature within a short acidification time and exfoliation time, and the preparation conditions are mild, the cycle is short, and the environment is green , the obtained photocatalyst has a large specific surface area, many active sites, stable performance, high loading of metals, oxides or dyes, and the loading of metals or oxides is 0.1%-50%, which can not only be excited by ultraviolet light, but also It can be excited by visible light, which improves the response of potassium niobate nanotubes to visible light and the performance of photocatalytic reduction of water to hydrogen production and photocatalytic degradation. 4-6 times that of nanoparticles, and the catalytic activity of the loaded potassium niobate nanotube photocatalyst is 20-30 times higher than that of pure potassium niobate nanotube under ultraviolet light, which is 10-15 times that of commercial grade P25TiO 2 photocatalyst.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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Non-Patent Citations (5)
| Title |
|---|
| Gaohui Du et al.Synthesis, modification and characterization of K4Nb6O17-type nanotubes.《Journal of Materials Chemistry》.2004,第14卷1437-1442. * |
| GaohuiDuetal.Synthesis modification and characterization of K4Nb6O17-type nanotubes.《Journal of Materials Chemistry》.2004 |
| Geoffrey B. Saupe et al.Nanoscale Tubules Formed by Exfoliation of Potassium Hexaniobate.《Chem. Mater.》.2000,第12卷(第6期),1556-1562. * |
| JP特开2003-126695A 2003.05.07 |
| 杨亚辉等.Ni、Co、Mn、Cu掺杂对K4Nb6O17光催化活性的影响.《材料导报》.2005,第19卷(第05期),117-119，124. * |
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