CN110128673B - Cerium-based metal organic framework for Cr(VI) detection, preparation method and application - Google Patents
Cerium-based metal organic framework for Cr(VI) detection, preparation method and application Download PDFInfo
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- CN110128673B CN110128673B CN201910467145.5A CN201910467145A CN110128673B CN 110128673 B CN110128673 B CN 110128673B CN 201910467145 A CN201910467145 A CN 201910467145A CN 110128673 B CN110128673 B CN 110128673B
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 117
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 57
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000001514 detection method Methods 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 230000000694 effects Effects 0.000 claims abstract description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 21
- 239000002073 nanorod Substances 0.000 claims abstract description 21
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 20
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
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- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims abstract description 8
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- FRHSFOIZFYYLRC-UHFFFAOYSA-N formic acid terephthalic acid Chemical compound OC=O.OC(=O)c1ccc(cc1)C(O)=O FRHSFOIZFYYLRC-UHFFFAOYSA-N 0.000 claims 1
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- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 4
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
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- YRNWIFYIFSBPAU-UHFFFAOYSA-N 4-[4-(dimethylamino)phenyl]-n,n-dimethylaniline Chemical compound C1=CC(N(C)C)=CC=C1C1=CC=C(N(C)C)C=C1 YRNWIFYIFSBPAU-UHFFFAOYSA-N 0.000 description 1
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- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
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- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
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- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
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Abstract
本发明涉及光学传感技术领域，具体公开了一种用于Cr(VI)检测的铈基金属有机框架、制备方法及应用。该铈基金属有机框架，是以具有模拟酶活性的二氧化铈纳米棒为模板，提供铈离子作为离子中心，加入对苯二甲酸，成核生长为铈基金属有机框架。所述的二氧化铈纳米棒，由六水合硝酸亚铈和氢氧化钠混合反应，经离心、洗涤、真空干燥而得到,该铈基金属有机框架应用于检测Cr(VI)。本发明首次应用牺牲模板法合成了铈基金属有机框架，具有比CeO2纳米材料更强的氧化酶活性及选择性，实现了对Cr(VI)的灵敏检测，具有灵敏度高、选择性好、简单和快速的优点，有良好的应用前景。
The invention relates to the technical field of optical sensing, and specifically discloses a cerium-based metal organic framework for Cr(VI) detection, a preparation method and an application. The cerium-based metal-organic framework uses a ceria nanorod with simulated enzyme activity as a template, provides cerium ions as an ion center, adds terephthalic acid, and nucleates and grows into a cerium-based metal-organic framework. The cerium dioxide nanorods are obtained by mixing reaction of hexahydrate cerium nitrate and sodium hydroxide, through centrifugation, washing and vacuum drying, and the cerium-based metal organic framework is used for detecting Cr(VI). The present invention uses the sacrificial template method to synthesize the cerium-based metal organic framework for the first time, which has stronger oxidase activity and selectivity than CeO 2 nanomaterials, realizes the sensitive detection of Cr(VI), and has the advantages of high sensitivity, good selectivity, The advantages of simplicity and speed have good application prospects.
Description
技术领域technical field
本发明属于光学传感技术领域，具体涉及一种用于Cr(VI)检测的铈基金属有机框架、制备方法及应用。The invention belongs to the technical field of optical sensing, and in particular relates to a cerium-based metal organic framework for Cr(VI) detection, a preparation method and an application.
背景技术Background technique
铬是地壳中含量排行第21的元素，存在于环境中的主要是两种氧化态Cr(III)和Cr(VI)。金属电镀和加工、皮革鞣制、工业冷却水的防腐和木材防腐处理等均可导致环境中铬浓度升高。Cr的两种氧化态具有明显不同的化学性质和人体毒性。Cr(III)是人体需要的微量元素，毒性较小，它可形成三价阳离子(或水解产物)，与矿物表面强烈结合并形成溶解度有限的金属氢氧化物。而Cr(VI)通常作为铬酸盐氧阴离子，是已知的人呼吸道致癌物质，除了致癌作用外，还发现一些含有Cr(VI)的化合物是强大的上皮刺激物和神经组织降解因子，同时它也倾向于在环境中移动，从而危及水质。世界卫生组织在《饮用水水质准则(第四版)》中明确规定水中总铬的最大污染水平为50μg/L。因此，对Cr(VI)的监测、准确鉴定和定量检测至关重要。到目前为止，除了传统的分析方法如质谱、电化学、色谱和荧光光谱法外，在水环境中直接检测Cr(VI)的方法很少。而且这些方法通常需要较长时间和复杂的操作，不适合快速有效地测定Cr(VI)。近年来，基于纳米酶材料的新兴色度策略由于检测稳定和抵抗复杂介质干扰的能力，在水污染物检测中具有广泛的应用。Chromium is the 21st most abundant element in the earth's crust, and exists in the environment mainly in two oxidation states, Cr(III) and Cr(VI). Metal plating and processing, leather tanning, preservative treatment of industrial cooling water, and wood preservative treatments can all contribute to elevated chromium concentrations in the environment. The two oxidation states of Cr have markedly different chemical properties and human toxicity. Cr(III) is a trace element needed by the human body, and it is less toxic. It can form trivalent cations (or hydrolysis products), which are strongly bound to the mineral surface and form metal hydroxides with limited solubility. While Cr(VI), usually as chromate oxyanion, is a known carcinogen of human respiratory tract, in addition to carcinogenic effects, some compounds containing Cr(VI) have also been found to be powerful epithelial stimulators and neural tissue degrading factors. It also tends to move through the environment, compromising water quality. The World Health Organization clearly stipulates that the maximum pollution level of total chromium in water is 50μg/L in the Guidelines for Drinking Water Quality (Fourth Edition). Therefore, the monitoring, accurate identification and quantitative detection of Cr(VI) are crucial. So far, there are few methods for the direct detection of Cr(VI) in aqueous environments, except for traditional analytical methods such as mass spectrometry, electrochemistry, chromatography, and fluorescence spectroscopy. Moreover, these methods usually require a long time and complicated operations, which are not suitable for fast and efficient determination of Cr(VI). In recent years, emerging colorimetric strategies based on nanoenzyme materials have been widely used in the detection of water pollutants due to the detection stability and the ability to resist interference from complex media.
氧化铈纳米材料具有高氧空位、缺陷和存在双氧化态等优异的理化性质，可有效吸附去除Cr(VI)(Mishra,P.K.；Kumar,R.；Rai,P.K.Surfactant-free one-pot synthesisof CeO2,TiO2 and Ti@Ce oxide nanoparticles for the ultrafast removal of Cr(VI)from aqueous media.Nanoscale,2018,10(15),7257-7269)。此外，氧化铈纳米材料在酸性介质中的低溶解度以及低毒性，使得其比用于水修复的其他金属氧化物更具吸引力。纳米酶作为新兴的纳米材料之一，具有比天然酶具有更高的稳定性和更低的成本，在生物传感器和纳米医学中得到广泛运用。氧化铈存在两种氧化价态及大量氧空穴而具有优异的纳米酶活性(Cao,F.；Zhang,Y.；Sun,Y.；Wang,Z.；Zhang,L.；Huang,Y.；Liu C.；Liu,Z.；Ren,J.；Qu,X.Ultrasmall nanozymes isolated within porous carbonaceous frameworks forsynergistic cancer therapy:enhanced oxidative damage and reduced energysupply.Chemistry of Materials,2018,30(21),7831-7839)。Cerium oxide nanomaterials have excellent physicochemical properties such as high oxygen vacancies, defects and the existence of double oxidation states, which can effectively adsorb and remove Cr(VI) (Mishra, PK; Kumar, R.; Rai, PKSurfactant-free one-pot synthesis of CeO 2 , TiO 2 and Ti@Ce oxide nanoparticles for the ultrafast removal of Cr(VI) from aqueous media. Nanoscale, 2018, 10(15), 7257-7269). In addition, the low solubility and low toxicity of ceria nanomaterials in acidic media make them more attractive than other metal oxides for water remediation. As one of the emerging nanomaterials, nanozymes have higher stability and lower cost than natural enzymes, and are widely used in biosensors and nanomedicine. Cerium oxide has two oxidation states and a large number of oxygen vacancies and has excellent nanozyme activity (Cao, F.; Zhang, Y.; Sun, Y.; Wang, Z.; Zhang, L.; Huang, Y. ; Liu C.; Liu, Z.; Ren, J.; Qu, X. Ultrasmall nanozymes isolated within porous carbonaceous frameworks forsynergistic cancer therapy: enhanced oxidative damage and reduced energysupply. Chemistry of Materials, 2018, 30(21), 7831- 7839).
金属有机框架(MOF)材料是当前的研究热点，基于MOF用于装载功能性材料，开发新类型的平台受到关注。与MOF相比，MOF与其他功能材料相结合的异质结构由于协同效应而显示出巨大的优势。牺牲模板法最早由Kitagawa课题组在2012年提出Pseudomorphicmineral replacement(即不平衡的矿物相转变为热力学上更稳定的相，涉及溶解与再沉淀，溶解动力学与新相的成核和结晶动力学相结合保留了被取代的母相的形状和尺寸)这一自然现象构建以氧化铝为模板的多孔配位聚合物，有机物与预先形成的金属氧化物母体相结合，通过Pseudomorphic mineral replacement使多孔配位聚合在分子尺度上形成与母体的保留同时发生(Reboul,J.；Furukawa,S.；Horike,N.；Tsotsalas,M.；Hirai,K.；Uehara,H.；Kondo,M.；Louvain,N.；Sakata,O.；Kitagawa,S.Mesoscopic architecturesof porous coordination polymers fabricated by pseudomorphicreplication.Nature materials,2012,11(8),717)。2017年Lu课题组应用牺牲模板法合成多种以金属氧化物为模板的金属有机框架，并通过改变有机配体浓度调节金属复合的金属纳米粒子在MOFs内的空间分布以提高催化效率(Yang,Q.；Liu,W.；Wang,B.；Zhang,W.；Zeng,X.；Zhang,C.；Qin,Y.；Sun,X.；Wu,T.；Liu,J.；Huo,F.；Lu,J.Regulating thespatial distribution of metal nanoparticles within metal-organic frameworksto enhance catalytic efficiency.Nature communications,2017,8,14429)。在牺牲模板法中，金属氧化物模板可以通过牺牲自身来提供金属离子，然后在没有任何表面改性的情况下引发MOF的生长。Metal-organic framework (MOF) materials are the current research hotspot, and the development of new types of platforms based on MOFs for loading functional materials has attracted attention. Compared with MOFs, the heterostructures of MOFs combined with other functional materials show great advantages due to the synergistic effect. The sacrificial template method was first proposed by Kitagawa's group in 2012. Pseudomorphicmineral replacement (i.e., the transformation of an unbalanced mineral phase into a thermodynamically more stable phase, involving dissolution and reprecipitation, dissolution kinetics and nucleation and crystallization kinetics of new phases) The combination retains the natural phenomenon of the shape and size of the substituted parent phase) to construct porous coordination polymers templated by alumina, organics are combined with pre-formed metal oxide precursors, and the porous coordination polymers are made through Pseudomorphic mineral replacement. Aggregation occurs at the molecular scale simultaneously with retention of the parent (Reboul, J.; Furukawa, S.; Horike, N.; Tsotsalas, M.; Hirai, K.; Uehara, H.; Kondo, M.; Louvain, N.; Sakata, O.; Kitagawa, S. Mesoscopic architectures of porous coordination polymers fabricated by pseudomorphicreplication. Nature materials, 2012, 11(8), 717). In 2017, Lu's group used the sacrificial template method to synthesize a variety of metal-organic frameworks with metal oxides as templates, and adjust the spatial distribution of metal-complexed metal nanoparticles in MOFs by changing the concentration of organic ligands to improve the catalytic efficiency (Yang, 2017). Q.; Liu, W.; Wang, B.; Zhang, W.; Zeng, X.; Zhang, C.; Qin, Y.; Sun, X.; Wu, T.; Liu, J.; Huo, F.; Lu, J. Regulating the spatial distribution of metal nanoparticles within metal-organic frameworks to enhance catalytic efficiency. Nature communications, 2017, 8, 14429). In the sacrificial template method, the metal oxide template can provide metal ions by sacrificing itself, and then trigger the growth of MOFs without any surface modification.
应用牺牲模板法来合成铈基金属有机框架，及将铈基金属有机框架的氧化酶活性与Cr(VI)-TMB新体系相结合，来构建Cr(VI)检测的比色新方法，尚未见到相关报道。Synthesis of cerium-based metal-organic frameworks by sacrificial template method, and combining the oxidase activity of cerium-based metal-organic frameworks with a new Cr(VI)-TMB system to construct a new colorimetric method for Cr(VI) detection, which has not yet been seen to related reports.
发明内容SUMMARY OF THE INVENTION
本发明所要解决的技术问题是：针对现有的Cr(VI)检测方法的缺陷与不足，提供一种用于Cr(VI)检测的铈基金属有机框架、制备方法及应用。本发明首次应用牺牲模板法合成了铈基金属有机框架，具有比CeO2纳米材料更强的氧化酶活性及选择性，实现了对Cr(VI)的灵敏检测，具有灵敏度高、选择性好、简单和快速的优点，有良好的应用前景。The technical problem to be solved by the present invention is to provide a cerium-based metal organic framework, preparation method and application for Cr(VI) detection in view of the defects and deficiencies of the existing Cr(VI) detection methods. The present invention uses the sacrificial template method to synthesize the cerium-based metal organic framework for the first time, which has stronger oxidase activity and selectivity than CeO 2 nanomaterials, realizes the sensitive detection of Cr(VI), and has the advantages of high sensitivity, good selectivity, The advantages of simplicity and speed have good application prospects.
本发明的原理是：The principle of the present invention is:
以具有模拟酶活性的二氧化铈纳米棒(CeO2NRs)为模板提供铈离子作为离子中心，加入对苯二甲酸后引发铈基金属有机框架(CeO2NRs-MOF)的成核生长，还保留了CeO2NRs的形态和特性。基于牺牲模板法形成的CeO2NRs-MOF比CeO2纳米材料具有更强的氧化酶活性和选择性，在无需H2O2存在的情况下，Cr(VI)可代替H2O2并与TMB构成Cr(VI)-TMB新体系，并氧化TMB显色，TMB在650nm处的紫外吸收峰随着Cr(VI)浓度的增加而增大，据此，构建基于铈基金属有机框架的氧化酶活性的简单、灵敏的比色法，用于对环境样品中Cr(VI)的定量分析及吸附研究。Using ceria nanorods (CeO 2 NRs) with simulated enzyme activity as a template to provide cerium ions as ionic centers, the addition of terephthalic acid triggers the nucleation growth of cerium-based metal organic frameworks (CeO 2 NRs-MOFs), and also The morphology and properties of CeO 2 NRs are preserved. CeO 2 NRs-MOFs formed based on sacrificial template method have stronger oxidase activity and selectivity than CeO 2 nanomaterials, and Cr(VI) can replace H 2 O 2 and combine with
本发明采用如下技术方案，来实现发明目的。The present invention adopts the following technical solutions to achieve the purpose of the invention.
首先，本发明提供了一种用于Cr(VI)检测的铈基金属有机框架。First, the present invention provides a cerium-based metal organic framework for Cr(VI) detection.
该铈基金属有机框架以具有模拟酶活性的二氧化铈纳米棒(CeO2NRs)为模板，提供铈离子作为离子中心，加入对苯二甲酸，成核生长为铈基金属有机框架(CeO2NRs-MOF)。The cerium-based metal-organic framework uses ceria nanorods (CeO 2 NRs) with simulated enzyme activity as a template, provides cerium ions as ionic centers, and adds terephthalic acid to nucleate and grow into a cerium-based metal-organic framework (CeO 2 ) . NRs-MOF).
进一步地，所述的二氧化铈纳米棒(CeO2NRs)，由六水合硝酸亚铈和氢氧化钠混合反应，经离心、洗涤、真空干燥而得到。Further, the cerium oxide nanorods (CeO 2 NRs) are obtained by mixing reaction of hexahydrate cerium nitrate and sodium hydroxide, centrifuging, washing and vacuum drying.
进一步地，所述的铈基金属有机框架(CeO2NRs-MOF)，经超纯水稀释分散成悬浊液，浓度为1mg/mL。Further, the cerium-based metal organic framework (CeO 2 NRs-MOF) was diluted with ultrapure water and dispersed into a suspension with a concentration of 1 mg/mL.
其次，本发明提供了一种用于Cr(VI)检测的铈基金属有机框架的制备方法。Secondly, the present invention provides a preparation method of a cerium-based metal organic framework for Cr(VI) detection.
该制备方法包括以下步骤：(1)二氧化铈纳米棒(CeO2NRs)的制备；(2)铈基金属有机框架(CeO2NRs-MOF)的成核生成；(3)超纯水稀释分散：得到浓度为1mg/mL的铈基金属有机框架(CeO2NRs-MOF)悬浊液。The preparation method includes the following steps: (1) preparation of ceria nanorods (CeO 2 NRs); (2) nucleation and generation of cerium-based metal organic frameworks (CeO 2 NRs-MOF); (3) dilution with ultrapure water Dispersion: A cerium-based metal organic framework (CeO 2 NRs-MOF) suspension with a concentration of 1 mg/mL was obtained.
进一步地，步骤(1)所述的氧化铈纳米棒(CeO2NRs)的制备，具体为：以质量份数计，将1份的六水合硝酸亚铈和10-12份的氢氧化钠溶于超纯水中，搅拌混合20-40分钟，95-105℃反应20-30小时，冷却至室温后，将产物依次用超纯水和乙醇离心洗涤2-4次，50-70℃真空干燥12-24小时，制得CeO2纳米棒。Further, the preparation of cerium oxide nanorods (CeO 2 NRs) described in step (1) is specifically: in parts by mass, dissolving 1 part of cerium nitrate hexahydrate and 10-12 parts of sodium hydroxide In ultrapure water, stir and mix for 20-40 minutes, react at 95-105°C for 20-30 hours, cool down to room temperature, wash the product with ultrapure water and ethanol by centrifugation for 2-4 times, and vacuum dry at 50-70°C In 12-24 hours, CeO2 nanorods were produced.
进一步地，步骤(2)所述的铈基金属有机框架(CeO2NRs-MOF)的成核生成，具体为：以质量份数计，将1份的CeO2纳米棒与含对苯二甲酸70-80份的DMF(N，N-二甲基甲酰胺)溶液混合，65-75℃反应10-15小时，冷却至室温后，将产物依次用DMF和乙醇离心洗涤2-4次，50-70℃真空干燥12-24小时，得到铈基金属有机框架。Further, the nucleation and generation of the cerium-based metal-organic framework (CeO 2 NRs-MOF) described in step (2) is specifically: in parts by mass, 1 part of CeO 2 nanorods and terephthalic acid-containing Mix 70-80 parts of DMF (N,N-dimethylformamide) solutions, react at 65-75° C. for 10-15 hours, and after cooling to room temperature, wash the product with DMF and ethanol by centrifugation for 2-4 times in turn, 50 -70 °C vacuum drying for 12-24 hours to obtain a cerium-based metal organic framework.
最后，本发明提供了一种铈基金属有机框架的应用。Finally, the present invention provides the application of a cerium-based metal organic framework.
该铈基金属有机框架应用于检测Cr(VI)。The Ce-based metal-organic framework was applied to detect Cr(VI).
所述的检测Cr(VI)，具体为：以体积份数计，将铈基金属有机框架(CeO2NRs-MOF)的悬浊液1份、TMB(3,3',5,5'-四甲基联苯胺)溶液0.1份、在0-5μM范围内不同浓度的Cr(VI)溶液与HEPES(4-羟乙基哌嗪乙磺酸)缓冲溶液0.5份混合，加超纯水稀释至溶液总体积5份，进行混合反应，立即采用紫外可见分光光度计测定混合反应溶液在330nm-800nm波长范围内的吸收光谱，根据TMB紫外吸收光谱强度与Cr(VI)浓度之间的线性关系，实现对Cr(VI)的灵敏检测。The detection of Cr(VI) is specifically: in parts by volume, 1 part of the suspension of cerium-based metal organic framework (CeO 2 NRs-MOF), TMB (3,3',5,5'- 0.1 part of tetramethylbenzidine) solution, Cr(VI) solution with different concentrations in the range of 0-5μM and 0.5 part of HEPES (4-hydroxyethylpiperazineethanesulfonic acid) buffer solution were mixed, and diluted with ultrapure water to The total volume of the solution was 5 parts, and the mixed reaction was carried out. Immediately, the absorption spectrum of the mixed reaction solution in the wavelength range of 330nm-800nm was measured by a UV-visible spectrophotometer. According to the linear relationship between the intensity of the UV absorption spectrum of TMB and the concentration of Cr(VI), Sensitive detection of Cr(VI) is achieved.
进一步地，所述的铈基金属有机框架悬浊液，浓度为1mg/mL；所述的TMB溶液，浓度为20mM。Further, the concentration of the cerium-based metal organic framework suspension is 1 mg/mL; the concentration of the TMB solution is 20 mM.
进一步地，所述的HEPES缓冲溶液，pH为4，浓度为100mM。Further, the pH of the HEPES buffer solution is 4 and the concentration is 100 mM.
有益效果：Beneficial effects:
(1)本发明应用牺牲模板法合成的铈基金属有机框架，具有比CeO2纳米材料更强的氧化酶活性。(1) The cerium-based metal organic framework synthesized by the sacrificial template method in the present invention has stronger oxidase activity than CeO 2 nanomaterials.
(2)本发明合成的铈基金属有机框架可氧化TMB显蓝色，同时还可选择性吸附高毒性Cr(VI)并还原为Cr(III)，在无需H2O2存在的情况下，Cr(VI)可代替H2O2和TMB构成氧化还原循环新体系。( 2 ) The cerium - based metal-organic framework synthesized by the present invention can oxidize TMB to show blue color, and at the same time, it can selectively adsorb highly toxic Cr(VI) and reduce it to Cr(III). Cr(VI) can replace H 2 O 2 and TMB to form a new redox cycle system.
(3)本发明将铈基金属有机框架的氧化酶活性与Cr(VI)-TMB新体系相结合，构建了检测Cr(VI)的比色新方法，实现了对环境水体中Cr(VI)的检测，具有灵敏度高、选择性好、简单和快速的优点，有良好的应用前景。(3) The present invention combines the oxidase activity of the cerium-based metal organic framework with the new Cr(VI)-TMB system to construct a new colorimetric method for detecting Cr(VI), and realizes the detection of Cr(VI) in environmental water. It has the advantages of high sensitivity, good selectivity, simplicity and rapidity, and has good application prospects.
附图说明Description of drawings
图1：铈基金属有机框架的TEM图。其中A为CeO2NRs的TEM图、B为CeO2NRs-MOF的TEM图；Figure 1: TEM image of a cerium-based metal-organic framework. where A is the TEM image of CeO 2 NRs, and B is the TEM image of CeO 2 NRs-MOF;
图2：CeO2NRs和CeO2NRs-MOF对Cr(VI)响应的紫外-可见吸收光谱图。Figure 2: UV-Vis absorption spectra of CeO 2 NRs and CeO 2 NRs-MOFs in response to Cr(VI).
图3：基于CeO2NRs-MOF的氧化酶活性检测Cr(VI)的原理示意图。Figure 3: Schematic diagram of the principle of detection of Cr(VI) based on the oxidase activity of CeO 2 NRs-MOF.
图4：比色法检测Cr(VI)的UV-Vis光谱图。Figure 4: UV-Vis spectrum of Cr(VI) detected by colorimetry.
图5A：比色法对不同浓度Cr(VI)响应的紫外-可见吸收光谱图；Figure 5A: UV-Vis absorption spectra of colorimetric response to different concentrations of Cr(VI);
图5B：Cr(VI)的浓度与TMB特征吸收峰强度之间的校准曲线。Figure 5B: Calibration curve between the concentration of Cr(VI) and the intensity of the characteristic absorption peak of TMB.
图6：比色法对Cr(VI)检测的选择性图。Figure 6: Selectivity plot for Cr(VI) detection by colorimetry.
具体实施方式Detailed ways
下面结合具体实施例对本发明作进一步的说明，但本发明并不限于以下实施例。所述方法如无特别说明均为常规方法。所述原材料如无特别说明均能从公开商业途径获得。The present invention will be further described below in conjunction with specific embodiments, but the present invention is not limited to the following embodiments. The methods are conventional methods unless otherwise specified. The raw materials can be obtained from open commercial sources unless otherwise specified.
实施例1：铈基金属有机框架的制备Example 1: Preparation of Cerium-Based Metal Organic Frameworks
将0.434g六水合硝酸亚铈和4.8g氢氧化钠溶于20mL超纯水中，搅拌混合30分钟，将混合溶液置于高压反应釜中于100℃反应24小时，冷却至室温后，将产物依次用超纯水和乙醇离心洗涤三次，再置于真空干燥箱中60℃过夜，制得CeO2纳米棒；将20mg CeO2纳米棒与含1.4952g对苯二甲酸的30mL DMF溶液混合，置于高压反应釜中于70℃反应12小时，冷却至室温后，将产物依次用DMF和乙醇离心洗涤三次，再置于60℃真空干燥箱中过夜，得到铈基金属有机框架(CeO2NRs-MOF)。Dissolve 0.434g of cerium nitrate hexahydrate and 4.8g of sodium hydroxide in 20mL of ultrapure water, stir and mix for 30 minutes, place the mixed solution in an autoclave at 100°C for 24 hours, and cool down to room temperature. Centrifugal washing with ultrapure water and ethanol three times in turn, and then placed in a vacuum drying oven at 60 °C overnight to obtain CeO2 nanorods; 20 mg CeO2 nanorods were mixed with 30 mL of DMF solution containing 1.4952 g of terephthalic acid, and set aside. The reaction was carried out at 70°C for 12 hours in an autoclave, and after cooling to room temperature, the product was centrifuged and washed three times with DMF and ethanol in turn, and then placed in a vacuum drying oven at 60°C overnight to obtain a cerium-based metal organic framework (CeO 2 NRs- MOF).
实施例2：铈基金属有机框架的制备Example 2: Preparation of Cerium-Based Metal Organic Frameworks
将0.434g六水合硝酸亚铈和4.34g氢氧化钠溶于20mL超纯水中，搅拌混合20分钟，将混合溶液置于高压反应釜中于95℃反应20小时，冷却至室温后，将产物依次用超纯水和乙醇离心洗涤二次，再置于50℃的真空干燥箱中12小时，制得CeO2纳米棒；将20mg CeO2纳米棒与含1.4g对苯二甲酸的30mL DMF溶液混合，置于高压反应釜中于65℃反应10小时，冷却至室温后，将产物依次用DMF和乙醇离心洗涤二次，再置于60℃真空干燥箱中12小时，得到铈基金属有机框架(CeO2NRs-MOF)。Dissolve 0.434g of cerous nitrate hexahydrate and 4.34g of sodium hydroxide in 20mL of ultrapure water, stir and mix for 20 minutes, place the mixed solution in an autoclave at 95°C for 20 hours, and cool down to room temperature. Centrifuge and wash twice with ultrapure water and ethanol in turn, and then place it in a vacuum drying box at 50 °C for 12 hours to prepare CeO2 nanorods; 20 mg CeO2 nanorods were mixed with 30 mL DMF solution containing 1.4 g terephthalic acid Mixed, placed in an autoclave at 65 °C for 10 hours, cooled to room temperature, the product was washed twice with DMF and ethanol centrifugation in turn, and then placed in a 60 °C vacuum drying oven for 12 hours to obtain a cerium-based metal organic framework (CeO 2 NRs-MOF).
实施例3：铈基金属有机框架的制备Example 3: Preparation of Cerium-Based Metal Organic Frameworks
将0.434g六水合硝酸亚铈和5.208g氢氧化钠溶于20mL超纯水中，搅拌混合40分钟，将混合溶液置于高压反应釜中于105℃反应30小时，冷却至室温后，将产物依次用超纯水和乙醇离心洗涤四次，再置于70℃真空干燥箱中24小时，制得CeO2纳米棒；将20mg CeO2纳米棒与含1.6g对苯二甲酸的30mL DMF溶液混合，置于高压反应釜中于75℃反应15小时，冷却至室温后，将产物依次用DMF和乙醇离心洗涤四次，再置于70℃真空干燥箱中24小时，得到铈基金属有机框架(CeO2NRs-MOF)。Dissolve 0.434g of cerium nitrate hexahydrate and 5.208g of sodium hydroxide in 20mL of ultrapure water, stir and mix for 40 minutes, place the mixed solution in an autoclave at 105°C for 30 hours, and cool down to room temperature. Centrifugal washing with ultrapure water and ethanol for four times in turn, and then placed in a vacuum drying oven at 70 °C for 24 hours to obtain CeO2 nanorods; 20 mg CeO2 nanorods were mixed with 30 mL of DMF solution containing 1.6 g of terephthalic acid. , placed in the autoclave and reacted at 75 ° C for 15 hours, after cooling to room temperature, the product was sequentially washed four times with DMF and ethanol centrifugation, and then placed in a 70 ° C vacuum drying oven for 24 hours to obtain a cerium-based metal organic framework ( CeO 2 NRs-MOF).
实施例4：铈基金属有机框架的表征Example 4: Characterization of Cerium-Based Metal Organic Frameworks
利用透射电子显微镜(TEM)对实施例1所得到的CeO2NRs-MOF的形貌进行表征，结果如图1所示。其中A为CeO2NRs的TEM图、B为CeO2NRs-MOF的TEM图。由CeO2NRs和CeO2NRs-MOF的TEM图可见，CeO2NRs和CeO2NRs-MOF均呈棒状结构，CeO2NRs的宽度约5-10nm、长度约120nm，CeO2NRs-MOF在CeO2NRs的外围包裹了一层厚度约2-5nm薄层。The morphology of the CeO 2 NRs-MOF obtained in Example 1 was characterized by transmission electron microscopy (TEM), and the results are shown in FIG. 1 . A is the TEM image of CeO 2 NRs, and B is the TEM image of CeO 2 NRs-MOF. From the TEM images of CeO 2 NRs and CeO 2 NRs-MOF, it can be seen that both CeO 2 NRs and CeO 2 NRs-MOF have rod - like structures. The width of CeO 2 NRs is about 5-10 nm and the length is about 120 nm. The periphery of the 2 NRs is wrapped with a thin layer about 2-5 nm thick.
利用X射线光电子能谱(XPS)对CeO2NRs-MOF的元素及价态组成进行表征。CeO2NRs和CeO2NRs-MOF的O 1s的XPS图谱表明，CeO2NRs在528.7eV和530.4eV处分别出现了Ce(III)-O和Ce(IV)-O的特征峰，CeO2NRs-MOF在528.9eV和530.7eV处的特征峰分别对应于Ce(III)-O和Ce(IV)-O，表明CeO2NRs和CeO2NRs-MOF均具有三价与四价铈的混合价态，使得二者均具备氧化酶活性；进一步对XPS进行分峰积分计算，Ce(III)-O/Ce(IV)-O比值为0.3874，比CeO2NRs的0.2641高，表明CeO2NRs-MOF中三价铈的含量比CeO2NRs多，表明CeO2NRs-MOF具有比CeO2NRs更强的氧化酶活性，这与文献中报道的氧化铈纳米酶活性随三价铈含量增加而增强相符合(Heckert,E.G.；Karakoti,A.S.；Seal,S.；Self,W.T.The role of ceriumredox state in the SOD mimetic activity of nanoceria.Biomaterials,2008,29(18),2705-2709)，表明本发明成功制备了具有强氧化酶活性的CeO2NRs-MOF。The elemental and valence compositions of CeO 2 NRs-MOF were characterized by X-ray photoelectron spectroscopy (XPS). The XPS spectra of O 1s of CeO 2 NRs and CeO 2 NRs-MOFs show that CeO 2 NRs have characteristic peaks of Ce(III)-O and Ce(IV)-O at 528.7 eV and 530.4 eV, respectively, CeO 2 NRs The characteristic peaks of -MOF at 528.9 eV and 530.7 eV correspond to Ce(III)-O and Ce(IV)-O, respectively, indicating that both CeO 2 NRs and CeO 2 NRs-MOF have mixed valences of trivalent and tetravalent cerium , so that both have oxidase activity; the XPS was further calculated by sub-peak integration, the Ce(III)-O/Ce(IV)-O ratio was 0.3874, which was higher than that of CeO 2 NRs 0.2641, indicating that CeO 2 NRs- The content of trivalent cerium in MOFs is more than that of CeO 2 NRs, indicating that CeO 2 NRs-MOFs have stronger oxidase activity than CeO 2 NRs, which is consistent with the reported ceria nanozyme activity in the literature that enhances with increasing cerium content Consistent (Heckert, EG; Karakoti, AS; Seal, S.; Self, WT The role of ceriumredox state in the SOD mimetic activity of nanoceria. Biomaterials, 2008, 29(18), 2705-2709), indicating that the present invention was successfully prepared CeO 2 NRs-MOF with strong oxidase activity was obtained.
采用紫外-可见吸收(UV-Vis)光谱法对CeO2NRs和CeO2NRs-MOF的氧化酶活性进行表征，图2为CeO2NRs和CeO2NRs-MOF对Cr(VI)响应的UV-Vis光谱图。将100μL 1mg/mL铈基金属有机框架、10μL 20mM TMB溶液、50μL 10μM的Cr(VI)溶液与50μL 100mM pH 4的HEPES缓冲溶液混合，加超纯水至溶液总体积为500μL，混合均匀后立即采用UV-2450型紫外可见分光光度计测定混合反应溶液在330nm-800nm波长范围内的吸收光谱。CeO2NRs无法在短时间内氧化TMB，因而在370nm和650nm处的吸收峰非常弱，而CeO2NRs-MOF的氧化酶活性更强，可快速氧化TMB显色，因此在370nm和650nm处出现了氧化型TMB的强吸收峰。The oxidase activities of CeO 2 NRs and CeO 2 NRs - MOF were characterized by ultraviolet-visible absorption (UV-Vis) spectroscopy. Vis spectrogram. Mix 100 μL of 1 mg/mL cerium-based metal organic framework, 10 μL of 20 mM TMB solution, 50 μL of 10 μM Cr(VI) solution with 50 μL of 100 mM HEPES buffer solution at pH 4, add ultrapure water to a total solution volume of 500 μL, and immediately after mixing well The absorption spectrum of the mixed reaction solution in the wavelength range of 330nm-800nm was measured by UV-2450 UV-Vis spectrophotometer. CeO 2 NRs cannot oxidize TMB in a short time, so the absorption peaks at 370 nm and 650 nm are very weak, while CeO 2 NRs-MOF has stronger oxidase activity and can rapidly oxidize TMB for color development, so it appears at 370 nm and 650 nm. The strong absorption peak of oxidized TMB was observed.
实施例5：基于CeO2NRs-MOF的氧化酶活性检测Cr(VI)的原理及可行性分析Example 5: Principle and Feasibility Analysis of Cr(VI) Detection Based on CeO 2 NRs-MOF Oxidase Activity
基于牺牲模板法制备的CeO2NRs-MOF构建比色法检测Cr(VI)的步骤简单，只需测量CeO2NRs-MOF、TMB和Cr(VI)的混合溶液的紫外光谱特征变化即可实现目标物的检测。与CeO2纳米材料相比，CeO2NRs-MOF具有更强的氧化酶活性和选择性，可在无H2O2存在的情况下直接氧化TMB显色以及选择性吸附Cr(VI)并还原成Cr(III)，Cr(VI)可代替常规使用的H2O2而与TMB构成氧化还原循环新体系，实现快速比色法检测Cr(VI)。检测原理如图3所示。The steps of constructing a colorimetric method to detect Cr(VI) based on CeO 2 NRs-MOF prepared by sacrificial template method are simple, and it only needs to measure the change of UV spectral characteristics of the mixed solution of CeO 2 NRs-MOF, TMB and Cr(VI), which can be realized target detection. Compared with CeO 2 nanomaterials, CeO 2 NRs-MOFs have stronger oxidase activity and selectivity, which can directly oxidize TMB for color development and selectively adsorb Cr(VI) and reduce it in the absence of H 2 O 2 To form Cr(III), Cr(VI) can replace the conventionally used H 2 O 2 and form a new redox cycle system with TMB to realize rapid colorimetric detection of Cr(VI). The detection principle is shown in Figure 3.
利用UV-Vis光谱法对本发明构建的比色方法进行可行性验证，图4为不同实验条件时采用本发明构建的比色法检测Cr(VI)的UV-Vis光谱图。由图4可见，在含10mM pH 4的HEPES的水溶液中，CeO2NRs-MOF(图中标为CeO2-MOF)、TMB以及Cr(VI)在330nm-800nm波长范围内均没有特征吸收峰，将上述三者进行两两混合也未出现明显的特征吸收峰，只有在CeO2NRs-MOF、TMB和Cr(VI)同时存在时才会在370nm和650nm处出现明显的氧化型TMB的特征吸收峰。以上结果表明，采用本发明方法制备的CeO2NRs-MOF具有良好的氧化酶活性，结合Cr(VI)-TMB氧化还原新体系，成功构建了比色新方法并可用于检测Cr(VI)。The feasibility of the colorimetric method constructed by the present invention is verified by UV-Vis spectroscopy. Figure 4 is a UV-Vis spectrogram of the colorimetric method constructed by the present invention to detect Cr(VI) under different experimental conditions. It can be seen from Figure 4 that in the aqueous solution containing 10 mM HEPES pH 4, CeO 2 NRs-MOF (marked as CeO 2 -MOF in the figure), TMB and Cr(VI) have no characteristic absorption peaks in the wavelength range of 330nm-800nm, There is no obvious characteristic absorption peak when the above three are mixed in pairs. Only when CeO 2 NRs-MOF, TMB and Cr(VI) coexist, the characteristic absorption of oxidized TMB will appear at 370 nm and 650 nm. peak. The above results show that the CeO 2 NRs-MOF prepared by the method of the present invention has good oxidase activity. Combined with the new Cr(VI)-TMB redox system, a new colorimetric method has been successfully constructed and can be used to detect Cr(VI).
实施例6：基于CeO2NRs-MOF构建的比色法对Cr(VI)的检测性能分析Example 6: Analysis of the detection performance of Cr(VI) by a colorimetric method based on CeO 2 NRs-MOF
将实施例1所得到的铈基金属有机框架经超纯水稀释分散成浓度1mg/mL的悬浊液100μL、20mM TMB溶液10μL、在0-5μM范围内不同浓度的Cr(VI)溶液与100mM pH 4的HEPES缓冲溶液50μL混合，加超纯水至溶液总体积为500μL，混合均匀后立即采用UV-2450型紫外可见分光光度计测定混合反应溶液在330nm-800nm波长范围内的吸收光谱，本发明构建的比色法对不同浓度Cr(VI)响应的紫外-可见吸收光谱图见图5A；Cr(VI)的浓度与TMB特征吸收峰强度之间的校准曲线见图5B。The cerium-based metal organic framework obtained in Example 1 was diluted with ultrapure water and dispersed into 100 μL of suspension with a concentration of 1 mg/mL, 10 μL of 20 mM TMB solution, Cr(VI) solutions with different concentrations in the range of 0-5 μM and 100 mM Mix 50 μL of pH 4 HEPES buffer solution, add ultrapure water until the total solution volume is 500 μL, and immediately use UV-2450 UV-Vis spectrophotometer to measure the absorption spectrum of the mixed reaction solution in the wavelength range of 330nm-800nm. The UV-Vis absorption spectrum of the colorimetric method constructed by the invention in response to different concentrations of Cr(VI) is shown in Figure 5A; the calibration curve between the concentration of Cr(VI) and the characteristic absorption peak intensity of TMB is shown in Figure 5B.
由图5A可见，随着Cr(VI)浓度的增大(0,0.03,0.05,0.1,0.2,0.4,0.6,0.8,1,2,3,4和5μM)，溶液的蓝色逐渐变深，650nm处的吸收峰强度逐渐增强；由图5B可见，650nm处的吸光度与750nm处基线的吸光度之差(ΔA＝A650nm-A750nm)与Cr(VI)浓度在30nM-5μM范围内呈良好的线性关系，检测限为20nM。比基于金纳米粒子配位的比色法检测Cr(VI)(线性范围0.5-2.5μM，检测限0.07μM)(Du,J.；Ge,H.；Gu,Q.；Du,H.；Fan,J.；Peng,X.Goldnanoparticle-based nano-probe for the colorimetric sensing of Cr3+ and Cr2O7 2-by the coordination strategy.Nanoscale,2017,9(48),19139-19144)、使用Zr4+MOF特异吸附和检测Cr(VI)(检测范围0.5-96μM，检测限77nM)(Rapti,S.；Sarma,D.；Diamantis,S.A.；Skliri,E.；Armatas,G.S.；Tsipis,A.C.；Hassan,Y.S.；Alkordi,M.；Malliakas,C.D.；Kanatzidis,M.G.；Lazarides T.；Plakatouras,J.C.；Lazarides,T.All in oneporous material:exceptional sorption and selective sensing of hexavalentchromium by using a Zr4+MOF.Journal of Materials Chemistry A,2017,5(28),14707-14719)、通过Schiff碱反应将壳聚糖与戊二醛交联合成非共轭聚合物荧光团用于选择性检测Cr(VI)(检测范围0-50μM，检测限0.22μM)(Song,J.；Zhou,H.；Gao,R.；Zhang,Y.；Zhang,H.；Zhang,Y.；Wang,G.；Wong,P.K.；Zhao,H.Selective determination of Cr(VI)byglutaraldehyde cross-linked chitosan polymer fluorophores.ACS sensors,2018,3(4),792-798)的效果好。可见，本发明方法制备的铈基金属有机框架用于检测Cr(VI)具有良好的灵敏性和可靠性。As can be seen from Figure 5A, with the increase of Cr(VI) concentration (0, 0.03, 0.05, 0.1, 0.2, 0.4, 0.6, 0.8, 1, 2, 3, 4 and 5 μM), the blue color of the solution gradually became darker , the intensity of the absorption peak at 650nm gradually increased; it can be seen from Figure 5B that the difference between the absorbance at 650nm and the absorbance of the baseline at 750nm (ΔA=A 650nm -A 750nm ) and the Cr(VI) concentration in the range of 30nM-5μM showed good results The linear relationship of , the detection limit is 20 nM. Colorimetric detection of Cr(VI) based on the coordination of gold nanoparticles (linear range 0.5-2.5 μM, detection limit 0.07 μM) (Du, J.; Ge, H.; Gu, Q.; Du, H.; Fan, J.; Peng, X. Gold nanoparticle-based nano-probe for the colorimetric sensing of Cr 3+ and Cr 2 O 7 2- by the coordination strategy. Nanoscale, 2017, 9(48), 19139-19144), using Specific adsorption and detection of Cr(VI) by Zr 4+ MOF (detection range 0.5-96 μM, detection limit 77 nM) (Rapti, S.; Sarma, D.; Diamantis, SA; Skliri, E.; Armatas, GS; Tsipis, AC ; Hassan, YS; Alkordi, M.; Malliakas, CD; Kanatzidis, MG; Lazarides, T.; Plakatouras , JC; Lazarides, T. Journal of Materials Chemistry A, 2017, 5(28), 14707-14719), Cross-association of chitosan and glutaraldehyde by Schiff base reaction to form a non-conjugated polymer fluorophore for selective detection of Cr(VI) ( Detection range 0-50μM, detection limit 0.22μM) (Song, J.; Zhou, H.; Gao, R.; Zhang, Y.; Zhang, H.; Zhang, Y.; Wang, G.; Wong, PK ; Zhao, H. Selective determination of Cr(VI) byglutaraldehyde cross-linked chitosan polymer fluorophores. ACS sensors, 2018, 3(4), 792-798) works well. It can be seen that the cerium-based metal organic framework prepared by the method of the present invention has good sensitivity and reliability for detecting Cr(VI).
实施例7：基于CeO2NRs-MOF构建的比色法对Cr(VI)检测的选择性Example 7: Selectivity of Cr(VI) detection by a colorimetric method based on CeO 2 NRs-MOF
考察了基于CeO2NRs-MOF构建的比色法对Cr(VI)检测的选择性，如图6所示。由图6可见，17种水中可能存在的阳离子和阴离子即使浓度为Cr(VI)浓度的十倍，如Cr(VI)为1μM、其它离子为10μM时，也几乎没有响应。这是由于CeO2NRs-MOF外层的MOF的尺寸选择效应以及显色体系中不存在H2O2避免了自身具有过氧化物酶活性的离子(如铁离子，铜离子)干扰的双重作用。综上所述，本发明方法对Cr(VI)的检测具有良好的选择性。The selectivity of the colorimetric method based on CeO 2 NRs-MOF for Cr(VI) detection was investigated, as shown in Figure 6. It can be seen from Figure 6 that the 17 kinds of cations and anions that may exist in water have almost no response even if the concentration is ten times the concentration of Cr(VI), such as 1 μM of Cr(VI) and 10 μM of other ions. This is due to the dual effect of the size selection effect of the MOF in the outer layer of CeO 2 NRs-MOF and the absence of H 2 O 2 in the color developing system to avoid the interference of ions with peroxidase activity (such as iron ions, copper ions) themselves. . In conclusion, the method of the present invention has good selectivity for the detection of Cr(VI).
同样地，将实施例2所制备的铈基金属有机框架与实施例3所制备的铈基金属有机框架，按照实施例4-7的所述方法，重复进行各项检测与实验，所得到的检测与实验结果，与实施例1所制备的铈基金属有机框架所进行实施例4-7的结果基本相同。Similarly, the cerium-based metal-organic framework prepared in Example 2 and the cerium-based metal-organic framework prepared in Example 3 were subjected to repeated detections and experiments according to the methods described in Examples 4-7, and the obtained The detection and experimental results are basically the same as the results of Examples 4-7 performed on the cerium-based metal organic framework prepared in Example 1.
以上对本发明的具体实施例进行了详细描述，但其只是作为范例，本发明并不限制于以上描述具体实施例。对于本领域技术人员而言，任何对本发明进行的等同修改和替代也都在本发明的范畴之中。因此，在不脱离本发明的精神和范围下所作的均等变换和修改，都涵盖在本发明范围内。The specific embodiments of the present invention have been described above in detail, but they are only used as examples, and the present invention is not limited to the specific embodiments described above. For those skilled in the art, any equivalent modifications and substitutions to the present invention are also within the scope of the present invention. Therefore, equivalent changes and modifications made without departing from the spirit and scope of the present invention are all included within the scope of the present invention.
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| CN108855069A (en) * | 2018-06-19 | 2018-11-23 | 华侨大学 | A kind of nano bar-shape Pt/CeO2The preparation method of loaded catalyst and the application in CO catalysis reaction |
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| CN108855069A (en) * | 2018-06-19 | 2018-11-23 | 华侨大学 | A kind of nano bar-shape Pt/CeO2The preparation method of loaded catalyst and the application in CO catalysis reaction |
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