WO2023024312A1 - Procédé de préparation de substrat amélioré par diffusion raman exaltée de surface (sers) à base de réaction de remplacement galvanique - Google Patents
Procédé de préparation de substrat amélioré par diffusion raman exaltée de surface (sers) à base de réaction de remplacement galvanique Download PDFInfo
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- WO2023024312A1 WO2023024312A1 PCT/CN2021/135064 CN2021135064W WO2023024312A1 WO 2023024312 A1 WO2023024312 A1 WO 2023024312A1 CN 2021135064 W CN2021135064 W CN 2021135064W WO 2023024312 A1 WO2023024312 A1 WO 2023024312A1
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- Prior art keywords
- sers
- reaction time
- sers signal
- solution
- sacrificial template
- Prior art date
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 claims abstract description 110
- 230000035484 reaction time Effects 0.000 claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 230000000694 effects Effects 0.000 claims abstract description 13
- 239000000523 sample Substances 0.000 claims abstract description 11
- 238000001069 Raman spectroscopy Methods 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 29
- 239000010931 gold Substances 0.000 claims description 23
- 238000006073 displacement reaction Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 20
- 239000013078 crystal Substances 0.000 claims description 15
- 238000013461 design Methods 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 238000000479 surface-enhanced Raman spectrum Methods 0.000 claims description 12
- 239000002105 nanoparticle Substances 0.000 claims description 11
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 10
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 10
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052737 gold Inorganic materials 0.000 claims description 10
- 229940112669 cuprous oxide Drugs 0.000 claims description 8
- 238000010586 diagram Methods 0.000 claims description 8
- 230000008859 change Effects 0.000 claims description 6
- 238000002474 experimental method Methods 0.000 claims description 5
- 238000011065 in-situ storage Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000010413 mother solution Substances 0.000 claims description 4
- 239000002082 metal nanoparticle Substances 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 229910000510 noble metal Inorganic materials 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- 238000001228 spectrum Methods 0.000 claims description 3
- 239000006193 liquid solution Substances 0.000 claims 1
- 238000011897 real-time detection Methods 0.000 claims 1
- 239000010949 copper Substances 0.000 description 21
- 239000010936 titanium Substances 0.000 description 13
- 230000003014 reinforcing effect Effects 0.000 description 5
- 230000001808 coupling effect Effects 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- JIDMEYQIXXJQCC-UHFFFAOYSA-L copper;2,2,2-trifluoroacetate Chemical compound [Cu+2].[O-]C(=O)C(F)(F)F.[O-]C(=O)C(F)(F)F JIDMEYQIXXJQCC-UHFFFAOYSA-L 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000009659 non-destructive testing Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- CUNPJFGIODEJLQ-UHFFFAOYSA-M potassium;2,2,2-trifluoroacetate Chemical compound [K+].[O-]C(=O)C(F)(F)F CUNPJFGIODEJLQ-UHFFFAOYSA-M 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- G01N21/01—Arrangements or apparatus for facilitating the optical investigation
-
- 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
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
Definitions
- the invention relates to the technical field of surface-enhanced Raman spectroscopy, in particular to a method for preparing a SERS-enhanced substrate based on an electrical displacement reaction.
- SERS Surface-enhanced Raman scattering
- the preparation of SERS-enhanced substrate is the key to this technology, and the quality of the enhanced substrate directly affects important performance indicators such as detection sensitivity and reproducibility.
- the SERS signal is related to factors such as the material of the reinforcing substrate, the size of the reinforcing elements (such as particles) on the surface of the substrate, and the spacing between the reinforcing elements.
- the optimization of the preparation conditions in the SERS preparation methods reported in the literature has certain shortcomings, that is, when the material is fixed, the size of the reinforcing element is often optimized first, and then the spacing between the reinforcing elements is optimized, or both are optimized at the same time. . Regardless of the optimization method, on the one hand, the optimized parameters are relatively small, which may not be close to the "best state" under the current experimental conditions; on the other hand, this optimization method is time-consuming and laborious, and also increases costs.
- a method for preparing a SERS-enhanced substrate based on an electrodisplacement reaction is provided, and an optimal SERS substrate can be obtained with simple steps under low-cost and high-efficiency experimental conditions.
- a method for preparing a SERS-enhanced substrate based on an electrodisplacement reaction comprising the following steps.
- step b Carrying out an electrodisplacement reaction between the sacrificial template in step a and a metal salt solution having a better SERS enhancement effect; at the same time, adding molecules to be studied or probe molecules into the reaction solution.
- the SERS signal of the system was detected in real time, so as to obtain the relationship diagram between the SERS signal and the electrodisplacement reaction time. According to this relationship diagram, the optimal preparation conditions of the SERS substrate in this experimental scheme can be known.
- the selection condition of the sacrificial template is: the selected sacrificial template material can be replaced by the metal salt in step b.
- the method of drawing the relationship graph between the SERS signal and the electrical displacement reaction time is as follows.
- step (3) the design of the corresponding material SERS substrate can be guided. That is, according to the size and spacing of the metal nanoparticles with strong SERS enhancement effect obtained under the optimal reaction conditions, as well as the ratio of the nanoparticles to the sacrificial template material, the influence of these parameters on the SERS signal is speculated, so as to provide a basis for the design of the corresponding SERS substrate. Provide an experimental basis.
- cuprous oxide is used as a sacrificial template, and gold is used as a metal with better SERS enhancement effect, and the preparation method of the SERS enhancement substrate includes the following steps.
- step (3) Extract the SERS spectrum in step (2), according to the drawing method of the relationship between the SERS signal and the electrical displacement reaction time, select 1 ⁇ 3 strong peaks, and read the peaks of these peaks in each SERS spectrum High, plot the electrodisplacement reaction time, and obtain the SERS signal intensity of these peaks and the electrodisplacement reaction time curve.
- the experimental condition corresponding to the maximum value of the ordinate of this curve is the optimal preparation condition of the SERS substrate under this experimental scheme.
- step (2) the Au nanoparticles grow from nothing, from small to large, from less to more, and the ratio of Au nanoparticles to Cu also changes from less to more, all of which change with the reaction time There is continuous change. Therefore, according to the results obtained in step (3), the design of the Cu-Au SERS substrate can be guided, that is, the size, spacing, and ratio of gold particles to Cu2O obtained under the optimal reaction conditions, these parameters can be speculated The impact on the SERS signal, thus providing an experimental basis for the design of the corresponding SERS substrate.
- the sacrificial template includes cuprous oxide material.
- the metal with better SERS enhancement effect includes gold.
- the probe molecules include crystal violet.
- the application optimizes the enhanced substrate of SERS on-site, and observes the impact of changes in the size of nanomaterials, particle spacing, and the coupling effect between different materials on the SERS signal in real time, which can be simple, convenient and low-cost , obtain the best SERS substrate with high efficiency; on the other hand, the preparation of SERS substrate through electro-displacement reaction can reduce the amount of precious metal materials, which is economical and environmentally friendly.
- step a using sacrificial templates made of different materials, it is possible to investigate in real time whether there is a coupling effect between different materials that is conducive to SERS signal enhancement; if there is, the coupling effect varies with the size, shape, and spacing of different materials. What about the relationship.
- step b the plotted SERS signal intensity and electrical displacement reaction time curve not only provides the optimal preparation conditions for the SERS substrate under the current experimental scheme, but also provides information such as the optimal particle size, the most The relevant parameters such as optimal particle spacing provide an experimental basis for the preparation of SERS substrates with corresponding materials.
- Fig. 1 is the SEM image of Example 1, which shows the electrodisplacement of Cu 2 O in the mixed solution of chloroauric acid solution and crystal violet for 500 s.
- Fig. 2 is the SERS spectra collected at different time periods during the electrodisplacement reaction of Cu 2 O in Example 2 in the mixed solution of chloroauric acid solution and crystal violet.
- Fig. 3 is a graph showing the variation of the SERS peak intensity of crystal violet in Example 3 at ⁇ 1580 cm -1 with the time of the electrodisplacement reaction.
- the present application provides a method for preparing a SERS-enhanced substrate based on an electrodisplacement reaction, including the following steps.
- step b Carrying out an electrodisplacement reaction between the sacrificial template in step a and a metal salt solution having a better SERS enhancement effect; at the same time, adding molecules to be studied or probe molecules into the reaction solution.
- the SERS signal of the system was detected in real time, so as to obtain the relationship diagram between the SERS signal and the electrodisplacement reaction time. According to this relationship diagram, the optimal preparation conditions of the SERS substrate in this experimental scheme can be known.
- the selection condition of the sacrificial template is: the selected sacrificial template material can be replaced by the metal salt in step b.
- the method of drawing the relationship graph between the SERS signal and the electrical displacement reaction time is as follows.
- step (3) the design of the corresponding material SERS substrate can be guided. That is, according to the size and spacing of the metal nanoparticles with strong SERS enhancement effect obtained under the optimal reaction conditions, as well as the ratio of the nanoparticles to the sacrificial template material, the influence of these parameters on the SERS signal is speculated, so as to provide a basis for the design of the corresponding SERS substrate. Provide an experimental basis.
- cuprous oxide is used as a sacrificial template, and gold is used as a metal with better SERS enhancement effect, and the preparation method of the SERS enhancement substrate thereof includes the following steps.
- step (3) Extract the SERS spectrum in step (2), according to the drawing method of the relationship between the SERS signal and the electrical displacement reaction time, select 1 ⁇ 3 strong peaks, and read the peaks of these peaks in each SERS spectrum High, plot the electrodisplacement reaction time, and obtain the SERS signal intensity of these peaks and the electrodisplacement reaction time curve.
- the experimental condition corresponding to the maximum value of the ordinate of this curve is the optimal preparation condition of the SERS substrate under this experimental scheme.
- step (2) the Au nanoparticles grow from nothing, from small to large, from less to more, and the ratio of Au nanoparticles to Cu also changes from less to more, all of which change with the reaction time There is continuous change. Therefore, according to the results obtained in step (3), the design of the Cu-Au SERS substrate can be guided, that is, the size, spacing, and ratio of gold particles to Cu2O obtained under the optimal reaction conditions, these parameters can be speculated The impact on the SERS signal, thus providing an experimental basis for the design of the corresponding SERS substrate.
- the sacrificial template includes a cuprous oxide material.
- the metal with better SERS enhancement effect includes gold.
- the probe molecule comprises crystal violet.
- Example 1 This example is the preparation of electrodeposited cuprous oxide/titanium sheet (Cu 2 O/Ti) sacrificial template. First, the polished and cleaned titanium sheet was used as the working electrode, the platinum sheet was used as the auxiliary electrode, and the saturated calomel electrode (SCE) was used as the reference electrode.
- SCE saturated calomel electrode
- the shape and size of Cu 2 O can be seen in FIG. 1 .
- Example 2 In this example, the Cu 2 O/Ti prepared in Example 1 was used as the sacrificial template, the 1 mmol/L crystal violet solution was used as the probe molecule mother solution, and the 1 mmol/L HAuCl 4 solution was used Replacement solution for precious metals.
- the step Cu 2 O/Ti sacrificial template was installed in the laboratory's own sealed in-situ Raman spectroelectrochemical cell. Quickly add 0.1 mL of 1 mmol/L crystal violet solution and 9.9 mL of 1 mmol/L HAuCl 4 solution into the spectroelectrochemical cell, and mix well. Start timing and detect the SERS signal at the same time. The SERS signal changes from weak to strong and then weak. About 1000 s after the experiment, several strong SERS peaks have dropped to less than a quarter of the strongest (reaction about 500 s). To be on the safe side, in this example, the experiment was carried out for a total of 3200 s. Different reactions The time SERS diagram is shown in Fig. 2.
- Embodiment 3 In this embodiment, first extract the SERS spectrum in embodiment 2, select the SERS peak at ⁇ 1580 cm - 1, read the peak height at ⁇ 1580 cm -1 in each SERS spectrum, Plot the reaction time of electrodisplacement. The curves of SERS signal intensity and electrodisplacement reaction time of these peaks are obtained, as shown in FIG. 3 .
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- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
Dans un procédé de préparation de substrat amélioré par SERS à base de réaction de remplacement galvanique, un sel métallique présentant un bon effet d'amélioration vis-à-vis de la spectroscopie Raman et un gabarit sacrificiel servent à effectuer une réaction de remplacement galvanique, tandis que des molécules à rechercher ou des molécules sondes sont simultanément ajoutées à la solution réactionnelle. Pendant la réaction de remplacement galvanique, un signal de SERS du système est détecté en temps réel pour obtenir un graphe relationnel du signal de SERS en fonction du temps de réaction de remplacement galvanique. Selon le graphe relationnel, une condition expérimentale optimale d'un substrat de SERS dans un programme expérimental peut être connue.
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CN202110974441.1 | 2021-08-24 | ||
CN202110974441.1A CN113720779B (zh) | 2021-08-24 | 2021-08-24 | 一种基于电置换反应的sers增强基底的制备方法 |
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Citations (6)
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CN103983628A (zh) * | 2013-12-13 | 2014-08-13 | 江南大学 | 一种铜网基叶片状金sers活性基底的制备方法 |
CN104550998A (zh) * | 2014-12-17 | 2015-04-29 | 浙江理工大学 | 一种金空心球/氧化亚铜纳米核壳结构的制备方法 |
CN105290393A (zh) * | 2014-06-03 | 2016-02-03 | 中国科学院苏州纳米技术与纳米仿生研究所 | 中空SiO2包空心Au笼纳米摇铃、其制备方法及应用 |
CN107099787A (zh) * | 2017-05-18 | 2017-08-29 | 江西师范大学 | 一种表面增强拉曼散射基底及其制备方法 |
CN108277484A (zh) * | 2018-01-22 | 2018-07-13 | 安徽师范大学 | 一种中空Ag-Au合金复合结构微纳阵列的制备方法 |
CN113720779A (zh) * | 2021-08-24 | 2021-11-30 | 东莞理工学院 | 一种基于电置换反应的sers增强基底的制备方法 |
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- 2021-08-24 CN CN202110974441.1A patent/CN113720779B/zh active Active
- 2021-12-02 WO PCT/CN2021/135064 patent/WO2023024312A1/fr unknown
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
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CN103983628A (zh) * | 2013-12-13 | 2014-08-13 | 江南大学 | 一种铜网基叶片状金sers活性基底的制备方法 |
CN105290393A (zh) * | 2014-06-03 | 2016-02-03 | 中国科学院苏州纳米技术与纳米仿生研究所 | 中空SiO2包空心Au笼纳米摇铃、其制备方法及应用 |
CN104550998A (zh) * | 2014-12-17 | 2015-04-29 | 浙江理工大学 | 一种金空心球/氧化亚铜纳米核壳结构的制备方法 |
CN107099787A (zh) * | 2017-05-18 | 2017-08-29 | 江西师范大学 | 一种表面增强拉曼散射基底及其制备方法 |
CN108277484A (zh) * | 2018-01-22 | 2018-07-13 | 安徽师范大学 | 一种中空Ag-Au合金复合结构微纳阵列的制备方法 |
CN113720779A (zh) * | 2021-08-24 | 2021-11-30 | 东莞理工学院 | 一种基于电置换反应的sers增强基底的制备方法 |
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CN113720779A (zh) | 2021-11-30 |
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