CN114184664A - Preparation method of Ti-ZIF-67 electrochemical sensor for detecting ammonium ions, product and application thereof - Google Patents
Preparation method of Ti-ZIF-67 electrochemical sensor for detecting ammonium ions, product and application thereof Download PDFInfo
- Publication number
- CN114184664A CN114184664A CN202111338638.2A CN202111338638A CN114184664A CN 114184664 A CN114184664 A CN 114184664A CN 202111338638 A CN202111338638 A CN 202111338638A CN 114184664 A CN114184664 A CN 114184664A
- Authority
- CN
- China
- Prior art keywords
- sheet
- zif
- metal titanium
- solution
- titanium sheet
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 ammonium ions Chemical class 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000010936 titanium Substances 0.000 claims abstract description 141
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 74
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 74
- 229910052751 metal Inorganic materials 0.000 claims abstract description 63
- 239000002184 metal Substances 0.000 claims abstract description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 17
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 238000011068 loading method Methods 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 24
- 239000000725 suspension Substances 0.000 claims description 18
- 238000002791 soaking Methods 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 239000010953 base metal Substances 0.000 claims description 12
- 238000005520 cutting process Methods 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 238000005498 polishing Methods 0.000 claims description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims description 12
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 11
- 238000001514 detection method Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000004480 active ingredient Substances 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 5
- 238000012372 quality testing Methods 0.000 claims 1
- 238000012360 testing method Methods 0.000 abstract description 23
- 230000035945 sensitivity Effects 0.000 abstract description 9
- 239000013543 active substance Substances 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 14
- 235000019270 ammonium chloride Nutrition 0.000 description 7
- 239000000463 material Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 2
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229960001149 dopamine hydrochloride Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 229940116269 uric acid Drugs 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
Abstract
The invention discloses a preparation method of a Ti-ZIF-67 electrochemical sensor for detecting ammonium ions, and a product and application thereof.A purple turbid liquid generated by mixing a cobalt nitrate solution and a dimethyl imidazole solution is vertically dipped in a pretreated metal titanium sheet to realize uniform loading of an active substance on the surface of the metal titanium sheet; heating in a constant-temperature water bath at 60 ℃ to ensure that the surface active substance stably grows on the Ti sheet; by utilizing the i-t Amperometric i-t Curve test function of the electrochemical workstation, the excellent performances of Ti-ZIF-67 such as specific selectivity, high sensitivity, high cycle test stability and the like on ammonium ions are tested. The Ti-ZIF-67 electrochemical sensor obtained by the invention has obvious selection on the test of ammonium ions, excellent test result, simple preparation process, convenience for large-scale production, easily available raw materials, low cost and good application prospect.
Description
Technical Field
The invention designs a preparation method of a novel electrochemical sensor, and particularly relates to a preparation method of a Ti-ZIF-67 electrochemical sensor for detecting ammonium ions, and a product and application thereof.
Background
The nano-scale composite metal oxide material and the functional nano-structure material have been widely applied in the field of electrochemical sensing due to excellent physical and chemical properties such as high specific surface area, excellent electrocatalysis and considerable internal biocompatibility. ZIF-67 is a MOFs material with zeolite-like three-dimensional topological framework structure, and there are many reports that ZIF-67-based nano-materials have been used to construct non-enzymatic electrochemical sensors when applying these materials to Glucose (Glucose), hydrogen peroxide (H)2O2) And good effect can be obtained when detecting dopamine hydrochloride (DA), Acrylic Acid (AA) and Uric Acid (UA).
Water is a source of life, all organisms can not boil in normal life, the quality of water quality is more critical to the quality of human life, ammonium ions in water are an important factor influencing the water quality, and water with the ammonia nitrogen content of less than 0.15mg/L is I-type according to the surface water environmental quality standard (GB 3838-2002) issued by the national environmental protection Bureau 2002 in 4, 26.
The traditional method for detecting ammonium ions is complex to operate, the detection period is long, the detected test waste materials are easy to pollute the environment, the cost is higher than that of a reusable electrochemical sensor, and therefore the detection efficiency is low in many application occasions. It is desirable to synthesize a high-efficiency electrochemical sensor which can specifically detect the concentration of ammonium ions in a solution, and has the advantages of low cost, rapid detection and short detection period.
Disclosure of Invention
The invention aims to provide a preparation method of a Ti-ZIF-67 electrochemical sensor for detecting ammonium ions.
Yet another object of the present invention is to: provides a Ti-ZIF-67 electrochemical sensor product for detecting ammonium ions, which is prepared by the method.
Yet another object of the present invention is to: provides an application of the product.
The purpose of the invention is realized by the following scheme: a preparation method of a Ti-ZIF-67 electrochemical sensor for detecting ammonium ions takes ZIF-67 as an active catalytic component and can be used for detecting the ammonium ion change in water quality, and comprises the following steps:
(1) pre-treating a base metal titanium sheet, namely cutting the metal titanium sheet into the size of 1cm by 2cm, polishing two sides of the metal titanium sheet, soaking the metal titanium sheet in 10% dilute hydrochloric acid, absolute ethyl alcohol and deionized water respectively, performing ultrasonic treatment for 15 minutes, taking out the metal titanium sheet, and washing the metal titanium sheet to obtain a pre-treated Ti sheet for later use;
(2) preparing Ti-ZIF-67: vertically fixing the Ti sheet at the bottom of a beaker to ensure that the loading capacity of the two sides of the Ti sheet is uniform and the same; preparing an active component ZIF-67 by using cobalt nitrate and dimethyl imidazole in a molar ratio of (1: 4) - (1: 16) to obtain a purple suspension; pouring the purple suspension into a pretreated Ti sheet beaker in advance until the solution is over the top of the Ti sheet, heating the solution in a 60 ℃ water bath kettle for 24 hours, taking out the solution, repeatedly washing away the purple particles loaded on the surface by using absolute ethyl alcohol and deionized water, and then drying the solution in a 60 ℃ drying oven for later use to obtain purple Ti-ZIF-67.
The invention also provides a Ti-ZIF-67 electrochemical sensor for detecting ammonium ions, which is prepared according to the method.
The invention also provides application of the Ti-ZIF-67 electrochemical sensor in detecting ammonium ions in water quality detection.
The test was completed by the chi-760 electrochemical workstation manufactured by Shanghai Chenghua, Inc. And the contents of selectivity, optimized voltage, sensitivity, placement stability, cycling stability and the like are tested respectively.
The specific selectivity and higher electrochemical sensitivity of the test voltage to ammonium ions under a certain specific voltage condition are obtained by optimizing the test voltage. The Ti-ZIF-67 electrochemical sensor subjected to heat treatment can quickly and stably detect ammonium ions in a solution and does not generate irritant gas in the process.
According to the invention, a simple one-step soaking method is adopted, the molar ratio of cobalt nitrate hexahydrate and dimethyl imidazole is regulated to obtain a ZIF-67 active substance, and the Ti-ZIF-67 electrochemical sensor is obtained by heating in a water bath at 60 ℃.
After electrochemical selectivity testing, the specificity of the compound for ammonium ions can be determined, and the compound does not respond to chloride ions, sodium ions, potassium ions, nitrate ions, sulfate ions and the like. The advantages of low cost, simple synthesis method, repeated utilization, quick response and the like are integrated, and the method has great application potential.
The invention discloses a Ti-ZIF-67 electrochemical sensor for detecting ammonium ions by using cobalt as an active site, which realizes real-time monitoring of the change of the ammonium ion concentration by using the change of the potential in a solution when the ammonium ion concentration changes, can obtain more same electrochemical sensors to the maximum extent by adopting a soaking method, avoids the waste of raw materials to the maximum extent, can prevent the situations of overhigh load capacity or uneven two surfaces of the Ti-ZIF-67 electrochemical sensor by adopting a vertical soaking method, and enhances the stability of the sensor by heating treatment at 60 ℃. The sensor not only has good electrochemical sensing performance, but also has excellent stability, and can avoid the generation of pungent odor gas in the test process.
The invention has the following advantages:
(1) the electrochemical sensor obtained by the invention has excellent activity, specific selectivity on ammonium ions, higher electrochemical sensing sensitivity on the ammonium ions under a certain voltage condition and extremely high detection speed.
(2) The electrochemical sensing performance of the Ti-ZIF-67 subjected to heating treatment at 60 ℃ is not influenced by hundreds of cycles of detection of ammonium ions, namely the Ti-ZIF-67 has good stability.
(3) The synthesis method is simple, safe, efficient and feasible, can be massively produced in a short time, is easy to obtain synthesis raw materials, is low in cost, and has a good application prospect.
Drawings
FIG. 1 is a graph showing the selectivity of Ti-ZIF-67 in the application example;
FIG. 2 is a graph of the 1.3V voltage of Ti-ZIF-67 in the application example;
FIG. 3 is a graph of the 1.4V voltage of Ti-ZIF-67 in the application example;
FIG. 4 is a graph of the 1.5V voltage of Ti-ZIF-67 in the application example;
FIG. 5 is a graph of the 1.6V voltage of Ti-ZIF-67 in the application example;
FIG. 6 sensitivity plot of Ti-ZIF-67 in the application example;
FIG. 7 is a graph showing the stability of Ti-ZIF-67 in the application example.
Detailed Description
The following examples illustrate the invention in detail: the present embodiment is applied on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following embodiments.
Example 1
A Ti-ZIF-67 electrochemical sensor for detecting ammonium ions takes ZIF-67 as an active catalytic component and is prepared by the following steps:
(1) pre-treating a base metal titanium sheet, namely cutting the metal titanium sheet into 1cm by 2cm, polishing two surfaces of the metal titanium sheet to be rough, soaking the metal titanium sheet in 10% dilute hydrochloric acid, absolute ethyl alcohol and deionized water respectively, performing ultrasonic treatment for 15 minutes, taking out the metal titanium sheet, and washing the metal titanium sheet to obtain a pre-treated Ti sheet for later use;
(2) preparing Ti-ZIF-67: vertically fixing the Ti sheet at the bottom of a beaker to ensure that the loading capacity of the two sides of the Ti sheet is uniform and the same; the molar ratio of the raw materials is 1: respectively preparing cobalt nitrate hexahydrate and a dimethyl imidazole solution according to the ratio of 8, and pouring the dimethyl imidazole solution into the cobalt nitrate solution to obtain a purple suspension liquid with an active ingredient of ZIF-67;
(3) pouring the purple suspension into a pretreated Ti sheet beaker in advance until the solution is over the top of the Ti sheet, heating the solution in a water bath kettle at 60 ℃ in the air atmosphere for 24 hours, taking out the solution, repeatedly washing away the purple particles loaded on the surface by using absolute ethyl alcohol and deionized water, and then drying the solution in a drying oven at 60 ℃ to obtain the Ti-ZIF-67 electrochemical sensor.
For the test of the Ti-ZIF-67 electrochemical sensor of this example, the following results were obtained:
(1) the Ti-ZIF-67 electrochemical sensor has 100% selectivity on ammonium ions and has no response on chloride ions, sodium ions, potassium ions, nitrate ions and sulfate ions.
(2) The Ti-ZIF-67 electrochemical sensor can detect the change of ammonium ions within three seconds.
(3) The Ti-ZIF-67 electrochemical sensor has the most obvious response to ammonium ions under the test voltage of 1.4V.
(4) The sensitivity of the Ti-ZIF-67 electrochemical sensor is calculated to be 2830 mu A.mmol-1L-1•cm-2。
(5) And through comparison and detection of one hundred times of cyclic tests of the ammonium ions, the stability of the repeated detection of the ammonium ions is obtained.
Example 2:
a Ti-ZIF-67 electrochemical sensor for detecting ammonium ions is prepared by the following steps, which are similar to the steps in the embodiment:
(1) pre-treating a base metal titanium sheet, namely cutting the metal titanium sheet into 1cm by 2cm, polishing two surfaces of the metal titanium sheet to be rough, soaking the metal titanium sheet in 10% dilute hydrochloric acid, absolute ethyl alcohol and deionized water respectively, performing ultrasonic treatment for 15 minutes, taking out the metal titanium sheet, and washing the metal titanium sheet to obtain a pre-treated Ti sheet for later use;
(2) preparing Ti-ZIF-67: vertically fixing the Ti sheet at the bottom of a beaker to ensure that the loading capacity of the two sides of the Ti sheet is uniform and the same; the molar ratio of the raw materials is 1: preparing cobalt nitrate hexahydrate and a dimethyl imidazole solution respectively according to the ratio of 4, and pouring the dimethyl imidazole solution into the cobalt nitrate solution to obtain a purple suspension liquid with an active ingredient of ZIF-67;
(3) pouring the purple suspension into a pretreated Ti sheet beaker in advance until the solution is over the top of the Ti sheet, heating the solution in a water bath kettle at 60 ℃ in the air atmosphere for 24 hours, taking out the solution, repeatedly washing away the purple particles loaded on the surface by using absolute ethyl alcohol and deionized water, and then drying the solution in a drying oven at 60 ℃ to obtain the Ti-ZIF-67 electrochemical sensor.
Example 3
A Ti-ZIF-67 electrochemical sensor for detecting ammonium ions is prepared by the following steps, which are similar to the steps in the embodiment:
(1) pre-treating a base metal titanium sheet, namely cutting the metal titanium sheet into 1cm by 2cm, polishing two surfaces of the metal titanium sheet to be rough, soaking the metal titanium sheet in 10% dilute hydrochloric acid, absolute ethyl alcohol and deionized water respectively, performing ultrasonic treatment for 15 minutes, taking out the metal titanium sheet, and washing the metal titanium sheet to obtain a pre-treated Ti sheet for later use;
(2) preparing Ti-ZIF-67: the molar ratio of the raw materials is 1: preparing cobalt nitrate hexahydrate and a dimethyl imidazole solution respectively according to the ratio of 6, and pouring the dimethyl imidazole solution into the cobalt nitrate solution to obtain a purple suspension liquid with an active ingredient of ZIF-67;
(3) and (3) putting the Ti sheet into the purple turbid liquid until the solution is submerged at the top of the Ti sheet, heating the Ti sheet in a water bath kettle at 60 ℃ in the air atmosphere for 24h, taking out the Ti sheet, repeatedly washing away the purple particles loaded with redundant surfaces by using absolute ethyl alcohol and deionized water, and then drying the Ti sheet in a drying oven at 60 ℃ to obtain the Ti-ZIF-67 electrochemical sensor.
Example 4
A Ti-ZIF-67 electrochemical sensor for detecting ammonium ions is prepared by the following steps, which are similar to the steps in the embodiment:
(1) pre-treating a base metal titanium sheet, namely cutting the metal titanium sheet into 1cm by 2cm, polishing two surfaces of the metal titanium sheet to be rough, soaking the metal titanium sheet in 10% dilute hydrochloric acid, absolute ethyl alcohol and deionized water respectively, performing ultrasonic treatment for 15 minutes, taking out the metal titanium sheet, and washing the metal titanium sheet to obtain a pre-treated Ti sheet for later use;
(2) preparing Ti-ZIF-67: the molar ratio of the raw materials is 1: preparing 12 parts of cobalt nitrate hexahydrate and dimethyl imidazole solution respectively, and pouring the dimethyl imidazole solution into the cobalt nitrate solution to obtain purple suspension liquid with an active ingredient of ZIF-67;
(3) and vertically placing the Ti sheet into the purple turbid liquid until the solution is submerged at the top of the Ti sheet, heating the Ti sheet in a water bath kettle at 60 ℃ in the air atmosphere for 24 hours, taking out the Ti sheet, repeatedly washing away the purple particles loaded with redundant surfaces by using absolute ethyl alcohol and deionized water, and then drying the Ti sheet in a drying oven at 60 ℃ to obtain the Ti-ZIF-67 electrochemical sensor.
Example 5
A Ti-ZIF-67 electrochemical sensor for detecting ammonium ions is prepared by the following steps, which are similar to the steps in the embodiment:
(1) pre-treating a base metal titanium sheet, namely cutting the metal titanium sheet into 1cm by 2cm, polishing two surfaces of the metal titanium sheet to be rough, soaking the metal titanium sheet in 10% dilute hydrochloric acid, absolute ethyl alcohol and deionized water respectively, performing ultrasonic treatment for 15 minutes, taking out the metal titanium sheet, and washing the metal titanium sheet to obtain a pre-treated Ti sheet for later use;
(2) preparing Ti-ZIF-67: the molar ratio of the raw materials is 1: preparing cobalt nitrate hexahydrate and a dimethyl imidazole solution respectively according to the ratio of 16, and pouring the dimethyl imidazole solution into the cobalt nitrate solution to obtain a purple suspension liquid with an active ingredient of ZIF-67;
(3) and vertically placing the Ti sheet into the purple turbid liquid until the solution is submerged at the top of the Ti sheet, heating the Ti sheet in a water bath kettle at 60 ℃ in the air atmosphere for 24 hours, taking out the Ti sheet, repeatedly washing away the purple particles loaded with redundant surfaces by using absolute ethyl alcohol and deionized water, and then drying the Ti sheet in a drying oven at 60 ℃ to obtain the Ti-ZIF-67 electrochemical sensor.
And (3) performing electrochemical sensing performance test by using a three-electrode system, and using a 0.1mol/L sodium sulfate solution as a working base solution. The three electrodes are respectively a working electrode, a reference electrode and a counter electrode. The working electrode is 1cm x 2cm Ti-ZIF-67 fixed on the electrode clamp; the reference electrode is a saturated calomel electrode; the counter electrode is a metal platinum electrode. Half of the working electrode was immersed in the solution during the test.
Application example
FIG. 1 selectivity test: the test is carried out by using an i-t Amperometric i-t Curve, the voltage is set to be 1.4V, after the current-time Curve is gentle, the ammonium chloride solution is dripped into the solution at 200s, and then sodium chloride, potassium chloride, sodium nitrate, potassium nitrate and ammonium chloride solutions with equal concentration are dripped into the solution at intervals of 50s when the current is gentle.
Fig. 2-5 optimize the voltage test: the test is carried out by using i-t Amperometrici-t Curve, ammonium chloride solution with equal concentration is used as an additive, different voltage values are used as independent variables, after a current-time Curve is gentle, ammonium chloride solution with equal concentration is dripped into the solution every 50s at 200s, and the ammonium chloride solution is dripped continuously for 5 times. FIG. 6 sensitivity test: the test is carried out by using i-t Amperometrici-t Curve, the voltage is set to be 1.4V, after the current-time Curve is gentle, the ammonium chloride solution is dripped into the solution every 50s at 200s, and the sensitivity is calculated according to the height of the step. The sensitivity is the magnitude of current value change caused by unit area reaction unit concentration detection solution.
Figure 7 stability test: testing by using i-t Amperometric i-t Curve, setting the voltage to be 1.4V, after the current-time Curve is gentle, dropwise adding ammonium chloride solution with equal concentration into the solution every 50s at 100s, wherein each dropwise adding 5 times is one test, the total test is 20 times, and the circulation reaches 100 times
Claims (8)
1. A preparation method of a Ti-ZIF-67 electrochemical sensor for detecting ammonium ions is characterized in that ZIF-67 is used as an active catalytic component, and comprises the following steps:
(1) pre-treating a base metal titanium sheet, namely cutting the metal titanium sheet into the size of 1cm by 2cm, polishing two sides of the metal titanium sheet, soaking the metal titanium sheet in 10% dilute hydrochloric acid, absolute ethyl alcohol and deionized water respectively, performing ultrasonic treatment for 15 minutes, taking out the metal titanium sheet, and washing the metal titanium sheet to obtain a pre-treated Ti sheet for later use;
(2) preparing Ti-ZIF-67: vertically fixing the Ti sheet at the bottom of a beaker to ensure that the loading capacity of the two sides of the Ti sheet is uniform and the same; preparing an active component ZIF-67 by using cobalt nitrate and dimethyl imidazole in a molar ratio of (1: 4) - (1: 16) to obtain a purple suspension;
(3) pouring the purple suspension into a pretreated Ti sheet beaker in advance until the solution is over the top of the Ti sheet, heating the solution in a 60 ℃ water bath for 24 hours, taking out the solution, repeatedly washing away the purple particles loaded on the surface by using absolute ethyl alcohol and deionized water, and then drying the solution in a 60 ℃ drying oven to obtain the Ti-ZIF-67 for later use.
2. The method of making a Ti-ZIF-67 electrochemical sensor for detecting ammonium ions for moats of claim 1, comprising the steps of:
(1) pre-treating a base metal titanium sheet, namely cutting the metal titanium sheet into 1cm by 2cm, polishing two surfaces of the metal titanium sheet to be rough, soaking the metal titanium sheet in 10% dilute hydrochloric acid, absolute ethyl alcohol and deionized water respectively, performing ultrasonic treatment for 15 minutes, taking out the metal titanium sheet, and washing the metal titanium sheet to obtain a pre-treated Ti sheet for later use;
(2) preparing Ti-ZIF-67: vertically fixing the Ti sheet at the bottom of a beaker to ensure that the loading capacity of the two sides of the Ti sheet is uniform and the same; the molar ratio of the raw materials is 1: respectively preparing cobalt nitrate hexahydrate and a dimethyl imidazole solution according to the ratio of 8, and pouring the dimethyl imidazole solution into the cobalt nitrate solution to obtain a purple suspension liquid with an active ingredient of ZIF-67;
(3) pouring the purple suspension into a pretreated Ti sheet beaker in advance until the solution is over the top of the Ti sheet, heating the solution in a water bath kettle at 60 ℃ in the air atmosphere for 24 hours, taking out the solution, repeatedly washing away the purple particles loaded on the surface by using absolute ethyl alcohol and deionized water, and then drying the solution in a drying oven at 60 ℃ to obtain the Ti-ZIF-67 electrochemical sensor.
3. The method of making a Ti-ZIF-67 electrochemical sensor for detecting ammonium ions for moats of claim 1, comprising the steps of:
(1) pre-treating a base metal titanium sheet, namely cutting the metal titanium sheet into 1cm by 2cm, polishing two surfaces of the metal titanium sheet to be rough, soaking the metal titanium sheet in 10% dilute hydrochloric acid, absolute ethyl alcohol and deionized water respectively, performing ultrasonic treatment for 15 minutes, taking out the metal titanium sheet, and washing the metal titanium sheet to obtain a pre-treated Ti sheet for later use;
(2) preparing Ti-ZIF-67: vertically fixing the Ti sheet at the bottom of a beaker to ensure that the loading capacity of the two sides of the Ti sheet is uniform and the same; the molar ratio of the raw materials is 1: preparing cobalt nitrate hexahydrate and a dimethyl imidazole solution respectively according to the ratio of 4, and pouring the dimethyl imidazole solution into the cobalt nitrate solution to obtain a purple suspension liquid with an active ingredient of ZIF-67;
(3) pouring the purple suspension into a pretreated Ti sheet beaker in advance until the solution is over the top of the Ti sheet, heating the solution in a water bath kettle at 60 ℃ in the air atmosphere for 24 hours, taking out the solution, repeatedly washing away the purple particles loaded on the surface by using absolute ethyl alcohol and deionized water, and then drying the solution in a drying oven at 60 ℃ to obtain the Ti-ZIF-67 electrochemical sensor.
4. The method of making a Ti-ZIF-67 electrochemical sensor for detecting ammonium ions for moats of claim 1, comprising the steps of:
(1) pre-treating a base metal titanium sheet, namely cutting the metal titanium sheet into 1cm by 2cm, polishing two surfaces of the metal titanium sheet to be rough, soaking the metal titanium sheet in 10% dilute hydrochloric acid, absolute ethyl alcohol and deionized water respectively, performing ultrasonic treatment for 15 minutes, taking out the metal titanium sheet, and washing the metal titanium sheet to obtain a pre-treated Ti sheet for later use;
(2) preparing Ti-ZIF-67: the molar ratio of the raw materials is 1: preparing cobalt nitrate hexahydrate and a dimethyl imidazole solution respectively according to the ratio of 6, and pouring the dimethyl imidazole solution into the cobalt nitrate solution to obtain a purple suspension liquid with an active ingredient of ZIF-67;
(3) and (3) putting the Ti sheet into the purple turbid liquid until the solution is submerged at the top of the Ti sheet, heating the Ti sheet in a water bath kettle at 60 ℃ in the air atmosphere for 24h, taking out the Ti sheet, repeatedly washing away the purple particles loaded with redundant surfaces by using absolute ethyl alcohol and deionized water, and then drying the Ti sheet in a drying oven at 60 ℃ to obtain the Ti-ZIF-67 electrochemical sensor.
5. The method of making a Ti-ZIF-67 electrochemical sensor for detecting ammonium ions for moats of claim 1, comprising the steps of:
(1) pre-treating a base metal titanium sheet, namely cutting the metal titanium sheet into 1cm by 2cm, polishing two surfaces of the metal titanium sheet to be rough, soaking the metal titanium sheet in 10% dilute hydrochloric acid, absolute ethyl alcohol and deionized water respectively, performing ultrasonic treatment for 15 minutes, taking out the metal titanium sheet, and washing the metal titanium sheet to obtain a pre-treated Ti sheet for later use;
(2) preparing Ti-ZIF-67: the molar ratio of the raw materials is 1: preparing 12 parts of cobalt nitrate hexahydrate and dimethyl imidazole solution respectively, and pouring the dimethyl imidazole solution into the cobalt nitrate solution to obtain purple suspension liquid with an active ingredient of ZIF-67;
(3) and vertically placing the Ti sheet into the purple turbid liquid until the solution is submerged at the top of the Ti sheet, heating the Ti sheet in a water bath kettle at 60 ℃ in the air atmosphere for 24 hours, taking out the Ti sheet, repeatedly washing away the purple particles loaded with redundant surfaces by using absolute ethyl alcohol and deionized water, and then drying the Ti sheet in a drying oven at 60 ℃ to obtain the Ti-ZIF-67 electrochemical sensor.
6. The method of making a Ti-ZIF-67 electrochemical sensor for detecting ammonium ions for moats of claim 1, comprising the steps of:
(1) pre-treating a base metal titanium sheet, namely cutting the metal titanium sheet into 1cm by 2cm, polishing two surfaces of the metal titanium sheet to be rough, soaking the metal titanium sheet in 10% dilute hydrochloric acid, absolute ethyl alcohol and deionized water respectively, performing ultrasonic treatment for 15 minutes, taking out the metal titanium sheet, and washing the metal titanium sheet to obtain a pre-treated Ti sheet for later use;
(2) preparing Ti-ZIF-67: the molar ratio of the raw materials is 1: preparing cobalt nitrate hexahydrate and a dimethyl imidazole solution respectively according to the ratio of 16, and pouring the dimethyl imidazole solution into the cobalt nitrate solution to obtain a purple suspension liquid with an active ingredient of ZIF-67;
(3) and vertically placing the Ti sheet into the purple turbid liquid until the solution is submerged at the top of the Ti sheet, heating the Ti sheet in a water bath kettle at 60 ℃ in the air atmosphere for 24 hours, taking out the Ti sheet, repeatedly washing away the purple particles loaded with redundant surfaces by using absolute ethyl alcohol and deionized water, and then drying the Ti sheet in a drying oven at 60 ℃ to obtain the Ti-ZIF-67 electrochemical sensor.
7. A Ti-ZIF-67 electrochemical sensor for detecting ammonium ions, prepared according to the method of any one of claims 1 to 6.
8. Use of the Ti-ZIF-67 electrochemical sensor of claim 7 for water quality testing for ammonium ion detection.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111338638.2A CN114184664B (en) | 2021-11-12 | Preparation method of Ti-ZIF-67 electrochemical sensor for detecting ammonium ions, product and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111338638.2A CN114184664B (en) | 2021-11-12 | Preparation method of Ti-ZIF-67 electrochemical sensor for detecting ammonium ions, product and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114184664A true CN114184664A (en) | 2022-03-15 |
| CN114184664B CN114184664B (en) | 2024-04-26 |
Family
ID=
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115112728A (en) * | 2022-06-30 | 2022-09-27 | 国纳纳米技术研究(河北)有限公司 | Preparation method of high-sensitivity electrochemical sensor for detecting hydrogen peroxide, product and application thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140083864A1 (en) * | 2012-09-21 | 2014-03-27 | Lonza, Inc. | Electrochemical sensors for testing water |
| CN105203612A (en) * | 2014-06-10 | 2015-12-30 | 中国科学院大连化学物理研究所 | Biosensor based on metal organic skeleton material and application thereof |
| CN105651826A (en) * | 2016-03-02 | 2016-06-08 | 李建中 | Ammonium ion concentration detecting system, method and application |
| CN109324099A (en) * | 2018-08-31 | 2019-02-12 | 盐城工学院 | A kind of volt-ampere of type ammonium ion electrochemica biological sensor and its preparation method and application |
| CN109507272A (en) * | 2018-11-16 | 2019-03-22 | 天津工业大学 | A kind of NiCoLDH@Au composite material based on ZIF-67 synthesis and its application in glucose sensor |
| CN110514729A (en) * | 2019-09-05 | 2019-11-29 | 吉林大学 | A kind of sensitive electrode and preparation method thereof detected for ammonia nitrogen Direct Electrochemistry in water |
| CN111239214A (en) * | 2020-03-25 | 2020-06-05 | 吉林大学 | Three-electrode type Pb (II) and Cu (II) electrochemical sensor, preparation method and application thereof |
| CN112362713A (en) * | 2020-11-24 | 2021-02-12 | 吉林大学 | Sensitive electrode material for direct electrochemical detection of ammonia nitrogen in water and preparation method thereof |
| CN112394095A (en) * | 2020-11-30 | 2021-02-23 | 江西农业大学 | Electrochemical sensor for selectively detecting nitrite ions and preparation method and application thereof |
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140083864A1 (en) * | 2012-09-21 | 2014-03-27 | Lonza, Inc. | Electrochemical sensors for testing water |
| CN105203612A (en) * | 2014-06-10 | 2015-12-30 | 中国科学院大连化学物理研究所 | Biosensor based on metal organic skeleton material and application thereof |
| CN105651826A (en) * | 2016-03-02 | 2016-06-08 | 李建中 | Ammonium ion concentration detecting system, method and application |
| CN109324099A (en) * | 2018-08-31 | 2019-02-12 | 盐城工学院 | A kind of volt-ampere of type ammonium ion electrochemica biological sensor and its preparation method and application |
| CN109507272A (en) * | 2018-11-16 | 2019-03-22 | 天津工业大学 | A kind of NiCoLDH@Au composite material based on ZIF-67 synthesis and its application in glucose sensor |
| CN110514729A (en) * | 2019-09-05 | 2019-11-29 | 吉林大学 | A kind of sensitive electrode and preparation method thereof detected for ammonia nitrogen Direct Electrochemistry in water |
| CN111239214A (en) * | 2020-03-25 | 2020-06-05 | 吉林大学 | Three-electrode type Pb (II) and Cu (II) electrochemical sensor, preparation method and application thereof |
| CN112362713A (en) * | 2020-11-24 | 2021-02-12 | 吉林大学 | Sensitive electrode material for direct electrochemical detection of ammonia nitrogen in water and preparation method thereof |
| CN112394095A (en) * | 2020-11-30 | 2021-02-23 | 江西农业大学 | Electrochemical sensor for selectively detecting nitrite ions and preparation method and application thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115112728A (en) * | 2022-06-30 | 2022-09-27 | 国纳纳米技术研究(河北)有限公司 | Preparation method of high-sensitivity electrochemical sensor for detecting hydrogen peroxide, product and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xiao et al. | TiO2 nanotube arrays fabricated by anodization in different electrolytes for biosensing | |
| CN108007998B (en) | Nickel oxide non-enzymatic glucose electrochemical sensor | |
| Gao et al. | Anatase TiO 2 based photoelectrochemical sensor for the sensitive determination of dopamine under visible light irradiation | |
| CN104192830A (en) | Preparing method of nitrogen-sulfur co-doped graphene by hydrothermal method | |
| CN104198551B (en) | Make Platinum Nanoparticles and the glass-carbon electrode of multi-walled carbon nano-tubes modification and the method using this electrode detection estradiol | |
| CN105203606A (en) | Preparation method and application of copper metal organic framework complex-based modified gold electrode | |
| CN104076077B (en) | A kind of nitrogen-doped titanium dioxide nanotube array enzyme electrode and its preparation method and application | |
| CN114113251A (en) | Preparation method of cobalt-based electrochemical sensor for stably detecting ammonium ions, product and application thereof | |
| CN109989070A (en) | Three-dimensional classification FeP nanometer sheet Electrocatalytic Activity for Hydrogen Evolution Reaction material and its preparation method and application | |
| CN104370943B (en) | A kind of [Cu2(HL)2(μ2-OH)2(H2o)5] preparation method and application | |
| CN107834079A (en) | A kind of implementation method for being used to improve aminic acid fuel battery electrooxidation activity | |
| Liu et al. | Simultaneous determination of vitamins B 2, B 6 and C using silver-doped poly (L-arginine)-modified glassy carbon electrode | |
| CN102706936B (en) | Preparation method of copper-copper oxide composite electrode | |
| CN102517604A (en) | Carbon-carrying core-shell type platinoid-platinum catalyst for indirect electrolytic hydrogen production and preparation method thereof | |
| CN114184664A (en) | Preparation method of Ti-ZIF-67 electrochemical sensor for detecting ammonium ions, product and application thereof | |
| CN114184664B (en) | Preparation method of Ti-ZIF-67 electrochemical sensor for detecting ammonium ions, product and application thereof | |
| CN108440578A (en) | A kind of two dimension Zn functional complexes and its preparation method and application | |
| CN111398379A (en) | Method for detecting tyrosine enantiomer by electrochemical chiral sensing | |
| CN107703203B (en) | Heavy metal detection device and detection method thereof | |
| CN110562956A (en) | Preparation method and application of ordered mesoporous carbon nanofiber array material | |
| CN111157594A (en) | Anatase phase titanium dioxide nanocone array COD sensor and preparation method thereof | |
| CN106044861B (en) | A kind of preparation method of three-dimensional branched nano material of manganese dioxide | |
| CN114538530A (en) | Basic cobalt carbonate nano material for electrochemical sensor and preparation method and application thereof | |
| CN114369241A (en) | Conductive polymer biosensor electrode material and preparation method and application thereof | |
| CN103412031A (en) | Reusable enzyme-free glucose detection device and method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |