CN113247869B - Preparation method of carbon nitride material, carbon nitride material prepared by preparation method and application of carbon nitride material - Google Patents
Preparation method of carbon nitride material, carbon nitride material prepared by preparation method and application of carbon nitride material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 89
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- -1 carbon nitrogen small molecules Chemical class 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 239000012472 biological sample Substances 0.000 claims abstract description 7
- 238000010306 acid treatment Methods 0.000 claims abstract description 5
- 238000001354 calcination Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 16
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 15
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 11
- 239000003446 ligand Substances 0.000 claims description 11
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 239000012621 metal-organic framework Substances 0.000 claims description 4
- 239000012300 argon atmosphere Substances 0.000 claims description 3
- 239000013168 zeolitic imidazolate framework-2 Substances 0.000 claims description 3
- 239000013169 zeolitic imidazolate framework-3 Substances 0.000 claims description 3
- 239000013172 zeolitic imidazolate framework-7 Substances 0.000 claims description 3
- 239000013174 zeolitic imidazolate framework-10 Substances 0.000 claims description 2
- 239000013175 zeolitic imidazolate framework-11 Substances 0.000 claims description 2
- 239000013176 zeolitic imidazolate framework-12 Substances 0.000 claims description 2
- 239000013155 zeolitic imidazolate framework-4 Substances 0.000 claims description 2
- 239000013170 zeolitic imidazolate framework-5 Substances 0.000 claims description 2
- 239000013171 zeolitic imidazolate framework-6 Substances 0.000 claims description 2
- 239000013173 zeolitic imidazolate framework-9 Substances 0.000 claims description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims 1
- 239000012535 impurity Substances 0.000 claims 1
- 239000002086 nanomaterial Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000007787 solid Substances 0.000 description 16
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 14
- 239000006228 supernatant Substances 0.000 description 11
- 239000000843 powder Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
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- 229960005070 ascorbic acid Drugs 0.000 description 7
- 235000010323 ascorbic acid Nutrition 0.000 description 7
- 239000011668 ascorbic acid Substances 0.000 description 7
- 239000008280 blood Substances 0.000 description 7
- 210000004369 blood Anatomy 0.000 description 7
- 230000005284 excitation Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 238000003763 carbonization Methods 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
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- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000004435 EPR spectroscopy Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000003574 free electron Substances 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- PXXJHWLDUBFPOL-UHFFFAOYSA-N benzamidine Chemical compound NC(=N)C1=CC=CC=C1 PXXJHWLDUBFPOL-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000017858 demethylation Effects 0.000 description 1
- 238000010520 demethylation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 239000012634 fragment Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000004776 molecular orbital Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
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- 229920000642 polymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
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- 238000002834 transmittance Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0605—Binary compounds of nitrogen with carbon
-
- 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
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/305—Electrodes, e.g. test electrodes; Half-cells optically transparent or photoresponsive electrodes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/86—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by NMR- or ESR-data
Abstract
The invention discloses a preparation method of a carbon nitride material, the carbon nitride material prepared by the preparation method and application thereof, and the preparation method comprises the following steps: calcining the precursor complex under the condition of inert atmosphere and high temperature to obtain a carbonized product; and (3) after the obtained carbonized product is subjected to acid treatment, washing with deionized water, centrifuging and drying to obtain the carbon nitride nanomaterial. The preparation method of the carbon nitride material is simple to operate, raw materials are easy to obtain, the prepared carbon nitride material with a novel five-membered ring structure overcomes the difficulty in thermodynamics and dynamics of the carbon nitride material prepared by taking five-membered ring carbon nitrogen small molecules as repeated units, has a very narrow energy band structure, can respond to near infrared light, can be effectively applied to the fields of photoelectrochemical biosensing and the like, and particularly can be applied to the photoelectrochemical biosensing of non-transparent biological samples.
Description
Technical Field
The invention relates to the technical field of material chemistry, in particular to a preparation method of a carbon nitride material, the carbon nitride material prepared by the method and application of the carbon nitride material.
Background
Carbon nitride is used as a novel graphite semiconductor material without metal elements, and has huge application prospects in the fields of small molecules, solar-chemical energy conversion, photoelectric biosensing and the like due to the unique molecular/electronic structure and surface properties, thereby being capable of inducing wide research interests. However, since the band gap of most of the carbon nitride materials reported so far is wide, the material is only responsive to ultraviolet light and part of visible light, which limits the utilization rate of the carbon nitride materials to sunlight; on the other hand, the application of materials in the fields of biosensing, infrared physiotherapy and the like is limited because short wavelength light (visible-ultraviolet light) has a poor light transmittance compared to long wavelength light. Therefore, the preparation of the carbon nitride material has important significance. However, currently, there is still a great challenge to adjusting the energy band structure of the carbon nitride material, and the absorption and utilization of sunlight are far from the practical requirements. Therefore, it is of great importance to develop a new method for preparing a carbon nitride material having a narrow band gap and an optical response range extending to the near infrared region.
Disclosure of Invention
The invention aims to: aiming at the problems existing in the prior art, the invention provides a preparation method of a carbon nitride material, and the method can prepare the carbon nitride nano material with a five-membered ring structure with a narrow band gap and near infrared light response.
The invention also provides the carbon nitride material prepared by the preparation method and application thereof.
The technical scheme is as follows: in order to achieve the above object, the preparation method of the carbon nitride material of the present invention comprises the following steps:
(1) Placing the precursor metal organic framework material in a crucible, and calcining under the inert atmosphere and high temperature conditions to obtain a carbonized product;
(2) And (3) performing acid treatment on the carbonized product obtained in the step (1), washing with deionized water, centrifuging and drying to obtain the carbon nitride material.
Wherein the precursor is a complex prepared from one or more five-membered ring ligands and metal ions.
Wherein the five-membered ring ligand comprises 2-methylimidazole or 1-methylimidazole, and the metal ion comprises Zn 2+ Or Co 2+ 。
Further, the complex includes ZIF-2, ZIF-3, ZIF-4, ZIF-5, ZIF-6, ZIF-10, ZIF-64, ZIF-8, ZIF-67, ZIF-7, ZIF-9, ZIF-11 or ZIF-12.
Wherein the inert atmosphere in the step (1) is nitrogen atmosphere or argon atmosphere. The gas flow rate is 100 mL/min-500 mL/min.
Wherein, the precursor in the step (1) is firstly placed in an inert atmosphere for 0.5 to 1.5 hours, and calcined under the high temperature condition, the temperature is raised to a specific temperature of 500 to 700 ℃ at a speed of 2 to 20 ℃ per minute, and the carbonization reaction is carried out for 0.5 to 5 hours. Preferably, the carbonization reaction is performed by raising the temperature to a specific temperature of 600 ℃ at a rate of 2 ℃ per minute to 10 ℃ per minute and maintaining the temperature for 3 hours.
Wherein, the acid treatment process in the step (2) is to put the black powdery carbonized product into concentrated hydrochloric acid for soaking for 10 to 24 hours.
Further, step (2) is washed to neutrality with deionized water, comprising: deionized water is added, ultrasonic treatment and centrifugation are carried out, the supernatant is taken to measure the pH value, and the operation is repeated until the pH value is close to 7 and is unchanged.
Further, the centrifugal speed in the step (2) is 13000rpm, and the centrifugal time is 5-10 minutes; the drying condition is that the vacuum drying is carried out at 50-120 ℃.
The carbon nitride material prepared by the preparation method of the carbon nitride material has five-membered ring basic units, and is a carbon nitride nano material with a five-membered ring structure.
The carbon nitride material prepared by the preparation method of the carbon nitride material is applied to photoelectrochemical sensing.
The carbon nitride material prepared by the preparation method of the carbon nitride material is applied to photoelectric biological sensing of a non-transparent biological sample.
The mechanism is as follows: at present, the preparation of carbon-nitrogen materials with five-membered ring carbon-nitrogen small molecules as repeated units has difficulty in thermodynamics and kinetics: such molecules typically have boiling points at 200 ℃ and it is difficult to reach polymerization temperatures (typically above 400 ℃) at which high polymers are formed; the five-membered ring has ring tension, and the product of six-membered ring is easier to form by high-temperature polymerization. The design principle of the invention is that the ligand is stabilized in advance by the stabilizing action of coordination bond formed by metal and ligand in the complex, the temperature during the disintegration of crystal is selected for polymerization, the coordination bond is opened at the moment, the ligand in the state of generating high-activity free radicals is easier to generate polymerization reaction, and the thermodynamic and kinetic difficulties are overcome. For example, FIG. 1 shows a thermogravimetric analysis of, for example, a metal organic framework material ZIF-8 and a ligand 2-methylimidazole constituting ZIF-8: the 2-methylimidazole crystal stabilized by intermolecular forces disintegrates at 185 ℃, while the ZIF-8 crystal stabilized by coordination bonds disintegrates markedly at 565 ℃. Thermogravimetric mass spectrometry analysis of fig. 2 also provides sufficient evidence that the ZIF-8 crystal disintegrates and simultaneously releases the free radical of the ligand 2-methylimidazole and the imidazole free radical and methane produced by the demethylation of 2-methylimidazole.
During the polymerization, unpaired electrons present in the free radical cannot pass through the formation of new chemical bondsComplete elimination, and thus a large number of unpaired electrons are present in such carbon nitrogen materials. C of repeating units with the most studied six-membered ring 3 N 4 In contrast, the electron paramagnetic resonance of the present invention (FIG. 3) demonstrates that the free electron number ratio C in the five-membered ring carbon nitride material is at the same mass 3 N 4 Two orders of magnitude higher. When there are a large number of unpaired electrons in the material, the molecular orbitals break up into alpha and beta orbitals due to the reduced symmetry. Electrons in the beta orbit absorb enough energy to transition into the infrared light so that the value of the optical band gap of such materials can be reduced by about 1eV (C 3 N 4 About 2.7 eV). FIG. 4 shows six-membered ring carbon nitride material C 3 N 4 And the photoelectric response of five-membered ring carbon nitride materials: in the presence of excitation light>At 420nm, the photocurrent of the five-membered ring carbon nitride material is up to C 3 N 4 More than 10 times of the total number of the components; and C when the excitation light is 808nm 3 N 4 The photocurrent has not been observed due to the inability to absorb the infrared light, while the five-membered ring carbon nitride material has a significant photoelectric response.
On the basis, the photoelectrode prepared by the prepared five-membered ring carbon nitride material successfully monitors the concentration of exogenous Ascorbic Acid (AA) in blood dynamically and in real time, which is the first realization of photoelectric detection in an opaque biological sample. Using the electrode shown in fig. 5, there was a significant increase in photocurrent each time exogenous ascorbic acid was added.
The invention synthesizes the carbon nitride with five-membered ring structure for the first time, the carbon nitride material in the prior art is all six-membered ring with repeated units, and the direct synthesis of the carbon nitride with five-membered ring structure has great difficulty, so the invention has great breakthrough, the invention directly takes the complex as a precursor, such as the carbon nitride with five-membered ring structure obtained by ZIF-8 carbonization, the preparation process is very simple, and the thermodynamic and kinetic difficulties of the carbon-nitrogen material prepared by five-membered ring carbon-nitrogen micromolecules with repeated units at present are effectively overcome.
The beneficial effects are that: compared with the prior art, the invention has the following advantages:
the invention provides a brand-new preparation method of a carbon nitride material, which has the advantages of simple and convenient preparation process, abundant raw material sources and low cost, and the prepared carbon nitride material is five-membered ring structured carbon nitride, has a very narrow energy band structure, is responsive to near infrared light, is more beneficial to development of application in photoelectrochemical biosensing and the like, and can be used for photoelectrobiosensing of non-transparent biological samples.
Drawings
FIG. 1 is a thermogravimetric analysis of the complex ZIF-8 and the ligand 2-methylimidazole constituting ZIF-8;
FIG. 2 is a thermogravimetric-mass spectrometry analysis of ZIF-8, (a) is methane, (b) is imidazole radical, and (c) is 2-methylimidazole radical;
FIG. 3 six-membered ring carbon nitride material C 3 N 4 And electron paramagnetic resonance intensity of the five-membered ring carbon nitride material;
FIG. 4 six-membered ring carbon nitride material C 3 N 4 And five-membered ring carbon nitride material are respectively arranged in>Photoelectric response at 420nm and 808nm excitation light, support electrolyte 0.1M KCl, applied bias voltage-0.3V (vs. Ag/AgCl electrode);
FIG. 5 is a photograph of an electrode used in an experiment, (a) an indium tin oxide electrode, (b) an indium tin oxide electrode modified with a five-membered ring carbon nitride material, and (c) a blood-coated electrode, wherein the experiment process uses the system in the third photograph;
FIG. 6 shows the photoelectric response of five-membered ring carbon nitride material after covering blood, at 808nm excitation light, with an applied bias of-0.5V (vs. indium tin oxide electrode).
Detailed Description
The invention is further described below with reference to specific embodiments and figures.
The experimental methods described in the examples, unless otherwise specified, are all conventional; the reagents and materials, unless otherwise specified, are commercially available.
Wherein: commercial ZIF-8 (particle size 100-400 nm) and ZIF-67 (particle size 300-600 nm) are available from Jiangsu Xianfeng nanomaterial technologies, inc., and the remaining MOF materials are available from Sian Ji Yue biotechnology, inc., or other commercially available materials.
Six-membered ring commercialized carbon nitride material C 3 N 4 Purchased from microphone, CAS:143334-20-7, cat: g862684 with purity not less than 95%.
Example 1
The preparation method of the carbon nitride material comprises the following specific operations:
(1) 30mg of commercial ZIF-8 (containing 2-methylimidazole, zn) was weighed out 2+ ) Placing the crucible in a 30mL ceramic crucible and covering a crucible cover, placing the crucible in a tubular furnace, introducing nitrogen for 1 hour at the gas flow rate of 500 mL/min, heating to 600 ℃ at the rate of 5 ℃/min under the nitrogen atmosphere, keeping for 3 hours, and naturally cooling to room temperature to obtain black powder.
(2) The black powder obtained in step (1) was placed in a sample bottle, 1ml of 38wt% hydrochloric acid was added dropwise, and the reaction was carried out for 24 hours.
(3) Adding deionized water into the mixture obtained in the step (2) for ultrasonic treatment, and centrifuging the obtained dispersion liquid at the speed of 13000rpm for 10 minutes.
(4) And (3) pouring out the supernatant, taking the solid, and repeating the operation of the step (3) until the pH value measured by the supernatant is close to 7 and is unchanged, and finally, keeping black solid.
(5) And (3) drying the black solid obtained in the step (4) in a vacuum drying oven at 110 ℃ for 12 hours to obtain the nano-sized carbon nitride material which is the five-membered ring carbon nitride material.
Thermogravimetric analysis of complex ZIF-8 and 2-methylimidazole, a ligand constituting ZIF-8 in step (1) as shown in fig. 1, from the second derivative of mass with respect to temperature, it was possible to determine that ZIF-8 was the starting position of the peak of loss mass at 565 ℃, and it was presumed that the crystal structure began to collapse at that temperature, and therefore this temperature was selected for carbonization. The thermogravimetric-mass spectrum of fig. 2 shows the molecular weight corresponding to the generated five-membered ring small molecular fragments, and confirms the five-membered ring carbon nitrogen small molecules generated in the decomposition process, which proves that the carbon nitride with the five-membered ring structure is synthesized for the second time, and the five-membered ring small molecules are generated at a proper carbonization temperature in the embodiment.
Using electron paramagnetic resonance instrumentsThe black solid obtained in the step (5) was tested (FIG. 3), and it was confirmed that the free electron number in the five-membered ring carbon nitride material prepared in the example 1 was higher than that of the six-membered ring commercialized carbon nitride material C under the same mass 3 N 4 Two orders of magnitude higher, such that the value of the optical band gap of such materials can be reduced by about 1eV (C 3 N 4 About 2.7 eV). FIG. 4 shows six-membered ring carbon nitride material C 3 N 4 And the photoelectric response of five-membered ring carbon nitride materials: in the presence of excitation light>At 420nm, the photocurrent of the five-membered ring carbon nitride material is up to C 3 N 4 More than 10 times of the total number of the components; and C when the excitation light is 808nm 3 N 4 Because the infrared light cannot be absorbed, no photocurrent is observed, and the five-membered ring carbon nitride material still has obvious photoelectric response, which indicates that the carbon nitride with the five-membered ring structure has response to near infrared light.
The five-membered ring carbon nitride material modified ITO prepared by the embodiment of the invention is used as a working electrode, and the other ITO electrode is used as a double-electrode system (figure 5) consisting of a pair/half reference electrode to dynamically and real-timely monitor the concentration of exogenous Ascorbic Acid (AA) in human whole blood. 100. Mu.L of blood (human whole blood) was dropped on five-membered ring carbon nitride modified ITO, and photoelectric sensing was performed in human whole blood, with a bias voltage of-0.5V to Ag/AgCl (saturated KCl solution) applied. Using the electrodes of fig. 5, the photo-electric signals were collected under the excitation of the laser light generated by the 808nm laser. As shown in FIG. 6, the enhanced photocurrent was linearly related to the concentration of exogenous ascorbic acid, with 20. Mu.M added every 100S, ranging from 20. Mu.M to 180. Mu.M, with a detection limit (3. Sigma./S) of 15.5. Mu.M, compared to the non-AA added blank. Furthermore, the fitted straight line has excellent linear correlation (R 2 =0.999), indicating a high accuracy and reliability in continuous monitoring. This is the first successful application of photo-biological sensing to non-transparent biological samples. Therefore, as an emerging narrow-bandgap semiconductor, the five-membered ring carbon nitride prepared by the method is applied to organisms, and has great potential in the aspect of realizing dynamic and real-time photoelectric biological sensing.
Example 2
(1) 30mg of commercial ZIF-7 (containing benzamidine) were weighedAzole, zn 2+ ) Placing the crucible in a 30mL ceramic crucible and covering a crucible cover, placing the crucible in a tubular furnace, introducing nitrogen for 0.5 hour at the gas flow rate of 200 mL/min, continuously heating to 610 ℃ at the speed of 2 ℃/min under the nitrogen atmosphere, keeping for 0.5 hour, and naturally cooling to room temperature to obtain black powder.
(2) The black powder obtained in step (1) was placed in a sample bottle, 1ml of 38wt% hydrochloric acid was added dropwise, and the reaction was carried out for 10 hours.
(3) Adding ionized water into the mixture obtained in the step (2) for ultrasonic treatment, and centrifuging the obtained dispersion liquid at a rotation speed of 5000rpm for 5 minutes.
(4) And (3) pouring out the supernatant, taking the solid, and repeating the operation of the step (3) until the pH value measured by the supernatant is close to 7 and is unchanged, and finally, keeping black solid.
(5) And (3) drying the black solid obtained in the step (4) in a vacuum drying oven at 110 ℃ for 12 hours to obtain the nano-sized carbon nitride material.
Example 3
(1) 30mg of commercial ZIF-67 (containing 2-methylimidazole, co) 2+ ) Placing the crucible in a 30mL ceramic crucible and covering a crucible cover, placing the crucible in a tubular furnace, introducing nitrogen for 0.5 hour at the gas flow rate of 200 mL/min, continuously heating to 550 ℃ at the speed of 10 ℃/min under the nitrogen atmosphere, keeping for 1.5 hours, and naturally cooling to room temperature to obtain black powder.
(2) The black powder obtained in step (1) was placed in a sample bottle, 1ml of 38wt% hydrochloric acid was added dropwise, and the reaction was carried out for 20 hours.
(3) Adding ionized water to the mixture obtained in the step (2) for ultrasonic treatment, and centrifuging the obtained dispersion liquid at the rotating speed of 13000rpm for 2 hours.
(4) And (3) pouring out the supernatant, taking the solid, and repeating the operation of the step (3) until the pH value measured by the supernatant is close to 7 and is unchanged, and finally, keeping black solid.
(5) And (3) drying the black solid obtained in the step (4) in a vacuum drying oven at 110 ℃ for 12 hours to obtain the nano-sized carbon nitride material.
Example 4
(1) 30mg of commercial ZIF-2 (containing imidazole, zn) 2+ ) Device for placing articlesAnd (3) putting the crucible into a 30mL ceramic crucible, covering a crucible cover, putting the crucible into a tubular furnace at a gas flow rate of 100 mL/min, introducing argon for 1.5 hours, continuously heating to 500 ℃ at a rate of 2 ℃/min under the argon atmosphere, keeping for 5 hours, and naturally cooling to room temperature to obtain black powder.
(2) The black powder obtained in step (1) was placed in a sample bottle, 1ml of 38wt% hydrochloric acid was added dropwise, and the reaction was carried out for 10 hours.
(3) Adding deionized water into the mixture obtained in the step (2) for ultrasonic treatment, and centrifuging the obtained dispersion liquid at the speed of 13000rpm for 5 minutes.
(4) And (3) pouring out the supernatant, taking the solid, and repeating the operation of the step (3) until the pH value measured by the supernatant is close to 7 and is unchanged, and finally, keeping black solid.
(5) And (3) drying the black solid obtained in the step (4) in a vacuum drying oven at 50 ℃ for 20 hours to obtain the nano-sized carbon nitride material.
Example 5
(1) 30mg of commercial ZIF-3 (containing imidazole, zn) 2+ ) Placing the crucible in a 30mL ceramic crucible and covering a crucible cover, placing the crucible in a tubular furnace, introducing nitrogen for 1 hour at the gas flow rate of 500 mL/min, continuously heating to 700 ℃ at the speed of 20 ℃/min under the nitrogen atmosphere, keeping for 1.5 hours, and naturally cooling to room temperature to obtain black powder.
(2) The black powder obtained in step (1) was placed in a sample bottle, 1ml of 38wt% hydrochloric acid was added dropwise, and the reaction was carried out for 15 hours.
(3) Adding deionized water into the mixture obtained in the step (2) for ultrasonic treatment, and centrifuging the obtained dispersion liquid at the speed of 13000rpm for 10 minutes.
(4) And (3) pouring out the supernatant, taking the solid, and repeating the operation of the step (3) until the pH value measured by the supernatant is close to 7 and is unchanged, and finally, keeping black solid.
(5) And (3) drying the black solid obtained in the step (4) in a vacuum drying oven at 120 ℃ for 10 hours to obtain the nano-sized carbon nitride material.
Comparative example 1
Comparative example 1 was prepared in the same manner as in example 1, except that: the imidazole or 2-methylimidazole is directly used for heating polymerization, and the five-membered ring carbon nitride material can not be obtained because the boiling point of the five-membered ring carbon nitride material is too low and can be completely volatilized at 200 ℃.
Claims (8)
1. The preparation method of the five-membered ring structured carbon nitride material for photoelectric biological sensing of a non-transparent biological sample is characterized by comprising the following steps:
(1) Calcining the precursor complex under the condition of inert atmosphere and high temperature to obtain a carbonized product;
(2) Performing acid treatment on the carbonized product obtained in the step (1), removing impurities, washing with deionized water, centrifuging and drying to obtain a carbon nitride material;
the precursor is a complex prepared from one or more five-membered ring ligands and metal ions; the five-membered ring ligand comprises imidazole, 2-methylimidazole or benzimidazole, and the metal ion comprises Zn 2+ Or Co 2+ ；
The calcination was carried out at a high temperature to raise the temperature to 600℃at a rate of 2℃per minute to 10℃per minute, and maintained for 3 hours.
2. The method of claim 1, wherein the complex comprises metal organic framework material ZIF-2, ZIF-3, ZIF-4, ZIF-5, ZIF-6, ZIF-10, ZIF-64, ZIF-8, ZIF-67, ZIF-7, ZIF-9, ZIF-11, or ZIF-12.
3. The method of producing a carbon nitride material according to claim 1, wherein the inert atmosphere in step (1) is a nitrogen atmosphere or an argon atmosphere.
4. The method of producing a carbon nitride material according to claim 1, wherein the precursor in step (1) is first placed in an inert atmosphere for 0.5 to 1.5 hours, and the high temperature condition is calcined to raise the temperature to 600 ℃ at a rate of 2 to 10 ℃/min, and is maintained for 3 hours.
5. The method of producing a carbon nitride material according to claim 1, wherein the acid treatment in step (2) is performed by immersing the carbonized product in concentrated hydrochloric acid for 10 hours to 24 hours.
6. A carbon nitride material prepared by the method of preparing a carbon nitride material according to claim 1, wherein the carbon nitride material has five-membered ring basic units.
7. Use of a carbon nitride material prepared by the method for preparing a carbon nitride material according to claim 1 in photoelectrochemical sensing.
8. Use of a carbon nitride material prepared by the method for preparing a carbon nitride material according to claim 1 in photoelectric biosensing of a non-transparent biological sample.
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