An ultra-sensitive sensing material for rapid detection of biological hydrogen sulfide and a preparation method thereof
By preparing Cu2O/CNF heterostructure materials, an ultrasensitive detection of hydrogen sulfide gas was achieved at room temperature using an electrochemical method. This solved the problems of expensive equipment and insufficient accuracy in existing technologies, and realized low-cost, high-precision hydrogen sulfide detection.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- LINYI UNIVERSITY
- Filing Date
- 2023-01-31
- Publication Date
- 2026-06-19
AI Technical Summary
Existing methods for detecting hydrogen sulfide gas are expensive and complex, and their detection accuracy at room temperature is insufficient to meet the requirements for detecting hydrogen sulfide exhaled through the mouth, hindering their use in daily life.
Cu2O/CNF heterostructure materials were prepared by electrochemical methods. The heterostructure interface was formed at room temperature by electrodeposition growth. The heterostructure interface barrier was used to detect changes in carrier concentration, achieving ultrasensitive detection of hydrogen sulfide gas.
It enables accurate detection of hydrogen sulfide at the ppb level at room temperature, simplifies the detection process, reduces equipment costs, and improves detection accuracy.
Smart Images
Figure CN115950923B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of electrochemical technology, and in particular to an ultrasensitive sensing material for rapid detection of biological hydrogen sulfide and its preparation method. Background Technology
[0002] Hydrogen sulfide is a colorless, highly toxic gas with a rotten egg odor. It has also been proven to be a very important endogenous gas molecule. Exhaled hydrogen sulfide can serve as a trace biomarker for the early diagnosis of lung diseases, halitosis, and airway inflammation. Currently, the generally accepted standard in the medical community is that the concentration of hydrogen sulfide in the exhaled breath of healthy individuals is 8–16 ppb. However, its concentration can change significantly when a person has a disease; for example, it can be higher than 0.1 ppm in patients with halitosis. Therefore, the ability to quickly and conveniently detect exhaled hydrogen sulfide is of great significance for the early diagnosis of diseases in humans.
[0003] Existing technologies for detecting hydrogen sulfide gas concentration include spectroscopic detection, chromatographic detection, and metal oxide semiconductor sensors. Spectroscopic and chromatographic detection methods are complex, requiring expensive equipment and highly skilled technicians. For example, fluorescence spectrometry in spectroscopic detection requires collecting the gas with a specific solution and detecting it using a fluorescence spectrophotometer, which is expensive in itself, with high maintenance and repair costs. Furthermore, its detection accuracy is insufficient for detecting exhaled hydrogen sulfide. While existing metal oxide semiconductor sensors have attracted attention due to their low cost and simple fabrication process, most require high operating temperatures, and their detection accuracy is far from meeting the requirements for detecting the concentration of exhaled hydrogen sulfide, hindering their use in daily life.
[0004] Therefore, improving the detection limit for hydrogen sulfide at room temperature is of great significance for the diagnosis of early human diseases. Summary of the Invention
[0005] The purpose of this invention is to provide an ultrasensitive sensing material for rapid detection of biological hydrogen sulfide and its preparation method, thereby solving the problems existing in the prior art.
[0006] To achieve the above-mentioned objectives, the present invention provides the following technical solution:
[0007] This invention provides a method for preparing an ultrasensitive sensing material for rapid detection of biological hydrogen sulfide, comprising the following steps:
[0008] Two electrodes are placed on a substrate, then an electrolyte is added between the two electrodes, and a coverslip is placed on top. The temperature is controlled to freeze the electrolyte, and then a deposition voltage is applied between the two electrodes. After deposition, the sensing material is obtained.
[0009] The electrolyte comprises the following raw materials: copper nitrate, nitric acid, carbon nanofibers (CNF), and water.
[0010] Preferably, in the above-mentioned method for preparing an ultrasensitive sensing material for rapid detection of biological hydrogen sulfide, the electrode is a copper electrode with a thickness of 25-35 μm, and the ratio of the length of the copper electrode, the width of the copper electrode, the distance between the two electrodes, and the volume of the electrolyte is 2-2.5 cm: 1-2 mm: 10-15 mm: 20-40 μL.
[0011] Preferably, in the above-mentioned method for preparing an ultrasensitive sensing material for rapid detection of biological hydrogen sulfide, the two electrodes are positioned parallel to each other.
[0012] Preferably, in the above-mentioned method for preparing an ultrasensitive sensing material for rapid detection of biological hydrogen sulfide, the substrate is a glass plate or a quartz plate.
[0013] Preferably, in the above-mentioned method for preparing an ultrasensitive sensing material for rapid detection of biological hydrogen sulfide, the ratio of copper nitrate, nitric acid, carbon nanofibers, and water in the electrolyte is: 20-40 mmol / L: 48-68 μL: 0.0001-0.0005 g: 48-60 mL.
[0014] Preferably, in the above-mentioned method for preparing an ultrasensitive sensing material for rapid detection of biological hydrogen sulfide, the temperature is -2.5 to -1.6°C, and the freezing time is 10 to 20 minutes.
[0015] Preferably, in the above-mentioned method for preparing an ultrasensitive sensing material for rapid detection of biological hydrogen sulfide, the deposition voltage is a DC voltage of 0.7–1.2V, and the deposition time is 30–45 min.
[0016] The present invention also provides a sensing material prepared by the above-described method for preparing an ultrasensitive sensing material for rapid detection of biological hydrogen sulfide.
[0017] As can be seen from the above technical solution, compared with the prior art, the present invention has the following beneficial effects:
[0018] This invention successfully fabricates a Cu2O / CNF heterostructure material through targeted structural design and electrochemical methods. Carbon nanofibers, as an excipient, are grown via electrodeposition and bond with cuprous oxide to form a clear heterostructure interface, thereby creating a heterostructure barrier. Because this barrier is highly sensitive to changes in carrier concentration, the resistance changes drastically when the heterostructure comes into contact with hydrogen sulfide gas, converting the weak gas molecule signal into a significant electrical signal. The reaction of cuprous oxide at room temperature to form metallic copper sulfide also alters its conductivity. Therefore, through the synergistic effect of these two mechanisms, ultrasensitive sensing of hydrogen sulfide gas can be achieved at room temperature, enabling precise detection of hydrogen sulfide at the ppb level. Attached Figure Description
[0019] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below.
[0020] Figure 1 Scanning electron microscope image of the sensing material prepared in Example 1;
[0021] Figure 2 The dynamic response of the sensing material prepared in Example 1 to hydrogen sulfide gas at a concentration of 5 ppb is shown in the figure.
[0022] Figure 3 The graph shows the relationship between the response of the sensing material prepared in Example 1 to hydrogen sulfide gas and the concentration of hydrogen sulfide gas. Detailed Implementation
[0023] This invention provides a method for preparing an ultrasensitive sensing material for rapid detection of biological hydrogen sulfide, comprising the following steps:
[0024] Two electrodes are placed on a substrate, then an electrolyte is added between the two electrodes, and a coverslip is placed on top. The temperature is controlled to freeze the electrolyte, and then a deposition voltage is applied between the two electrodes. After deposition, the sensing material is obtained.
[0025] The electrolyte comprises the following raw materials: copper nitrate, nitric acid, carbon nanofibers, and water.
[0026] In this invention, the specific method for adding the electrolyte is: dropwise addition.
[0027] In this invention, the specific method for controlling the temperature is as follows: a circulating water bath is used to control the temperature.
[0028] In this invention, after the deposition is completed, the process further includes: removing the substrate, rinsing it with water 3 to 5 times, and then placing the substrate in a natural environment at room temperature to dry for 2 days.
[0029] In this invention, the electrode is preferably a copper electrode; the thickness of the copper electrode is preferably 25-35 μm, more preferably 25, 26, 28, 30, 32, 33 or 35 μm, and even more preferably 28 or 30 μm; the length of the copper electrode, the width of the copper electrode, the distance between the two electrodes, and the volume ratio of the electrolyte are preferably 2-2.5 cm: 1-2 mm: 10-15 mm: 20-40 μL, more preferably 2.1-2.4 cm: 1.2-1.8 mm: 11-14 mm: 22-36 μL, and even more preferably 2.3 cm: 1.5 mm: 13 mm: 30 μL.
[0030] In this invention, the two electrodes are preferably positioned parallel to each other.
[0031] In this invention, the substrate is preferably a glass sheet or a quartz sheet, more preferably a glass sheet.
[0032] In this invention, the preferred ratio of copper nitrate, nitric acid, carbon nanofibers, and water in the electrolyte is 20–40 mmol / L: 48–68 μL: 0.0001–0.0005 g: 48–60 mL, more preferably 22–36 mmol / L: 50–65 μL: 0.0002–0.0004 g: 50–58 mL, and even more preferably 32 mmol / L: 55 μL: 0.0003 g: 53 mL.
[0033] In this invention, the temperature is preferably -2.5 to -1.6°C, more preferably -2.5, -2.4, -2.2, -2.0, -1.8 or -1.6°C, and even more preferably -2.0 or -1.8°C; the freezing time is preferably 10 to 20 minutes, more preferably 10, 12, 14, 15, 16, 18 or 20 minutes, and even more preferably 15 or 16 minutes.
[0034] In this invention, the deposition voltage is preferably a DC voltage; the deposition voltage is preferably 0.7 to 1.2V, more preferably 0.7, 0.8, 0.9, 1.0, 1.1 or 1.2V, and even more preferably 0.9 or 1.0V; the deposition time is preferably 30 to 45 min, more preferably 30, 32, 34, 35, 36, 38, 40, 42 or 45 min, and even more preferably 38 or 40 min.
[0035] The present invention also provides a sensing material prepared by the above-described method for preparing an ultrasensitive sensing material for rapid detection of biological hydrogen sulfide.
[0036] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0037] Example 1
[0038] (1) Place two copper electrodes with a thickness of 30 μm, a length of 2 cm, and a width of 1 mm in parallel on an insulating growth substrate glass slide at the bottom of the growth chamber. The substrate is 20 mm wide and 20 mm long, and the gap between the two copper electrodes is 10 mm. Add 25 μL of electrolyte between the two copper electrodes, and then cover with a coverslip, ensuring that there are no air bubbles in the electrolyte between the coverslip and the substrate. The electrolyte consists of 20 mmol / L copper nitrate, 50 μL nitric acid, 0.0001 g carbon nanofibers, and 50 mL ultrapure water.
[0039] (2) The growth chamber was cooled and kept at -1.6℃ using a circulating water bath. After 15 minutes, the electrolyte formed a uniform ice layer. Then, a DC growth voltage of 0.7V was applied between the two copper electrodes to allow the cuprous oxide nanowires to begin deposition. After 30 minutes of deposition, the substrate was removed and rinsed three times with ultrapure water. The substrate was then placed in a natural environment at room temperature to dry for 2 days to obtain the sensing material attached to the substrate.
[0040] Scanning electron microscope images of the sensor material prepared above are shown below. Figure 1 As shown in the figure, carbon nanofibers are very prominent in the material and are tightly wrapped and grown together by cuprous oxide nanowires.
[0041] The dynamic response of the sensor material prepared above to hydrogen sulfide gas at a concentration of 5 ppb is shown in the figure below. Figure 2 As shown in the figure, the sensing material reacts very rapidly to low concentrations of hydrogen sulfide and exhibits a significant response, meaning that this sensing material can achieve rapid and accurate detection of hydrogen sulfide at the ppb level at room temperature.
[0042] The relationship between the response of the prepared sensing material to hydrogen sulfide gas and the concentration of hydrogen sulfide gas is shown in Figure 3. As can be seen from the figure, the relationship between its response and concentration can be divided into two segments, with 20 ppb as the inflection point, and each segment maintains a good linear relationship.
[0043] Example 2
[0044] (1) Place two copper electrodes with a thickness of 25 μm, a length of 2.2 cm, and a width of 1 mm in parallel on an insulating growth substrate glass slide at the bottom of the growth chamber. The substrate is 20 mm wide and 22 mm long, and the gap between the two copper electrodes is 12 mm. Add 30 μL of electrolyte between the two copper electrodes, then cover with a coverslip and ensure that there are no air bubbles in the electrolyte between the coverslip and the substrate. The electrolyte consists of 25 mmol / L copper nitrate, 65 μL nitric acid, 0.0003 g carbon nanofibers, and 65 mL ultrapure water.
[0045] (2) The growth chamber was cooled and kept at -2.0℃ using a circulating water bath. After 20 minutes, the electrolyte formed a uniform ice layer. Then, a DC growth voltage of 0.8V was applied between the two copper electrodes to allow the cuprous oxide nanowires to begin deposition. After 35 minutes of deposition, the substrate was removed and rinsed three times with ultrapure water. The substrate was then placed in a natural environment at room temperature to dry for 2 days to obtain the sensing material attached to the substrate.
[0046] Example 3
[0047] (1) Place two copper electrodes with a thickness of 30 μm, a length of 2 cm, and a width of 1 mm in parallel on an insulating growth substrate glass slide at the bottom of the growth chamber. The substrate is 20 mm wide and 20 mm long, and the gap between the two copper electrodes is 10 mm. Add 35 μL of electrolyte between the two copper electrodes, cover with a coverslip, and ensure that there are no air bubbles in the electrolyte between the coverslip and the substrate. The electrolyte consists of 35 mmol / L copper nitrate, 50 μL nitric acid, 0.0002 g carbon nanofibers, and 50 mL ultrapure water.
[0048] (2) The growth chamber was cooled and kept at -2.2℃ using a circulating water bath. After 12 minutes, the electrolyte formed a uniform ice layer. Then, a DC growth voltage of 1.2V was applied between the two copper electrodes to allow the cuprous oxide nanowires to begin deposition. After 30 minutes of deposition, the substrate was removed and rinsed three times with ultrapure water. The substrate was then placed in a natural environment at room temperature to dry for 2 days to obtain the sensing material attached to the substrate.
[0049] Example 4
[0050] (1) Place two copper electrodes with a thickness of 30 μm, a length of 2 cm, and a width of 1 mm in parallel on an insulating growth substrate glass slide at the bottom of the growth chamber. The substrate is 20 mm wide and 20 mm long, and the gap between the two copper electrodes is 10 mm. Add 32 μL of electrolyte between the two copper electrodes, cover with a coverslip, and ensure that there are no air bubbles in the electrolyte between the coverslip and the substrate. The electrolyte consists of 36 mmol / L copper nitrate, 60 μL nitric acid, 0.0005 g carbon nanofibers, and 60 mL ultrapure water.
[0051] (2) The growth chamber was cooled and kept at -2.5℃ using a circulating water bath. After 15 minutes, the electrolyte formed a uniform ice layer. Then, a DC growth voltage of 1.0V was applied between the two copper electrodes to allow the cuprous oxide nanowires to begin deposition. After 35 minutes of deposition, the substrate was removed and rinsed three times with ultrapure water. The substrate was then placed in a natural environment at room temperature to dry for 2 days to obtain the sensing material attached to the substrate.
[0052] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.
Claims
1. A method for preparing an ultrasensitive sensing material for rapid detection of biological hydrogen sulfide, characterized in that, Includes the following steps: Two electrodes are placed on a substrate, then an electrolyte is added between the two electrodes, and a coverslip is placed on top. The temperature is controlled to freeze the electrolyte, and then a deposition voltage is applied between the two electrodes. After deposition, the sensing material is obtained. The electrolyte comprises the following raw materials: copper nitrate, nitric acid, carbon nanofibers, and water; The concentration of copper nitrate in the electrolyte is 20~40 mmol / L; the ratio of nitric acid, carbon nanofibers and water in the electrolyte is 48~68µL: 0.0001~0.0005g: 48~60mL; The deposition voltage is a DC voltage, the deposition voltage is 0.7~1.2V, and the deposition time is 30~45min; The ultrasensitive sensing material used for rapid detection of biological hydrogen sulfide is based on a Cu2O / CNF heterostructure material.
2. The method for preparing the ultrasensitive sensing material for rapid detection of biological hydrogen sulfide according to claim 1, characterized in that, The electrode is a copper electrode with a thickness of 25~35µm. The ratio of the length of the copper electrode, the width of the copper electrode, the distance between the two electrodes, and the volume of the electrolyte is 2~2.5cm:1~2mm:10~15mm:20~40µL.
3. The method for preparing the ultrasensitive sensing material for rapid detection of biological hydrogen sulfide according to claim 1 or 2, characterized in that, The two electrodes are positioned parallel to each other.
4. The method for preparing the ultrasensitive sensing material for rapid detection of biological hydrogen sulfide according to claim 3, characterized in that, The substrate is a glass sheet or a quartz sheet.
5. The method for preparing the ultrasensitive sensing material for rapid detection of biological hydrogen sulfide according to claim 4, characterized in that, The temperature is -2.5 to -1.6℃, and the freezing time is 10 to 20 minutes.
6. The sensing material prepared by the method for preparing the ultrasensitive sensing material for rapid detection of biological hydrogen sulfide according to any one of claims 1 to 5.