CN108872204B - Preparation and application of two-dimensional porous graphene/cuprous oxide composite material - Google Patents

Preparation and application of two-dimensional porous graphene/cuprous oxide composite material Download PDF

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CN108872204B
CN108872204B CN201810389934.7A CN201810389934A CN108872204B CN 108872204 B CN108872204 B CN 108872204B CN 201810389934 A CN201810389934 A CN 201810389934A CN 108872204 B CN108872204 B CN 108872204B
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cuprous oxide
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CN108872204A (en
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陈佳
邱洪灯
李湛
王莉
黄艳妮
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Lanzhou Institute of Chemical Physics LICP of CAS
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Abstract

The invention discloses a preparation method of a two-dimensional porous graphene/cuprous oxide composite material, which comprises the steps of adding copper chloride dihydrate into aqueous dispersion of graphene oxide, carrying out ultrasonic treatment for 5-30 min, and carrying out suction filtration to obtain a mixture of copper chloride and graphene oxide; then placing the mixture in an oven at 40-60 ℃ for drying, and then placing the mixture in a muffle furnace for calcining to obtain a crude product; and (3) repeatedly washing the crude product with water and absolute ethyl alcohol, and drying to obtain the two-dimensional porous graphene/cuprous oxide composite material. In a chemiluminescence system generated by oxidizing luminol with hydrogen peroxide, the composite material has a good linear relationship between logarithmic values of chemiluminescence intensity concentration at 425 nm, and the linear range is 1.0 multiplied by 10‑8 M~8.0×10‑4 Therefore, the compound has wide application prospect in the fields of catalysis, biochemical analysis and detection and the like.

Description

Preparation and application of two-dimensional porous graphene/cuprous oxide composite material
Technical Field
The invention relates to a preparation method of a two-dimensional porous graphene/cuprous oxide composite material, which is mainly used as a catalyst for catalyzing oxydol to oxidize luminol to generate a chemiluminescence reaction and belongs to the field of composite materials and the technical field of biological detection.
Background
Luminol, also known as luminol, the name British 5-Amino-2, 3-dihydro-1, 4-phthalazinedione. It is a yellow crystal or beige powder at normal temperature, and is a relatively stable chemical reagent. Meanwhile, luminol is a strong acid and has certain stimulation effect on eyes, skin and respiratory tract. In forensic science, the luminol reaction is called aminobenzoyl-hydrazine reaction, and blood marks which are long before scrubbing can be identified. Luminol is used biologically to detect the presence of copper, iron and cyanide in cells. Luminol was synthesized as early as 1853. In 1928, chemists first discovered that this compound has a wonderful property that it emits blue light when oxidized. Several years later, it has been thought to use this property to detect blood traces. Blood contains hemoglobin, and oxygen inhaled from the air is transported to all parts of the body by the protein. Hemoglobin contains iron, which catalyzes the decomposition of hydrogen peroxide, converting hydrogen peroxide into water and singlet oxygen, which reoxidizes luminol to make it glow. In the examination of blood stains, luminol reacts with heme (a protein in hemoglobin responsible for oxygen transport) to give blue-green fluorescence. The detection method is extremely sensitive, can detect blood with a content of only one millionth, and can detect even a small drop of blood into a large vat of water.
Luminol emits light only after treatment with an oxidizing agent. A mixed aqueous solution of hydrogen peroxide and a hydroxide base is generally used as the activator. Under the catalysis of iron compounds, hydrogen peroxide is decomposed into oxygen and water: 2H2O2→ O2 + 2 H2And O. Potassium ferricyanide is often used in the laboratory as a source of iron catalyst, while the forensic catalyst is precisely the iron in hemoglobin. Enzymes in many biological systems can also catalyze the decomposition reaction of hydrogen peroxide. The nano material has catalytic enzyme-like performance and can be used for catalyzing hydrogen peroxide (H)2O2) Oxidative Luminol (Luminol) produces chemiluminescence. Cu was used in document 1 (Nano Lett. 2017, 17, 2043 to 2048)2+GO nano-particles to catalyze the oxidation of luminol by hydrogen peroxide to generate chemiluminescence, but Cu is used2+Concentration of-GO nanoparticles 10 μ g mL−1The linear range of the hydrogen peroxide is 0 to 1.5 multiplied by 10-3 M; document 2 (ACS Nano 2017, 11, 3247-3253) uses Cu2+-g-C3N4The nano particles are used as a catalyst to catalyze the luminol to be oxidized by hydrogen peroxide to generate chemiluminescence, and the concentration of the used material is 5.0 mu g mL−1The results show that the hydrogen peroxide is 0 to 2 multiplied by 10-3There is a good linear relationship in the M range. However, the nanoparticles Cu reported in documents 1 and 22+-GO、Cu2+-g-C3N4The luminol is oxidized by the catalytic hydrogen peroxide to generate chemiluminescence which can only be generated in the range of 0-2 multiplied by 10 times of the hydrogen peroxide-3M is effective in the range of M.
Disclosure of Invention
The invention aims to provide a preparation method of a two-dimensional porous graphene/cuprous oxide composite material;
the invention also aims to provide the prepared two-dimensional porous graphene/cuprous oxide composite material as a catalyst for catalyzing hydrogen peroxide (H)2O2) Oxidation of Luminol (Luminol) produces a chemiluminescent reaction.
Preparation of (I) two-dimensional porous graphene/cuprous oxide composite material
The method for preparing the two-dimensional porous graphene/cuprous oxide composite material comprises the steps of adding copper chloride dihydrate into aqueous dispersion of graphene oxide, performing ultrasonic treatment for 5-30 min, and performing suction filtration to obtain a mixture of copper chloride and graphene oxide; drying the mixture in an oven at 40-60 ℃, then putting the dried mixture on an alcohol lamp for ignition, and repeatedly burning until brick-red porous graphene covered by cuprous oxide appears to obtain a crude product; or placing the mixture in a drying oven at 40-60 ℃ for drying, then placing the mixture in a muffle furnace, and calcining for 1-5 min at 420-450 ℃ to obtain a crude product; and washing the crude product with water and absolute ethyl alcohol to remove impurities, and drying to obtain the two-dimensional porous graphene/cuprous oxide composite material.
The concentration of the graphene oxide dispersion liquid is 1-10 g/L; the mass ratio of the copper chloride dihydrate to the graphene oxide is 100: 1-800: 1.
Structure of (II) porous graphene/cuprous oxide composite material
1. Transmission Electron Microscopy (TEM) and elemental mapping
For the two-dimensional porous graphene/cuprous oxide composite material, the appearance needs to be observed by using a transmission electron microscope. Fig. 1A is a Transmission Electron Microscope (TEM) of a two-dimensional porous graphene/cuprous oxide composite. It can be seen that a large amount of cuprous oxide particles exist on the surface of the graphene, and a large amount of two-dimensional nanopores (represented by white dots) exist on the surface of the graphene. Fig. 1B is a dark field STEM diagram of a two-dimensional porous graphene/cuprous oxide composite material, and fig. 1C-F are element mapping diagrams of corresponding elements in the composite material. Wherein C: C-K; d: O-K; e: Cu-K; f: Cu-L. As can be seen from fig. 1B and fig. 1C-F, the composite material mainly includes C, O, Cu three elements.
2. Energy spectrum (EDX) diagram
Fig. 2 is an EDX diagram of a two-dimensional porous graphene/cuprous oxide composite. As can be seen from the spectrum, the material is composed of C, O, Cu three elements, and the result is also completely consistent with the element mapping diagram in FIGS. 1C-F.
3. X-ray photoelectron spectroscopy (XPS) full and fine spectra
Fig. 3A is an XPS survey of a two-dimensional porous graphene/cuprous oxide composite, also illustrating that the two-dimensional porous graphene/cuprous oxide composite consists essentially of C, O and Cu. FIG. 3B is C1SFrom the fine spectrum of (A), it was confirmed that C-C (sp) was present in the composite material3，284.6 eV), C−O (sp2286.0 eV) and C = O (sp)2287.8 eV) bond, FIG. 3C is O1SThe two peaks of the fine spectrum at 530.7 eV and 531.7 eV respectively correspond to the Cu in the composite material2O lattice oxygen and hydroxyl oxygen on the surface of the composite material, wherein a spectrum peak at 532.8 eV corresponds to a C-OH/C-O-C bond in the composite material or the lattice oxygen of copper oxide; FIG. 3D is Cu2pWherein the peaks at 952.6 eV and 932.7 eV correspond to Cu 2p of cuprous oxide in the composite material3/2And Cu 2p1/2The peaks, at 934.6 and 953.7 eV, demonstrate the presence of a small amount of copper oxide.
4. XRD pattern
FIG. 4 is an XRD (X-ray diffraction) pattern of a two-dimensional porous graphene/cuprous oxide composite material, and it can be seen from the XRD pattern that the content of reduced graphene oxide is 21.2o(002) crystal face of the porous graphene/cuprous oxide composite material (NPG/Cu)2O) is present. In addition, the composite material has a series of typical diffraction peaks at 29.4, 36.4, 42.2, 61.3, 73.6 and 77.3 degrees, which respectively correspond to the (110), (111), (200), (220), (311) and (222) crystal planes of the cubic nano cuprous oxide in the composite material, and the peaks are sharp and have stronger diffraction intensity, which shows that the crystallinity is better.
5. Raman spectrum
Fig. 5 is a raman spectrum of the composite material. From the Raman spectrumIt was found that D-, G-and 2D/G' -bands of graphene were also present in the composite material, in addition at 124 cm−1，147 cm−1，218 cm−1And 628 cm−1The band of (B) proves Cu2The presence of O.
(III) performance of two-dimensional porous graphene/cuprous oxide composite material
Fig. 6 is a comparison of catalytic performance of a two-dimensional porous graphene/cuprous oxide composite material with that of pure cuprous oxide, two-dimensional porous graphene, and reductive graphene oxide/cuprous oxide composite materials. Wherein (i) lumineol (0.5mM) + H2O2(7 mM)； (ii) luminol (0.5 mM)+ H2O2 (7mM)+ Cu2O (5.0 μg mL−1)； (iii) luminol (0.5 mM)+ H2O2 (7mM)+NPG(5.0μg mL−1)；(iv) luminol(0.5mM)+H2O2(7mM)+ rGO/Cu2O nanocomposite (5.0μg mL−1)； (v) luminol (0.5mM)+H2O2 (7mM)+ NPG/Cu2O nanocomposite (5.0μg mL−1). As can be seen from fig. 6, the two-dimensional porous graphene/cuprous oxide composite material prepared by the method has the optimal catalytic performance.
The catalytic schematic of the composite material prepared by the present invention is shown in fig. 7. The catalysis principle is as follows: the two-dimensional porous graphene/cuprous oxide composite material serves as a peroxide mimic enzyme and has a catalytic effect. Under an alkaline condition, the two-dimensional porous graphene/cuprous oxide composite material can catalyze hydrogen peroxide to oxidize luminol to generate excited phthalate anions, and when the two-dimensional porous graphene/cuprous oxide composite material is transited to a ground state, light radiation is generated at 425 nm.
FIG. 8 is a chemiluminescence spectrogram (A) and H of a two-dimensional porous graphene/cuprous oxide composite material catalyzing oxydol to oxidize luminol2O2Standard graph (B). In FIG. A, NPG/Cu2The concentration of the O composite material is 5.0 mug mL−1The concentration of luminol is 0.5mM, curves a to k correspond to H2O2Are 0, 0.05, 0.1, 0.2, 0.5, 0.8, 1, 2, 3, 5 and 7 Mm, respectively. It can be seen from FIG. 8A thatThe catalytic performance of the composite material is gradually enhanced along with the increase of the concentration of the hydrogen peroxide. As can be seen from FIG. 8B, the system has a good linear relationship between the chemiluminescence intensity at 425 nm and the concentration of hydrogen peroxide, and the linear range is 0-7 × 10-3 M。
In addition, in a two-dimensional porous graphene/cuprous oxide composite material-luminol-hydrogen peroxide catalytic system, reduced Nicotinamide Adenine Dinucleotide (NADH) is introduced at the same time, and the chemiluminescence intensity of the system is gradually weakened. FIG. 9 is a schematic diagram of NADH detection. The possible reasons are two-fold: (1) the chemiluminescence spectrum of the luminol is partially overlapped with the absorption spectrum of NADH, so that chemiluminescence resonance energy transfer exists between the luminol and the NADH; (2) after NADH is added, the composite material can catalyze hydrogen peroxide to oxidize luminol to generate chemiluminescence and can catalyze hydrogen peroxide to oxidize NADH to generate NAD+The latter process also consumes a portion of the hydrogen peroxide, so the chemiluminescence intensity detected at 425 nm decreases with increasing NADH concentration.
FIG. 10 is a chemiluminescence spectrogram (A) of a two-dimensional porous graphene/cuprous oxide composite material-hydrogen peroxide-luminol system after NADH with different concentrations is added and a standard curve chart (B) of NADH. In FIG. A, NPG/Cu2The concentration of the O composite material is 5.0 mug mL−1The concentration of luminol is 0.5mM, H2O2Was 7 mM, and the concentrations of NADH corresponding to curves a to l were 0, 0.01, 0.02, 0.05, 0.2, 2, 5, 20, 50, 80, 200 and 800. mu.M, respectively. From FIG. 10A, it can be seen that the chemiluminescence intensity of the system gradually decreased as the concentration of NADH increased. As can be seen from FIG. 10B, the system exhibited a good linear relationship between the chemiluminescence intensity at 425 nm and the logarithmic value of NADH concentration, with a linear range of 1.0X 10-8 M~8.0×10-4 M, the detection range has obvious advantages compared with the results reported in the literature.
In conclusion, the two-dimensional porous graphene/cuprous oxide composite material prepared by the invention has the advantages that a large number of two-dimensional nano-scale holes and cuprous oxide nano-cubes are distributed on the surface, the specific surface area is larger, the activity is higher, and the two-dimensional porous graphene/cuprous oxide composite material has a very wide application prospect in the fields of catalysis, biochemical analysis and detection and the like.
Drawings
Fig. 1 is an electron microscope characterization image of a two-dimensional porous graphene/cuprous oxide composite material, wherein a is a TEM image of the two-dimensional porous graphene/cuprous oxide composite material; b is a dark field STEM diagram of the two-dimensional porous graphene/cuprous oxide composite material; C-F is an element mapping diagram of corresponding elements in the composite material.
Fig. 2 is an EDX diagram of a two-dimensional porous graphene/cuprous oxide composite.
FIG. 3 shows XPS full spectrum and C of two-dimensional porous graphene/cuprous oxide composite material1S、O1S、Cu2pFine spectrum of (2). Fig. 4 is an XRD pattern of the two-dimensional porous graphene/cuprous oxide composite material.
Fig. 5 is a raman spectrum of a two-dimensional porous graphene/cuprous oxide composite material.
Fig. 6 is a comparison of catalytic performance of a two-dimensional porous graphene/cuprous oxide composite material with that of pure cuprous oxide, two-dimensional porous graphene, and reductive graphene oxide/cuprous oxide composite materials.
Fig. 7 is a catalysis schematic diagram of chemiluminescence generated by two-dimensional porous graphene/cuprous oxide composite material catalyzing oxydol to oxidize luminol.
FIG. 8 is a chemiluminescence spectrogram (A) and H of a two-dimensional porous graphene/cuprous oxide composite material catalyzing oxydol to oxidize luminol2O2Standard graph (B).
FIG. 9 is a schematic diagram of NADH detection.
FIG. 10 is a chemiluminescence spectrogram (A) of a two-dimensional porous graphene/cuprous oxide composite material-hydrogen peroxide-luminol system after NADH with different concentrations is added and a standard curve chart (B) of NADH.
Detailed Description
The preparation method, the catalysis and the detection performance of the two-dimensional porous graphene/cuprous oxide composite material are further explained by the specific embodiment.
Example 1
And ultrasonically dispersing graphene oxide in water to prepare 2.5 g/L graphene oxide dispersion liquid. And (3) taking 8.0 mL of 2.5 g/L graphene oxide dispersion liquid, and carrying out normal-temperature ultrasonic treatment for 15 min. 2.0 g of copper chloride dihydrate was weighed, dissolved in the above dispersion, and subjected to ultrasonic treatment at room temperature for 10 min. Performing suction filtration, drying the mixture in a drying oven at 60 ℃, putting the dried mixture in a muffle furnace at 430 ℃, and burning for 2 min to see that brick-red porous graphene covered by cuprous oxide appears, namely a crude product; and washing the crude product with ultrapure water for 5 times, washing with ethanol for 3 times, removing impurities and drying to obtain the two-dimensional porous graphene/cuprous oxide composite material. The chemiluminescence catalytic performance of the two-dimensional porous graphene/cuprous oxide composite material is completely consistent with the result shown in fig. 9.
Example 2
And ultrasonically dispersing graphene oxide in water to prepare 1.0 g/L graphene oxide dispersion liquid. Taking 10.0 mL of 1.0 g/L graphene oxide dispersion liquid, and carrying out normal-temperature ultrasonic treatment for 10 min. 2.5 g of copper chloride dihydrate was weighed, dissolved in the dispersion, and sonicated at room temperature for 15 min. Performing suction filtration, drying the mixture in a 50 ℃ oven, placing the dried mixture in a 450 ℃ muffle furnace, and burning for 1min to see that brick red cuprous oxide covered porous graphene appears, namely a crude product; and washing the crude product with ultrapure water for 5 times, washing with ethanol for 3 times, removing impurities and drying to obtain the two-dimensional porous graphene/cuprous oxide composite material. The chemiluminescence catalytic performance of the two-dimensional porous graphene/cuprous oxide composite material is basically consistent with the result shown in example 1.
Example 3
And ultrasonically dispersing graphene oxide in water to prepare 1.0 g/L graphene oxide dispersion liquid. Taking 50.0 mL of 1.0 g/L graphene oxide dispersion liquid, and carrying out ultrasonic treatment at normal temperature for 20 min. 16.0 g of copper chloride dihydrate was weighed, dissolved in the above dispersion, and subjected to ultrasonic treatment at room temperature for 30 min. Performing suction filtration, drying the mixture in a 60 ℃ drying oven, placing the dried mixture in a 420 ℃ muffle furnace, and burning for 5 min to see that brick red cuprous oxide covered porous graphene appears, namely a crude product; and washing the crude product with ultrapure water for 10 times, washing with ethanol for 3 times, removing impurities and drying to obtain the two-dimensional porous graphene/cuprous oxide composite material. Compared with the results of example 1, the chemiluminescence catalytic performance of the two-dimensional porous graphene/cuprous oxide composite material is slightly reduced.
Example 4
And ultrasonically dispersing graphene oxide in water to prepare 5.0 g/L graphene oxide dispersion liquid. Taking 2.0 mL of graphene oxide dispersion liquid, and carrying out ultrasonic treatment at normal temperature for 5 min; weighing 1.6 g of copper chloride dihydrate, dissolving in the dispersion, and performing ultrasonic treatment at room temperature for 20 min; performing suction filtration, then placing the mixture in a drying oven at 40 ℃, igniting the mixture by using an alcohol lamp, and repeatedly burning the mixture until brick-red cuprous oxide-covered porous graphene appears to be a crude product; and washing the crude product with ultrapure water for 5 times, washing with ethanol for 3 times, removing impurities and drying to obtain the two-dimensional porous graphene/cuprous oxide composite material. Compared with the results of example 1, the chemiluminescence catalytic performance of the two-dimensional porous graphene/cuprous oxide composite material is remarkably reduced.
Example 5
And ultrasonically dispersing graphene oxide in water to prepare 10.0 g/L graphene oxide dispersion liquid. Taking 1.0 mL of 10.0 g/L graphene oxide dispersion liquid, and carrying out normal-temperature ultrasonic treatment for 5 min. Weighing 4.0 g of copper chloride dihydrate, dissolving the copper chloride dihydrate in 7 mL of ultrapure water, uniformly mixing the solution with the graphene oxide dispersion liquid, and carrying out ultrasonic treatment at room temperature for 30 min. Performing suction filtration, then placing the mixture in a drying oven at 50 ℃, igniting the mixture by using an alcohol lamp, and repeatedly burning the mixture until brick-red cuprous oxide-covered porous graphene appears to be a crude product; and washing the crude product with ultrapure water for 5 times, washing with ethanol for 3 times, removing impurities and drying to obtain the two-dimensional porous graphene/cuprous oxide composite material. Compared with the results of example 3, the chemiluminescence catalytic performance of the two-dimensional porous graphene/cuprous oxide composite material is slightly reduced.
Example 6
And ultrasonically dispersing graphene oxide in water to prepare 5.0 g/L graphene oxide dispersion liquid. Taking 2.0 mL of 5.0 g/L graphene oxide dispersion liquid, and carrying out normal-temperature ultrasonic treatment for 5 min. Weighing 2.0 g of copper chloride dihydrate, dissolving the copper chloride dihydrate in 6 mL of ultrapure water, uniformly mixing the solution with the graphene oxide dispersion liquid, and carrying out ultrasonic treatment at room temperature for 5 min. Performing suction filtration, then placing the mixture in a drying oven at 60 ℃, igniting the mixture by using an alcohol lamp, and repeatedly burning the mixture until brick-red cuprous oxide-covered porous graphene appears to be a crude product; and washing the crude product with ultrapure water for 5 times, washing with ethanol for 3 times, removing impurities and drying to obtain the two-dimensional porous graphene/cuprous oxide composite material. The chemiluminescence catalytic performance of the two-dimensional porous graphene/cuprous oxide composite material is basically consistent with the result shown in example 1.
According to the embodiment, in the process of preparing the composite material, the mass ratio of the copper chloride dihydrate to the graphene oxide is controlled to be within the range of 100: 1-800: 1, and the optimal concentration of the copper chloride dihydrate is 250 g/L, above which the catalytic performance of the copper chloride dihydrate is weakened; the calcining temperature in the muffle furnace is controlled to be 420-450 ℃, and in order to achieve a better analysis effect, the combustion time is gradually reduced along with the increase of the temperature in the range.

Claims (4)

1. A preparation method of a two-dimensional porous graphene/cuprous oxide composite material comprises the steps of adding copper chloride dihydrate into graphene oxide aqueous dispersion, carrying out ultrasonic treatment for 5-30 min, and carrying out suction filtration to obtain a mixture of copper chloride and graphene oxide; placing the mixture in a drying oven at 40-60 ℃ for drying, then igniting the mixture by using an alcohol lamp for repeated combustion until porous graphene covered by brick red cuprous oxide appears to obtain a crude product, or placing the mixture in the drying oven at 40-60 ℃ for drying, and then placing the mixture in a muffle furnace for calcining to obtain the crude product; washing the crude product to remove impurities, and drying to obtain the two-dimensional porous graphene/cuprous oxide composite material; the mass ratio of the copper chloride dihydrate to the graphene oxide is 100: 1-800: 1; the calcination in the muffle furnace is carried out for 1 min-5 min at the temperature of 420-450 ℃.
2. The preparation method of the two-dimensional porous graphene/cuprous oxide composite material according to claim 1, characterized by comprising the following steps: the concentration of the graphene oxide aqueous dispersion is 1-10 g/L.
3. The preparation method of the two-dimensional porous graphene/cuprous oxide composite material according to claim 1, characterized by comprising the following steps: the washing is repeated washing with water and absolute ethyl alcohol.
4. The application of the two-dimensional porous graphene/cuprous oxide composite material prepared by the method of claim 1 as a catalyst to catalyze luminol oxidation by hydrogen peroxide to generate a chemiluminescence reaction.
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CN109908866B (en) * 2019-03-28 2021-12-31 中国科学院兰州化学物理研究所 Method for preparing two-dimensional magnetic porous carbon composite material through calcination and application thereof
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