CN113398970A - ZnO nanowire array/three-dimensional nitrogen-doped rGO nanotube composite material and preparation method and application thereof - Google Patents
ZnO nanowire array/three-dimensional nitrogen-doped rGO nanotube composite material and preparation method and application thereof Download PDFInfo
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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Abstract
The invention provides a ZnO nanowire array/three-dimensional nitrogen-doped rGO nanotube composite material and a preparation method and application thereof, wherein the preparation method comprises the following steps: preparing a graphene oxide suspension by taking graphite powder as a raw material; pretreating melamine sponge, soaking the pretreated melamine sponge in a graphene oxide suspension, drying the graphene oxide composite sponge, and calcining for the first time to obtain 3 DN-rGO; dispersing zinc acetate in ethanol to form a mixed solution A, soaking 3DN-rGO in the mixed solution A, and carrying out secondary calcination to form ZnO seed crystal N-rGO; mixing zinc nitrate, urea and hexamethylenetetramine to form a mixed solution B, soaking ZnO seed crystal N-rGO in the mixed solution B, and carrying out hydrothermal treatmentAnd (3) reacting, namely, rinsing the reaction product and then calcining for the third time to obtain the ZnO nanowire array/three-dimensional nitrogen-doped rGO nanotube composite material. The composite material prepared by the invention shows excellent photocatalytic activity and simultaneously has good CO2The adsorption performance is good when the catalyst is used for photocatalytic reduction of carbon dioxide.
Description
Technical Field
The invention relates to the technical field of semiconductor photocatalytic reduction of carbon dioxide, in particular to a ZnO nanowire array/three-dimensional nitrogen-doped rGO nanotube composite material and a preparation method and application thereof.
Background
With the large consumption of fossil fuels, the energy crisis and the greenhouse effect are the two most critical problems on earth in the 21 st century, and the search for renewable clean energy is urgent and necessary to guarantee the long-term development of human society. Among them, photocatalytic reduction of carbon dioxide is an effective means for reducing the level of carbon dioxide and simultaneously generating CH3OH and CH4And the like. However, photocatalytic reduction of CO2High electron-hole recombination rate, high reduction driving force requirement, and CO2The problems of low absorption capacity, low light utilization efficiency and the like still greatly limit the practical application of the light-absorbing material. In particular electron transfer to CO2To realize CO2The process of activation is also difficult to achieve.
Since the discovery of graphene gf (graphene) in 2004, such two-dimensional (2D) sp2The hybrid material has been widely used in photocatalytic applications due to its special physicochemical properties, and in particular, the successful preparation of a three-dimensional (3D) graphene framework containing macropores and an interconnected network further stimulated the research interest in this field. The interconnected structure of the 3D graphene framework not only maintains the excellent inherent properties of the 2D graphene nanoparticles, but also makes it possible to couple semiconductor nanoparticles in such a 3D structure.
The introduction of foreign atoms into the graphene lattice can cause the distortion of electron spin density and charge redistribution on the graphene, so that a unique "activation region" is formed on the surface of the graphene, and can be used as an active center of a photocatalytic reaction. Among various dopants, nitrogen is a neighboring element of carbon and is easily doped, so that nitrogen-doped graphene has attracted wide attention, and doped nitrogen can be used for adsorbing CO2The basic center of the molecule improves the absorption performance of carbon dioxide. Therefore, the nitrogen-doped three-dimensional graphene framework is expected to become an ideal cocatalyst and carrier, and is coupled with a semiconductor photocatalyst to enhance CO2Adsorption and photocatalytic Properties of。
Disclosure of Invention
In view of the above, the invention aims to provide a ZnO nanowire array/three-dimensional nitrogen-doped rGO nanotube composite material and a preparation method thereof, so as to solve the problem of low efficiency of the existing photocatalytic reduction of carbon dioxide.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a preparation method of a ZnO nanowire array/three-dimensional nitrogen-doped rGO nanotube composite material comprises the following steps:
s1, preparing a graphene oxide suspension by taking graphite powder as a raw material;
s2, dipping the pretreated melamine sponge into the graphene oxide suspension to obtain graphene oxide composite sponge, drying the graphene oxide composite sponge, calcining for the first time, and removing a polymer template to obtain three-dimensional nitrogen-doped reduced graphene oxide 3 DN-rGO;
s3, dispersing zinc acetate in ethanol to form a mixed solution A, soaking 3DN-rGO in the mixed solution A, and carrying out secondary calcination to form ZnO seed crystal N-rGO;
s4, mixing zinc nitrate, urea and hexamethylenetetramine to form a mixed solution B, soaking the ZnO seed crystal N-rGO in the mixed solution B, uniformly stirring, carrying out hydrothermal reaction, rinsing a reaction product, carrying out third calcination, and carrying out post-treatment to obtain the ZnO nanowire array/three-dimensional nitrogen-doped rGO nanotube composite material.
In the above technical solution, optionally, in S1, the concentration of the graphene oxide suspension is 2.3 g/L.
In the above technical solution, optionally, in S2, the pretreatment is to wash the melamine sponge with ethanol, and then dry the melamine sponge at 80 ℃ for 12 hours.
In the above technical solution, optionally, in S2, the calcination temperature of the first calcination is 500-.
In the above technical solution, optionally, in S3, the mass ratio of the zinc acetate to the 3DN-rGO is 0.1-20%, the calcination temperature of the second calcination is 190-210 ℃, and the calcination time is 18-22 min.
In the above technical solution, optionally, in S4, the molar ratio of the zinc nitrate, the urea, and the hexamethylenetetramine is (0.1-1): (0.1-1): (0.1-1).
In the above technical scheme, optionally, in S4, the hydrothermal reaction temperature is 60-120 ℃, and the reaction time is 10-14 h.
In the above technical solution, optionally, in S4, the calcination temperature of the third calcination is 440-460 ℃, and the calcination time is 1-1.5 h.
The invention also aims to provide a ZnO nanowire array/three-dimensional nitrogen-doped rGO nanotube composite material, which is prepared by adopting the preparation method of the ZnO nanowire array/three-dimensional nitrogen-doped rGO nanotube composite material, wherein the composite material comprises a 3D nitrogen-doped rGO nanotube framework and a ZnO nanowire array growing on the surface of the 3D nitrogen-doped rGO nanotube framework, the 3D nitrogen-doped rGO nanotube framework is of a net-shaped porous structure, and the ZnO nanowire array is vertically arranged and covered on the surface of the 3D nitrogen-doped rGO nanotube framework.
The third purpose of the invention is to provide the application of the ZnO nanowire array/three-dimensional nitrogen-doped rGO nanotube composite material in the field of photocatalytic reduction of carbon dioxide.
Compared with the prior art, the ZnO nanowire array/three-dimensional nitrogen-doped rGO nanotube composite material and the preparation method and application thereof have the following advantages:
(1) the invention adopts the 3DN-rGO nanotube framework, is beneficial to the uniform growth of the ZnO nanotube, can effectively improve the separation of electron-hole pairs, and can be used as CO2Thereby promoting CO by in situ growth of ZnO nanowire arrays on 3DN-rGO2Activation and reduction of (2).
(2) The ZnO nanowire array/three-dimensional nitrogen-doped rGO nanotube composite material prepared by the invention shows excellent photocatalytic activity and simultaneously has good CO2Adsorption property, promotes the separation of photon-generated carriers, and is used for the catalysis of the photocatalytic reduction of carbon dioxideThe effect is good.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, a brief description will be given below to the drawings required for the description of the embodiments or the prior art, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without inventive exercise.
FIG. 1(a) is an XRD pattern of GO, N-RGO, ZnO/N-RGO and ZnO as described in examples of the present invention; FIG. 1(b) is a TG curve of melamine foam, N-rGO, ZnO/N-rGO and ZnO; FIG. 1(c) is a Raman spectrum of GO, NrGO, ZnO/N-RGO and ZnO; FIG. 1(d) ATR-FTIR spectra for GO and N-rGO;
FIG. 2 is a graph of the nitrogen adsorption-desorption isotherms and corresponding pore size distribution curves (inset) for ZnO, ZnO/N-rGO and N-rGO according to an embodiment of the present invention;
FIG. 3 shows the CO pair of ZnO, ZnO/N-rGO, GO and N-rGO in the embodiment of the present invention2Adsorption isotherms of (a);
FIG. 4(a) is an XPS measurement spectrum of N-rGO, ZnO/N-rGO and ZnO (A) according to an embodiment of the present invention; FIGS. 4(b) - (d) are high resolution XPS spectra of C1s, N1b, Zn2p for different samples, respectively; FIG. 4(e) is the bonding configuration of the N atom in N-rGO;
FIG. 5(a) is a graph of photocatalytic CO of N-rGO, pure ZnO, ZnO/N-rGO and commercial ZnO (c-ZnO) under 300W xenon lamp illumination2Reduction of CH3OH performance comparison graph; FIG. 5(b) is a schematic view of13CO2And12CO2CH generated on ZnO/N-rGO sample as carbon source3GC-MS spectrum of OH;
FIG. 6(a) is a schematic diagram of the three-dimensional porous structure of ZnO/N-rGO according to an embodiment of the present invention; FIG. 6(b) is a diagram of ZnO/N-rGO photocatalytic CO in accordance with an embodiment of the present invention2The reduction strengthening mechanism is shown schematically.
Detailed Description
The principles and features of this invention are described below in conjunction with specific embodiments, the examples given are intended to illustrate the invention and are not intended to limit the scope of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict. The terms "comprising," "including," "containing," and "having" are intended to be inclusive, i.e., that additional steps and other ingredients may be added without affecting the result.
The invention provides a preparation method of a ZnO nanowire array/three-dimensional nitrogen-doped rGO nanotube composite material, which comprises the following steps:
s1, preparing a graphene oxide suspension by taking graphite powder as a raw material;
s2, dipping the pretreated melamine sponge into a graphene oxide suspension to obtain a graphene oxide composite sponge, drying the graphene oxide composite sponge, calcining for the first time, and removing a polymer template to obtain three-dimensional nitrogen-doped reduced graphene oxide 3 DN-rGO;
s3, mixing zinc acetate Zn (CH)3COO)2·2H2Dispersing O in ethanol to form a mixed solution A, soaking 3DN-rGO in the mixed solution, and carrying out secondary calcination to form zinc oxide ZnO seed crystal N-rGO;
s4, mixing zinc nitrate Zn (NO)3)2.6H2Mixing O, urea and Hexamethylenetetramine (HMTA) to form a mixed solution B, soaking ZnO seed crystal N-rGO in the mixed solution B, uniformly stirring, carrying out hydrothermal reaction, rinsing a reaction product, carrying out third calcination, and carrying out post-treatment to obtain the ZnO nanowire array/three-dimensional nitrogen-doped rGO nanotube composite material.
According to the invention, the three-dimensional nitrogen-doped reduced graphene oxide 3DN-rGO is used as a framework, so that the uniform growth of the ZnO nanotube is facilitated, the separation of electron-hole pairs can be effectively improved, and the carbon dioxide can be used as CO2Adsorption and reduction of active centres (N-centres for pyrrole and pyridine). CO can thus be promoted by in-situ growth of ZnO nanowire arrays (ZnO NWAS) on 3DN-rGO2Activation and reduction of (2). The invention is madeThe preparation method is simple and easy to copy, and simultaneously proves that the N-rGO is a promising photo-reduction CO2The multifunctional cocatalyst is suitable for popularization.
Specifically, in step S1, a Graphene Oxide (GO) suspension is prepared from natural graphite powder by an improved Hummers method, and the concentration of the graphene oxide suspension is 2.3 g/L. In addition, 80% ethanol was added to the suspension to ensure uniform calcination during subsequent preparation.
In step S2, the pretreatment is to wash the melamine sponge with ethanol, dry the washed melamine sponge at 80 ℃ for 12h, and calcine the melamine sponge at 500-600 ℃ for 2.5-3.5 min.
The method specifically comprises the following steps: washing melamine sponge with ethanol for 3 times under the ultrasonic condition, drying at 80 ℃ for 12h, then soaking the melamine sponge in graphene oxide suspension for multiple times of pressurization to ensure the saturated absorption of GO in the melamine sponge, then calcining the melamine sponge with ethanol flame (about 550 ℃) for 3min, and removing the polymer template to obtain 3 DN-rGO.
In the step S3, the mass ratio of zinc acetate to 3DN-rGO is (0.1% -20%); the calcination temperature of the second calcination is 190-210 ℃, the calcination time is 18-22min, preferably, the calcination temperature is 200 ℃, and the calcination time is 20 min.
In step S4, zinc nitrate Zn (NO)3)2.6H2The molar ratio of O, urea and hexamethylenetetramine is (0.1-1): (0.1-1): (0.1-1). The temperature of the hydrothermal reaction is 60-120 ℃, the reaction time is 10-14h, preferably, the temperature of the hydrothermal reaction is 100 ℃, and the reaction time is 12 h. The calcination temperature of the third calcination is 440-460 ℃, and the calcination time is 1-1.5h, preferably, the calcination temperature of the third calcination is 450 ℃ and the calcination time is 1 h.
The invention also aims to provide a ZnO nanowire array/three-dimensional nitrogen-doped rGO nanotube composite material, which is prepared by adopting the preparation method of the ZnO nanowire array/three-dimensional nitrogen-doped rGO nanotube composite material.
The ZnO nanowire array/three-dimensional nitrogen-doped rGO nanotube composite material comprises a 3D nitrogen-doped rGO nanotube framework and a ZnO nanowire array growing on the surface of the 3D nitrogen-doped rGO nanotube framework, wherein the 3D nitrogen-doped rGO nanotube framework is of a net-shaped porous structure, and the ZnO nanowire array is vertically arranged and covered on the surface of the 3D nitrogen-doped rGO nanotube framework.
The ZnO nanowire array/three-dimensional nitrogen-doped rGO nanotube composite material prepared by the invention shows excellent photocatalytic activity and simultaneously has good CO2The adsorption performance promotes the separation of photon-generated carriers, and the catalytic effect for photocatalytic reduction of carbon dioxide is good.
The third purpose of the invention is to provide the application of the ZnO nanowire array/three-dimensional nitrogen-doped rGO nanotube composite material in the aspect of photocatalytic reduction of carbon dioxide.
On the basis of the above embodiments, the present invention is further illustrated below by combining a preparation method based on a ZnO nanowire array/three-dimensional nitrogen-doped rGO nanotube composite material and performance analysis. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are examples of experimental procedures not specified under specific conditions, generally according to the conditions recommended by the manufacturer. Unless otherwise indicated, percentages and parts are by mass.
Example 1
The embodiment provides a preparation method of a ZnO nanowire array/three-dimensional nitrogen-doped rGO nanotube composite material, which comprises the following steps:
1) graphite powder is used as a raw material, an improved Hummers method is adopted to prepare graphene oxide suspension liquid with the concentration of 2.3g/L, and 80% ethanol is added;
2) washing melamine sponge with ethanol, drying at 80 ℃ for 12h, soaking in graphene oxide suspension, and calcining with ethanol flame at about 550 ℃ for 3min to obtain 3 DN-rGO;
3) 220mg of Zn (CH)3COO)2·2H2Dispersing O in 100mL of ethanol to form a mixed solution A, soaking 10mg of 3DN-rGO in the solution for 0.5h, and then calcining at 200 ℃ for 20min to form a seed layer of zinc oxide ZnO nanoparticles (namely ZnO seed N-rGO);
s4, soaking ZnO seed crystal N-rGO in 50mL of mixed solution B consisting of 0.75g of zinc nitrate, 0.31g of urea and 0.35g of hexamethylenetetramine, transferring the mixed solution B into a 100mL stainless steel autoclave lined with Teflon, carrying out hydrothermal reaction for 12 hours at 100 ℃, rinsing the autoclave with deionized water, and calcining the rinsed autoclave for 1 hour at 450 ℃ to remove residual organic compounds, thereby obtaining the ZnO nanowire array/three-dimensional nitrogen-doped rGO nanotube composite material.
Performance analysis was performed on the ZnO nanowire array/three-dimensional nitrogen-doped rGO nanotube composite material prepared in example 1.
FIG. 1(a) is an XRD spectrum of GO, N-RGO, ZnO/N-RGO and ZnO, and a Cu-Ka light source is adopted to perform phase structure analysis on a prepared sample by using a D/Max-2500 type X-ray diffractometer.
From fig. 1(a), it can be seen that the X-ray diffraction pattern of GO has a main peak at about 2 q-10 °, corresponding to a lattice spacing of about 0.9 nm. After flame heat treatment with ethanol, this peak disappeared, and a new broad diffraction peak appeared around 24 °, indicating that GO was efficiently reduced to rGO. For pure zinc oxide, there are several characteristic diffraction peaks corresponding to hexagonal phase ZnO, and after combining with N-rGO, the characteristic peaks of ZnO can be clearly observed, but because of the lower content of N-rGO, no diffraction peak of N-rGO is observed in the figure.
FIG. 1(b) is a TG curve of melamine foam, N-rGO, ZnO/N-rGO and ZnO; thermogravimetric analysis (TGA) was carried out using FC-60A (Shimadzu Japan) in air at 10 ℃ for min-1The temperature rise rate of (3).
As can be seen from fig. 1(b), melamine starts to decompose at about 400 ℃. Thus, the calcination temperature of the ethanol flame (about 550 ℃) is high enough to disintegrate the melamine foam template and generate N-containing material, inducing the formation of N-doped rGO nanotubes with a 3D framework. The weight loss of the ZnO sample was negligible, while the weight loss of the ZnO/N-rGO composite sample was about 4.0 wt.%, indicating that the ZnO/N-rGO sample contained about 4.0 wt.% of N-rGO.
To further confirm the presence of the carbon material on the ZnO/N-rGO catalyst, raman spectroscopy was performed. FIG. 1(c) is a Raman spectrum of GO, NrGO, ZnO/N-RGO and ZnO with 633nm Ar+A raman spectrum of the sample was obtained using a raman spectrometer (manufactured by Renishaw invia, UK) with a laser as an excitation light source.
As can be seen in FIG. 1(c), the Raman spectrum of N-rGO is around 1350cm-1And 1600cm-1There are two main peaks, corresponding to disordered sp respectively2Carbon (D band) and ordered graphite (G band). Furthermore, the D/G intensity ratio of the N-rGO samples increased (from 0.93 to 1.04) compared to the GO precursor, indicating a reduction in GO, these two characteristic peaks of rGO being clearly observable in ZnO/N. In addition, the ZnO can be detected at 436cm on the composite sample-1(E2) The presence of N-rGO and ZnO is further confirmed.
FIG. 1(d) ATR-FTIR spectra of GO and N-rGO, with attenuated Total reflectance fluorescence transfer Infrared Spectroscopy (ATR-FTIR) analysis of GO and N-rGO functional groups. As can be seen in FIG. 1(d), for GO, 1723cm-1、1620cm-1、1374cm-1、1223cm-1And 1027cm-1Peaks of (a) may be assigned to C ═ O, aromatic C ═ C groups, carboxyl groups C-O, epoxide/ether groups C-O-C, and alkoxy/alkoxy groups C-OH stretching vibrations, respectively. However, all of these non-sp2The carbon bonds were either reduced or disappeared after ethanol flame treatment, which means that GO was reduced to rGO, the successful formation of N-doped rGO.
The ZnO nanowire array/three-dimensional nitrogen-doped rGO nanotube composite material prepared in example 1 was used to perform adsorption performance analysis.
FIG. 2 is a plot of the nitrogen adsorption-desorption isotherms and corresponding pore size distribution curves for ZnO, ZnO/N-rGO and N-rGO. The nitrogen adsorption-desorption isotherms for all samples were type IV, indicating the presence of mesopores, according to the Brunauer-Deming-teller (bddt) classification. Furthermore, all samples had slit-like pores in the high pressure range of 0.8-1.0, due to stacking of graphene nanoplatelets and crossing of ZnO nanowires. At high pressure (P/P0) (close to 1.0), the isotherms of all samples showed higher adsorption, which means that large mesopores and macropores were formed. Wherein, the aperture of ZnO/N-rGO is mainly distributed at about 40nm, which is caused by the hierarchical structure formed on the surface of ZnO/N-rGO.
TABLE 1 specific surface area (SBET), pore volume and CO2 adsorption for ZnO, N-rGO and ZnO/N-rGO samples
Table 1 calculates the specific surface area, pore volume and CO2 adsorption capacity of ZnO, N-rGO and ZnO/N-rGO samples, and it can be seen from Table 1 that the ZnO/N-rGO has the highest BET specific surface area and pore volume due to the unique three-dimensional porous framework structure, so that enough active centers can be provided, and charge transfer and diffusion kinetics are facilitated, thereby improving the photocatalytic performance.
FIG. 3 shows ZnO, ZnO/N-rGO, GO and N-rGO vs. CO2Adsorption isotherm of (1). As can be seen from FIG. 3, pure zinc oxide exhibits very low CO due to its low specific surface area and poor surface properties2Adsorption capacity; GO shows higher CO due to a two-dimensional layered structure with abundant functional groups on the surface2Adsorption capacity; N-rGO shows stronger CO than GO2Adsorption capacity, which can be attributed to the sp content in N-rGO22D planes of bonded carbon atoms and a unique 3D porous skeletal structure. In addition, the alkalinity of the carbonaceous metal ore can be further improved by N doping, and Lewis-acid (CO) is used for improving the alkalinity of the carbonaceous metal ore2) the/Lewis-base (N atom) interaction serves to anchor the CO2The alkaline site function of (3); ZnO/N-rGO composite material pair CO2Has stronger adsorption capacity and is beneficial to CO2Molecular activation and photocatalytic CO2Acceleration of the reduction reaction.
To analyze the change in surface chemical composition and electron density of the samples, X-ray photoelectron spectroscopy measurements were performed on an ESCALAB 250Xi electron spectrometer using Al K α as the light source.
FIG. 4(a) is XPS measurement spectra of N-rGO, ZnO/N-rGO and ZnO (A) as described in examples of the present invention, FIGS. 4(b) - (d) are high resolution XPS spectra of C1s, N1b, Zn2p, respectively, for different samples, FIG. 4 demonstrates the presence of elements in the N-rGO, ZnO/N-rGO and ZnO samples, and the spectra of C and N clearly demonstrate that N has been successfully doped into the RGO lattice. The mode of doping N atoms is shown in fig. 4 (e).
Compared with pure N-rGO, the combination energy of pyridine type N, pyrrole type N and graphite type N in ZnO/N-rGO moves to the direction of low combination energy, which shows that the electron density of N-rGO is increased. Furthermore, as shown in FIG. 4(d), the opposite shifts of Zn2p and N1s in ZnO/N-rGO reveal the transfer of electrons from ZnO to N-RGO, and these results clearly demonstrate an efficient path for the rapid transfer of electrons from ZnO to N-RGO, which facilitates charge separation in photocatalytic reactions.
To test photocatalytic CO of the prepared samples2Reduction performance. Photocatalytic CO (carbon monoxide) by adopting ZnO nanowire array/three-dimensional nitrogen-doped rGO nanotube composite material prepared in example 12Reduction test, the procedure was as follows:
first, 100mg of photocatalyst was introduced into a reactor, and 15mL of deionized water was added to the reactor to disperse the photocatalyst; then, drying the dispersion at 80 ℃, forming a layer of film at the bottom of the reactor, and sealing and blowing the film for 30min by using nitrogen to form an anaerobic state; using NaHCO in the reactor3(84mg, charged to the reactor before sealing) and 2mol L-1H of (A) to (B)2Chemical reaction of aqueous SO4 solution (0.2mL, sealed and injected into the reactor) to produce CO2And H2O steam; then, the reactor was placed under a 300W xenon lamp (vertical 10cm) for 1 hour, and finally 1ml of the mixed gas was extracted from the reactor and measured by GC2014C gas chromatograph (Shimadzu, Japan) equipped with a Flame Ionization Detector (FID). By using13CO2The carbon source was verified by isotopic tracing experiments. Except that isotopically labelled sodium bicarbonate (NaH) is used13CO3Cambridge isotope laboratory Co., USA) and H2SO4CO produced from aqueous solution2And H2In addition, after 1 hour of photocatalytic reaction, 250. mu.L of the mixed gas was taken out of the reactor, and the product was analyzed with a gas chromatography-mass spectrometer (6980N network GC system-5975 inert mass selective detector, Agilent technologies, USA).
FIG. 5(a) is a graph of photocatalytic CO of N-rGO, pure ZnO, ZnO/N-rGO and commercial ZnO (c-ZnO) under 300W xenon lamp illumination2Reduction of CH3OH Performance comparison plot showing photocatalytic CO of prepared samples2Reduction performance. As can be seen from fig. 5(a), the control experiment confirmed that no reduction product was detected in the absence of photocatalyst, carbon source or light. These results clearly show that CO2The photocatalytic reduction of (a) is indeed carried out by a photocatalytic reaction, which does not show photocatalytic activity due to the zero-band-gap characteristic of N-rGO. Meanwhile, the photoproduction electron-hole pair has high recombination speed, small specific surface area and CO2Poor absorption capacity, photocatalytic production of CH from pure ZnO and commercial ZnO prepared3The OH performance is relatively low. In contrast, ZnO/N-RGO has a higher CH3OH formation rate of 1.51mmol h-1g-1About 2.3 times as much as pure ZnO. Photocatalytic CO2The improvement in reduction activity is attributed to its unique three-dimensional porous framework structure and the advantages of N-rGO.
FIG. 5(b) is a schematic view of13CO2And12CO2CH generated on ZnO/N-rGO sample as carbon source3GC-MS spectrum of OH, as can be seen in FIG. 5(b), produced CH3OH does come from carbon dioxide rather than contaminated carbon species in the sample13CO2And12CO2the isotope peak of m/z 33.1 detected in the photocatalytic reduction of (1) can be attributed to13CH3OH, indicating that the photo-reduction product is derived from13CO2。
Fig. 6 is a photocatalysis mechanism of a ZnO/N-rGO nanocomposite, and fig. 6(a) is a schematic diagram of a three-dimensional porous structure of ZnO/N-rGO according to an embodiment of the present invention, and first, N-rGO has a huge three-dimensional porous framework and a large specific surface area, and can be used as a suitable carrier for uniform growth of a ZnO nanowire array (see fig. 6 a). The uniform and compact growth of ZnO nanowire arrays on N-rGO facilitates the formation of heterojunctions between these two components. Secondly, the N-rGO can be used as an electron acceptor and a electron transporter, and photogenerated electrons in a conduction band of the N-rGO can be well transferred to the NrGO, so that the separation of holes and electrons is facilitated. In addition, graphite N in the N-rGO can be used as an electron migration activation region, so that electrons can be rapidly and effectively transferred from ZnO to pyrroleNitrogen and pyridine nitrogen. On the other hand, pyrrole and pyridine N on the edges or defects of N-rGO can act as CO due to interaction of Lewis acid-base and hydrogen bonds2Adsorbed and activated active centers. Thus, with the aid of multiple electrons and protons, CO2Reduced to methanol on pyrrole and pyridine N. On the other hand, water molecules can be oxidized to oxygen by photogenerated holes in the valence band of ZnO, while the remaining protons will participate in CO2And (4) carrying out reduction reaction. In addition, the three-dimensional layered porous framework structure enables ZnO/N-rGO to have higher specific surface area and larger pore volume, provides numerous transfer channels for molecular diffusion dynamics, and improves the utilization efficiency of light due to reflection and scattering of light. In general, the 3DN-rGO nanotube framework can be used as a promoter with three functions, supports the uniform growth of a ZnO nanotube, effectively improves the separation of electron-hole pairs, and plays a role in adsorbing and reducing an active center by CO 2. Due to these advantages, the ZnO/N-rGO composite material can obtain excellent photocatalytic reduction of CO2And (4) performance.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A preparation method of a ZnO nanowire array/three-dimensional nitrogen-doped rGO nanotube composite material is characterized by comprising the following steps:
s1, preparing a graphene oxide suspension by taking graphite powder as a raw material;
s2, dipping the pretreated melamine sponge into the graphene oxide suspension to obtain graphene oxide composite sponge, drying the graphene oxide composite sponge, calcining for the first time, and removing a polymer template to obtain 3 DN-rGO;
s3, dispersing zinc acetate in ethanol to form a mixed solution A, soaking 3DN-rGO in the mixed solution A, and carrying out secondary calcination to form ZnO seed crystal N-rGO;
s4, mixing zinc nitrate, urea and hexamethylenetetramine to form a mixed solution B, soaking the ZnO seed crystal N-rGO in the mixed solution B, uniformly stirring, carrying out hydrothermal reaction in a high-pressure hydrothermal kettle, rinsing a reaction product, carrying out third calcination, and carrying out post-treatment to obtain the ZnO nanowire array/three-dimensional nitrogen-doped rGO nanotube composite material.
2. The method according to claim 1, wherein in S1, the concentration of the graphene oxide suspension is 2.3 g/L.
3. The method according to claim 1, wherein the pretreatment in S2 comprises washing the melamine sponge with ethanol, and drying at 80 deg.C for 12 h.
4. The preparation method as claimed in claim 3, wherein in S2, the calcination temperature of the first calcination is 500-600 ℃, and the calcination time is 0.5-3.5 min.
5. The preparation method as claimed in claim 1, wherein in S3, the mass ratio of the zinc acetate to the 3DN-rGO is 0.1-20%, the calcination temperature of the second calcination is 190-210 ℃, and the calcination time is 1-25 min.
6. The method according to any one of claims 1 to 5, wherein the molar ratio of the zinc nitrate, the urea and the hexamethylenetetramine in S4 is (0.1-1): (0.1-1): (0.1-1).
7. The preparation method according to claim 6, wherein the hydrothermal reaction temperature in S4 is 60-120 ℃ and the reaction time is 10-14 h.
8. The preparation method as claimed in claim 7, wherein in S4, the calcination temperature of the third calcination is 440-460 ℃, and the calcination time is 1-1.5 h.
9. A ZnO nanowire array/three-dimensional nitrogen-doped rGO nanotube composite material is characterized by being prepared by the preparation method of the ZnO nanowire array/three-dimensional nitrogen-doped rGO nanotube composite material as claimed in any one of claims 1 to 8, wherein the composite material comprises a 3D nitrogen-doped rGO nanotube framework and a ZnO nanowire array growing on the surface of the 3D nitrogen-doped rGO nanotube framework, the 3D nitrogen-doped rGO nanotube framework is of a net-shaped porous structure, and the ZnO nanowire array vertically covers the surface of the 3D nitrogen-doped rGO nanotube framework.
10. An application of a ZnO nanowire array/three-dimensional nitrogen-doped rGO nanotube composite material in the field of photocatalytic reduction of carbon dioxide.
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