CN112206804A - TiO 22/g-C3N4Preparation method of composite photocatalyst and preparation method of hydrogen - Google Patents
TiO 22/g-C3N4Preparation method of composite photocatalyst and preparation method of hydrogen Download PDFInfo
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- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/613—
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- B01J35/633—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The embodiment of the invention discloses TiO2/g‑C3N4A preparation method of a composite photocatalyst belongs to the field of chemistry, and comprises the following steps: dispersing graphite-phase carbon nitride and titanium dioxide in a solvent according to a mass ratio of 1-7: 9-3, and heating and volatilizing the solvent at 50-100 ℃ until a dry powdery mixture is obtained; and annealing the mixture at the temperature of 200-550 ℃ for 1-3 hours at the heating speed of 1-8 ℃/min to obtain the titanium dioxide/graphite phase carbon nitride composite photocatalyst. The catalyst can effectively promote the rapid separation of a photon-generated carrier at a junction interface, thereby improving the photocatalytic activity of the photon-generated carrier.
Description
Technical Field
The embodiment of the invention relates to the field of chemistry, in particular to TiO2/g-C3N4A preparation method of the composite photocatalyst and a preparation method of hydrogen.
Background
With the development of times and science and technology, energy becomes a serious problem affecting national development patterns, geopolitics, environmental protection and ecology. As a representative of new energy, hydrogen energy represents a future development direction of new energy.
In the conventional method, hydrogen gas can be obtained by electrolysis of water, dehydrogenation reaction, or cracking. However, this method has disadvantages in that these techniques need to be carried out under high temperature conditions or require high energy consumption, and cannot be applied on a large scale. Another new approach has been to produce hydrogen by decomposing water with a semiconductor photocatalyst, which is low cost, chemically stable and environmentally friendly, and has been considered as one of the ideal options. However, because ZnO has a large forbidden band width (3.7eV), ultraviolet light must be used to excite the hydrogen production activity, but the ultraviolet light in sunlight only accounts for about 4%, and the application of ZnO in photocatalytic hydrogen production is also limited due to the excessively fast recombination rate of photon-generated carriers, resulting in an excessively low hydrogen production efficiency.
Disclosure of Invention
The embodiment of the invention provides TiO2/g-C3N4The preparation method of the composite photocatalyst comprises the following steps:
dispersing graphite-phase carbon nitride and titanium dioxide in a solvent according to a mass ratio of 1-7: 9-3, and heating and volatilizing the solvent at 50-100 ℃ until a dry powdery mixture is obtained;
and annealing the mixture at the temperature of 200-550 ℃ for 1-3 hours at the heating speed of 1-8 ℃/min to obtain the titanium dioxide/graphite phase carbon nitride composite photocatalyst.
Specifically, the titanium dioxide/graphite phase carbon nitride composite photocatalyst is a Z-shaped heterojunction.
Specifically, the titanium dioxide is in a layered floret shape.
Specifically, the graphite phase carbon nitride is in the form of nano-platelets.
Specifically, the method further comprises the following steps:
adding tetrabutyl titanate into an acetic acid solution, stirring, placing the prepared solution into a high-pressure kettle, and heating to 120-160 ℃ in a high-temperature furnace for 10-12 hours;
and after the reaction is finished, naturally cooling the high-pressure kettle to room temperature, obtaining a reaction product through centrifugal separation, cleaning the product, and drying at 50-80 ℃ for at least 12 hours to obtain the titanium dioxide.
Specifically, the method further comprises the following steps:
mixing and dissolving ammonium chloride and dicyandiamide according to the mass ratio of 3-7: 1;
heating the obtained solution at the temperature of 80-120 ℃ until a powdery substance is obtained;
sintering the powdery substance for at least 3 hours at the temperature of 400-700 ℃ to obtain the graphite-phase carbon nitride.
Specifically, ammonium chloride and dicyandiamide are in a mass ratio of 5: 1.
Specifically, the mass ratio of graphite-phase carbon nitride to titanium dioxide is 1:1.
Specifically, the solvent is methanol or ethanol.
The embodiment of the invention provides a preparation method of hydrogen, which comprises the following steps:
dispersing the titanium dioxide/graphite phase carbon nitride composite photocatalyst prepared in the embodiment into triethanolamine containing chloroplatinic acid aqueous solution according to the mass ratio of 1: 1.5-3;
degassing the mixed solution by using nitrogen for at least 20 minutes to remove air, and irradiating by using a xenon lamp for at least 20 minutes to perform photocatalysis to obtain hydrogen.
The heterojunction structure constructed by the semiconductor material obtained by the embodiment of the invention can effectively promote the rapid separation of a photon-generated carrier at a junction interface, thereby improving the photocatalytic activity of the photon-generated carrier. Compared with the traditional heterojunction structure, the direct Z-type heterojunction can endow the composite photocatalyst with stronger oxidation reduction capability, higher separation rate of a photon-generated carrier and the spectral response of the photon-generated carrier moving to a long wavelength, so that the hydrogen production efficiency can be further improved. In addition, besides the intrinsic performance of the photocatalyst, the mesoporous-macroporous structure is also an important factor influencing the catalytic performance of the photocatalyst. Compared with the traditional low-dimensional nano material, the photocatalyst with the three-dimensional hierarchical structure can simultaneously have large specific surface area, a mesoporous structure, a large number of reaction active points and higher light utilization efficiency, and because light rays can realize refraction and multiple reflection in the photocatalyst, the photocatalytic activity is enhanced.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a diagram of TiO preparation provided in the example of the present invention2/g-C3N4A flow diagram of the composite photocatalyst;
FIG. 2 is a side view of an X-ray diffraction spectrum provided by an embodiment of the present invention;
FIG. 3 is a Scanning Electron Microscope (SEM) and High Resolution Transmission Electron Microscope (HRTEM) microstructure test chart of the photocatalyst provided by the embodiment of the invention;
FIG. 4 is a photoelectron spectroscopy test chart and a thermogravimetric analysis side view provided by an embodiment of the present invention;
fig. 5 is a uv-vis spectroscopy test chart provided in an embodiment of the present invention;
FIG. 6 is a hydrogen verification test chart provided in accordance with an embodiment of the present invention;
FIG. 7 is a photoluminescence spectrum test chart, a photoelectric response chart and an electrochemical impedance spectrum test chart provided by an embodiment of the invention;
fig. 8 is a heterojunction energy band test chart provided by the embodiment of the invention.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
Dispersing graphite-phase carbon nitride and titanium dioxide in a solvent according to a mass ratio of 1-7: 9-3, and heating and volatilizing the solvent at 50-100 ℃ until a dry powdery mixture is obtained;
and secondly, annealing the mixture at the temperature of 200-550 ℃ at the heating speed of 1-8 ℃/min for 1-3 hours to obtain the titanium dioxide/graphite phase carbon nitride composite photocatalyst.
Specifically, the titanium dioxide/graphite phase carbon nitride composite photocatalyst prepared by the method is a Z-shaped heterojunction.
It should be noted that titanium dioxide is in a layered flower shape, and graphite phase carbon carbonitride is in a nano-sheet shape.
Specifically, the preparation method of the graphite phase carbon nitride comprises the following steps:
adding tetrabutyl titanate into an acetic acid solution, stirring, placing the prepared solution into a high-pressure kettle, and heating to 120-160 ℃ in a high-temperature furnace for 10-12 hours;
and after the reaction is finished, naturally cooling the high-pressure kettle to room temperature, obtaining a reaction product through centrifugal separation, cleaning the product, and drying at 50-80 ℃ for at least 12 hours to obtain the titanium dioxide.
Specifically, the preparation method of the graphite phase carbon nitride comprises the following steps:
mixing and dissolving ammonium chloride and dicyandiamide according to the mass ratio of 3-7: 1;
heating the obtained solution at the temperature of 80-120 ℃ until a powdery substance is obtained;
sintering the powdery substance for at least 3 hours at the temperature of 400-700 ℃ to obtain the graphite-phase carbon nitride.
Preferably, the ammonium chloride and the dicyandiamide are in a mass ratio of 5:1, and the mass ratio of the graphite-phase carbon nitride to the titanium dioxide is 1:1.
Specifically, the solvent is methanol or ethanol.
The embodiment of the invention also provides a preparation method of hydrogen, and the catalyst used in the method is the titanium dioxide/graphite phase carbon nitride composite photocatalyst prepared in the embodiment. The specific method comprises the following steps:
dispersing the titanium dioxide/graphite phase carbon nitride composite photocatalyst into triethanolamine containing chloroplatinic acid aqueous solution according to the mass ratio of 1: 1.5-3;
degassing the mixed solution by using nitrogen for at least 20 minutes to remove air, and irradiating by using a xenon lamp for at least 20 minutes to perform photocatalysis to obtain hydrogen.
Examples
1. Preparation of TiO2
1ml of tetrabutyltitanate was added to 30ml of acetic acid to obtain a solution A.
After vigorously stirring the solution A for 10 minutes, the solution A was sealed in a Teflon autoclave having a capacity of 50ml, and the Teflon autoclave was placed in a high temperature furnace, and the solution A was heated at 140 ℃ for 12 hours.
After the reaction is finished, the high-pressure kettle is naturally cooled to room temperature, a reaction product B is obtained through centrifugal separation, and the reactant B is carefully cleaned by water and absolute ethyl alcohol.
Drying the cleaned reactant B at 70 ℃ for 24 hours to obtain layered fresh flower-like TiO2。
2. Preparation of g-C3N4：
10g of ammonium chloride and 2g of dicyandiamide were dissolved in 80ml of deionized water and vigorously stirred for one hour to give solution C.
Solution C was dried at 100 ℃ until dry powder D was obtained.
Sintering the dry powdery substance D in a muffle furnace at 550 ℃ for 4 hours to obtain the graphite-phase carbon nitride (g-C)3N4)。
3. Preparation of TiO2/g-C3N4Composite photocatalyst
10g of C3N4And adding the nanosheets into 70mL of methanol, and performing ultrasonic treatment for 1 hour to obtain a uniform dispersion solution F.
0.5g of TiO2Adding into the above dispersion F, and heating to volatilize the solvent at 70 deg.C until drying to obtain dry powder material G.
Annealing the obtained dry powder substance G at 550 ℃ for 2 hours at the heating speed of 5 ℃/min to obtain TiO2/g-C3N4A composite photocatalyst is provided.
4. Production of hydrogen
50mg TiO in a sealed glass system2/g-C3N4The composite photocatalyst is dispersed in the H-containing solution2PtCl6(34. mu.L, 0.1mg/mL) of an aqueous solution in 100mL triethanolamine (TEOA, 10 vol%).
For the above solution N2Degassing was carried out for 30min to remove air.
The solution was irradiated with a 350W xenon lamp. The amount of hydrogen produced after the photocatalysis was analyzed by gas chromatography (SP-7820, TCD).
As shown in FIG. 1, FIG. 1 is a process for preparing TiO2/g-C3N4The flow chart of the composite photocatalyst is shown schematically.
When g-C3N4Is TiO 22/g-C3N4The experiments were carried out at a mixture mass ratio of 10%, 30%, 50%, 70%, where CNTx is the ratio where x is 10%, 30%, 50%, 70%.
TiO as shown in the following FIG.2/g-C3N4A composite photocatalyst is illustrated. Two important indexes of the photocatalyst activity, namely specific surface area and porosity, are shown in the table I. As can be seen from Table I, with g-C3N4The specific surface area is gradually increased and the specific volume is also increased when the content is increased. The large specific surface area and specific volume provide more reactive sites and promote the adsorption of reactants, thus contributing to the enhancement of photocatalytic activity.
Table one physical Properties of photocatalyst
FIG. 2a is TiO2CNT10, CNT30, CNT50, CNT70 and g-C3N4X-ray diffraction pattern. To TiO 22The samples, whose diffraction peaks at 25.5 °,37.7 °,48.2 ° and 54.1 ° correspond to the (101), (004), (200) and (105) planes, respectively, represent TiO2An anatase phase was present. g-C3N4Characteristic peaks are shown at 13.1 ° and 27.5 °, corresponding to the (100) and (002) planes. The 13.1 ° peak indicates that g-C3N4 is a layered structure, as measured by the 27.5 ° peakThe g-C can be calculated3N4The interplanar spacing was 0.324 nm. No peak shift was observed for CNTx, indicating TiO2And g-C3N4In TiO2/g-C3N4The interlayer structure of the composite photocatalyst structure is not changed.
FIG. 2b shows TiO2，g-C3N4And TiO2/g-C3N4Fourier transform Infrared Spectroscopy (FT-IR) of a composite photocatalyst. To TiO 22Sample at 475cm-1The absorption bands of (a) represent the tensile vibration modes of Ti-O and Ti-O-Ti in anatase crystals. For g-C3N4For example, 807, 1241,1324,1408, and 1580cm-1Peak position of (1) is g-C3N4Characteristic peak of (2). The above characteristic peaks were also observed in the CNTx sample, indicating that TiO2And g-C3N4In TiO2/g-C3N4The composite photocatalyst is not damaged.
FIGS. 2c to 2d show the results of the nitrogen adsorption and desorption tests of the catalyst. As can be seen from fig. 2c, for all samples, a type IV isotherm was shown, indicating the presence of mesopores. Further, on TiO2The hysteresis curve indicates H2 type mesopores having a pore structure, and H2 type mesopores are generally present in TiO2As can be seen on the nanoparticles. In addition, with g-C3N4The proportion of the mesoporous material in the CNTx is increased, and a hysteresis curve gradually shows layered H3 mesoporous. Combinations of H2 and H3 type mesopores were seen in the samples of CNT50 and CNT 70. H3 type mesopores are generally present in the g-C layer3N4In the structure.
Figure 2d is a graph of the pore size distribution. For TiO2And g-C3N4In other words, the pore size exhibits a bimodal distribution. For TiO2The sizes of the mesopores are mainly 3.5nm and 10nm for g-C3N4In particular, the sizes of the mesopores are mainly 3.8nm and 32 nm. The pore size was confirmed to be TiO2And g-C3N4All have mesoporous structures. Further analysis shows that for TiO2In a wordThe mesoporous size is more than 10 nm. For g-C3N4In other words, the size of the mesopores is mainly as much as 32 nm. To TiO 22And g-C3N4The mixed structure CNTx, mesoporous distribution, shows three pore size distributions, one of which is between 10nm and 32nm and 12nm, from which it can be concluded that TiO2And g-C3N4The mixture was very homogeneous. The blue shift of the peak position exhibited in CNTx is due to the small mesopore sizes of 10nm and 12 nm. As is clear from FIG. 2d, with g-C in CNTx3N4The surface area of the CNTx is obviously higher than that of pure TiO due to the increase of the content2(51.2m2/g) due to g-C3N4Has a large specific surface area (76.5 m)2In terms of/g). And the large specific surface area can provide more catalytic sites, thereby improving the performance of the photocatalyst. Specifically, the specific surface area of the CNT50 sample reached 61.1m2G, significantly higher than pure TiO2Thus, it is expected that enhanced photocatalytic activity can be obtained. Albeit g-C3N4Has the largest specific surface area, however, the photocatalytic activity of the CNT50 sample will also be improved due to the synergistic effect caused by the recombination.
FIG. 3 shows the microstructure of the photocatalyst under Scanning Electron Microscopy (SEM) and High Resolution Transmission Electron Microscopy (HRTEM). FIG. 3a is TiO2SEM picture of (1), from which TiO is seen2The sample has a layered spherical shape and flower-like structure with a diameter of several microns, and the nanosheets are assembled disorderly on the spherical structure. FIG. 3b is g-C3N4Nanosheet structure diagram, a typical graphene-like layered structure can be observed, indicating graphitic phase g-C formed after calcination3N4Nanosheets. These SEM images are consistent with the XRD analysis structure described previously. Figure 3c shows a SEM image of CNT50 in which the layered structure with flowers and spheres remains well, indicating calcination vs TiO2The morphology of (2) has no significant effect. However, for g-C3N4Nanosheets, g-C due to shrinkage caused by high temperature calcination3N4The layered structure shows a slight collapse. Further observations, shown in FIG. 3c, found that TiO2MicrospheresAnchored in wrinkled g-C3N4On the surface of the nanoplatelets. FIG. 3d is a typical CNT50 HRTEM image with lattice fringes with a spacing of 0.35nm made of anatase TiO2Is caused by the (101) plane of (a). For g-C3N4Nanoplatelets, which have relatively small crystallinity, no lattice fringes are observed. High crystallinity indicates high structural regularity and low defect density, and can increase g-C3N4The conductivity of the sample promotes the separation of photon-generated carriers, thereby improving the photocatalytic activity.
FIG. 4 is a photoelectron spectroscopy (XPS) study of the electrochemical structure of a composite photocatalyst. For the CNT50 sample, the measured spectrum of fig. 4a shows the signals for C, N, Ti, and O in the CNT 50. For g-C3N4O signal and TiO in2C signal in (C), suspected of contamination from air or equipment. FIG. 4b shows CNTs 50 and g-C3N4Medium high resolution C1s spectrum. The spectrum can be subdivided into two spectra, derived from g-C for a peak position of the binding energy at 284.8eV3N4Sp2 carbon hybridization signal in (a) and carbon by-products of graphitization. In addition, it is located at 288.2eV (for g-C)3N4) And 288.6eV (for CNT50) are derived from sp3 hybridization of N-C-N. Notably for CNT50, the above peak positions are relative to g-C3N4There is a significant forward shift, which should be due to the TiO in the CNT502And g-C3N4Is caused by a strong interaction. FIG. 4C is g-C3N4High resolution with N1s in CNT 50. Similarly, the spectral peak with binding energy at 398.5eV is derived from C-N ═ N in the C chain. Similarly, the N signal in CNT50 is relative to g-C3N4With a negative bias of 0.5eV, again indicating TiO 50 in the CNT502And g-C3N4Not only TiO2And g-C3N4Simple mixing of (1). Further, similar binding energy peak shifts were also found in the O1s and Ti2p spectra, and the above conclusion was further confirmed. While a close contact interface with strong interaction facilitates charge separation and transport for the formation of high quality heterojunctionsIs very important.
FIG. 4f is a thermogravimetric analysis of the sample, and from FIG. 4f, thermogravimetric analysis (TGA) was used to analyze g-C3N4The proportion of the compound photocatalyst and the thermal stability of the photocatalyst. TiO 22The thermal stability is better maintained until 800 ℃, and the g-C3N4It has been completely decomposed at 720 ℃. For the CNT50 sample, the total mass loss was 52.7% at temperatures above 720 deg.C, which is comparable to g-C3N4The complete decomposition is relevant at 720 ℃ and the percentage loss confirms the TiO2And g-C3N4The nominal proportions in CNT50 are quite accurate.
The light absorption properties of the photocatalyst can be seen in the ultraviolet-visible spectrum (UV-vis) of FIG. 5 a. For TiO2Its absorption peak is below 400nm because of its large bandwidth (-3.2 eV). For g-C3N4The absorption peak is extended to 430nm due to g-C3N4With a narrow bandwidth (-2.9 eV). For CNTx, there is a significant red shift in the absorption peak, which also means TiO2And g-C3N4Strong interaction between them. For the CNT50 sample, its light absorption range is g-C3N4In close proximity. Meanwhile, the narrower bandwidth means that under the same illumination intensity, more photogenerated electron-hole pairs can be generated, and the electron-hole pairs are in TiO2And g-C3N4The heterojunction interface is easier to separate, and compared with a single catalyst, the photocatalysis effect of the catalyst is improved.
Under the sun illumination, the TiO is treated2/g-C3N4The ability of the composite photocatalyst to generate hydrogen was verified. As shown in FIG. 6a, pure TiO2Using only energy in the ultraviolet spectrum, pure g-C3N4Has a faster electron-hole pair recombination rate, and thus for pure TiO2And g-C3N4In all, a lower hydrogen yield was exhibited. But adding TiO2And g-C3N4After mixing, a large increase in hydrogen production occurred. Such as an optimized CNT50 sample, whichThe hydrogen production rate reaches 4128 mu mol/h/g, and the product is TiO21.9 times of that of (A), and g-C3N47.7 times of. The reason for the improvement of the hydrogen production rate is that first, TiO2/g-C3N4The composite photocatalyst has a wider light absorption range, so that more photo-generated electron-hole pairs can be generated; second, TiO2And g-C3N4The high-quality heterojunction formed between the two layers leads the composite photocatalyst to have better separation efficiency and transportation of electron hole pairs; third, TiO2/g-C3N4The composite photocatalyst has larger specific surface area and can provide more catalytic activation points.
In addition to this, TiO2/g-C3N4The composite photocatalyst also has excellent stability. As seen in fig. 6b, for TiO2/g-C3N4After the composite photocatalyst is repeatedly used for three times under the same condition, the hydrogen amount generated by catalysis of the CNT50 does not fall, and the good photocatalytic stability of the CNT50 is reflected. Also as seen in FIG. 6c, TiO was further confirmed by comparing the FT-IR spectra of the old and new CNT50 samples, where no visible difference was found between the two lines2/g-C3N4The stability of the composite photocatalyst.
Fig. 7a is a photoluminescence spectrum (PL), with higher PL intensity indicating faster electron-hole pair recombination, meaning that the photocatalytic effect is weakened. As seen in FIG. 7a, at 450nm, g-C3N4Showed the highest PL intensity, CNT70 showed a moderate PL intensity. Lower PL intensity was shown for optimized CNT 50. This result is consistent with the higher hydrogen production rate of CNT 50.
FIGS. 7 b-c are the photoelectric response diagram and the electrochemical impedance spectrum. As shown in fig. 7b, compare to TiO2And g-C3N4CNTs 50 have a strong photocurrent density. Fig. 7c is an EIS Nyquist plot showing that CNT50 exhibits the smallest radius of the circular arc, indicating that CNT50 has a lower internal resistance to charge transport and thus higher photocatalytic activity.
Further, hydroxyl radical (. OH) can react with Terephthalic Acid (TA) to produce hydroxyterephthalic acid (TAOH), which produces fluorescence at 425nm under laser irradiation at 315nm, and thus can be used as a method for detecting the production of. OH. As shown in FIG. 7d, for the CNT50 sample, the PL intensity at 425nm monotonically increased with increasing illumination time. The phenomenon shows that OH free radicals are generated along with the consumption of holes, so that efficient electron-hole pair separation is caused, and the phenomenon is very important in the photocatalytic hydrogen production process.
FIG. 8 is TiO2/g-C3N4The heterojunction energy band diagram. Based on a standard hydrogen electrode, TiO2The valence band and the conduction band of (A) are respectively 2.91 and-0.29 eV, g-C3N4The valence and conduction bands were 1.68 and-1.22 eV, respectively. And E (. OH/OH)-) And E (. OH/H)2O) has an oxidation potential of 1.99eV and 2.68eV, respectively, and H2O/H2The reduction potential of (a) is-0.59 eV. Hypothesis of TiO2/g-C3N4The interface follows a conventional type II heterojunction, then H2O/H2Reduction potential and TiO2Has a potential difference of 0.3eV, which results in the free electrons not being able to pass from the TiO2Into H2In O to H2And O is separated. However, this is contrary to what we have actually observed is hydrogen production. Likewise, holes cannot be drawn from g-C3N4Valence band of to OH-Or H2And (4) in O. Thus, as an explanation, TiO2And g-C3N4Should be a Z-type heterojunction.
The electron hole transport mode should be as follows: TiO 22Electrons in the conduction band with g-C3N4Hole recombination in the valence band with TiO2In its valence band and g-C3N4The electrons in (b) accumulate in their conduction band (see fig. 8). Thus by constructing a Z-type heterojunction, the potential barrier for charge transfer disappears, resulting in TiO2/g-C3N4The heterojunction has excellent photocatalytic performance.
The foregoing is only a partial embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. TiO 22/g-C3N4The preparation method of the composite photocatalyst is characterized by comprising the following steps:
dispersing graphite-phase carbon nitride and titanium dioxide in a solvent according to a mass ratio of 1-7: 9-3, and heating and volatilizing the solvent at 50-100 ℃ until a dry powdery mixture is obtained;
and annealing the mixture at the temperature of 200-550 ℃ for 1-3 hours at the heating speed of 1-8 ℃/min to obtain the titanium dioxide/graphite phase carbon nitride composite photocatalyst.
2. The TiO of claim 12/g-C3N4The preparation method of the composite photocatalyst is characterized in that the titanium dioxide/graphite phase carbon nitride composite photocatalyst is a Z-shaped heterojunction.
3. The TiO of claim 12/g-C3N4The preparation method of the composite photocatalyst is characterized in that the titanium dioxide is in a layered fresh flower shape.
4. The TiO of claim 12/g-C3N4The preparation method of the composite photocatalyst is characterized in that graphite phase carbon nitride is in a nano-sheet shape.
5. The TiO of claim 32/g-C3N4The preparation method of the composite photocatalyst is characterized by further comprising the following steps:
adding tetrabutyl titanate into an acetic acid solution, stirring, placing the prepared solution into a high-pressure kettle, and heating to 120-160 ℃ in a high-temperature furnace for 10-12 hours;
and after the reaction is finished, naturally cooling the high-pressure kettle to room temperature, obtaining a reaction product through centrifugal separation, cleaning the product, and drying at 50-80 ℃ for at least 12 hours to obtain the titanium dioxide.
6. The TiO of claim 42/g-C3N4The preparation method of the composite photocatalyst is characterized by further comprising the following steps:
mixing and dissolving ammonium chloride and dicyandiamide according to the mass ratio of 3-7: 1;
heating the obtained solution at the temperature of 80-120 ℃ until a powdery substance is obtained;
sintering the powdery substance for at least 3 hours at the temperature of 400-700 ℃ to obtain the graphite-phase carbon nitride.
7. The TiO of claim 62/g-C3N4The preparation method of the composite photocatalyst is characterized in that ammonium chloride and dicyandiamide are in a mass ratio of 5: 1.
8. The TiO of claim 12/g-C3N4The preparation method of the composite photocatalyst is characterized in that the mass ratio of graphite phase carbon nitride to titanium dioxide is 1:1.
9. The TiO of claim 12/g-C3N4The preparation method of the composite photocatalyst is characterized in that the solvent is methanol or ethanol.
10. A method for producing hydrogen, characterized in that the TiO according to any one of claims 1 to 9 is used2/g-C3N4Dispersing the composite photocatalyst into triethanolamine containing chloroplatinic acid aqueous solution according to the mass ratio of 1: 1.5-3;
degassing the mixed solution by using nitrogen for at least 20 minutes to remove air, and irradiating by using a xenon lamp for at least 20 minutes to perform photocatalysis to obtain hydrogen.
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