CN109126856B - Preparation method of visible light photocatalyst with tight connection - Google Patents
Preparation method of visible light photocatalyst with tight connection Download PDFInfo
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- CN109126856B CN109126856B CN201811211860.4A CN201811211860A CN109126856B CN 109126856 B CN109126856 B CN 109126856B CN 201811211860 A CN201811211860 A CN 201811211860A CN 109126856 B CN109126856 B CN 109126856B
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- 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
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- B01J35/23—
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- B01J35/39—
-
- B01J35/51—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention belongs to the field of preparation of photocatalysts, in particular to a preparation method of a visible light photocatalyst with close connection, which solves the problem that pure g-C is adopted at present3N4The photocatalyst has the technical problems of low catalytic activity, narrow spectral response range and CdS photo-corrosion. The invention comprises the following steps: (1) g-C3N4The material is synthesized by a high-temperature thermal polymerization method with melamine as a precursor; (2) the hollow microsphere CdS is synthesized by a hydrothermal method by taking thiourea as a sulfur source; (3) CdS/g-C3N4The composite photocatalyst is synthesized by a low-temperature calcination method. The invention provides CdS/g-C3N4The composite photocatalyst can realize high-efficiency degradation of organic pollutants, has good settling property and is beneficial to separation and recovery of the composite photocatalyst. Because the two are closely connected, the separation and transfer of photo-generated charges at the connecting interface of the composite photocatalyst can be accelerated, the photocatalytic activity of the composite photocatalyst is enhanced, and the cycle stability of the composite photocatalyst is improved.
Description
Technical Field
The invention belongs to the field of preparation of photocatalysts, and particularly relates to a preparation method of a tightly-connected visible-light photocatalyst.
Background
Organic pollutants in the industrial wastewater pollute water, harm human health and destroy an ecological system. Solar energy is a clean energy source and is a cheap and available renewable energy source. The semiconductor photocatalyst is used as an environment-friendly material, can degrade organic pollutants by using solar energy, and is expected to purify water[1]. Up to now, TiO2The photocatalyst is recognized as one of the most potential photocatalysts, but the photocatalyst has high electron-hole recombination rate and wide energy band gap, can only respond to the wave band of the ultraviolet region, and the practical application of the photocatalyst is severely limited[2-3]. Therefore, the search for a photocatalyst that is highly efficient in responding to the visible light region is a key point for the development of photocatalysis to be put to practical use. Wang in 2009[4]Etc. report g-C for the first time3N4Photolysis of water to produce hydrogen in the visible region, and then a large number of references are made to g-C3N4The study of the system has been reported[5-7]。g-C3N4Has the advantages of good physical and chemical stability, good electronic structure band gap energy (2.7 eV), simple synthetic method, low preparation cost, no toxicity, easy modification and the like. But pure g-C3N4The method has the practical problems of high photoproduction electron-hole recombination rate, small specific surface area, low utilization rate of visible light, poor recycling capability and the like. The CdS semiconductor is an important ii-IV semiconductor with a narrow bandgap (2.4 eV) as the visible light active material commonly used for PEC sensing. The CdS photocatalyst can expand the visible light absorption range to 520 nm due to a proper band gap structure, and solar energy is fully utilized[8]. But the CdS photocatalyst has high photoproduction electron-hole recombination rate and low photocatalytic activity; self-light corrosion can occur under the irradiation of visible light, thereby reducing the cycle stability of the material[9]And the like.
Relevant documents
[1] L. Q. Jing, W. Zhou, G. H.Tian and H. G. Fu. Surface tuning for oxide-based nanomaterials as efficient photocatalysts, Chem Soc Rev., 2013, 42 (24), 9509-9549.
[2].G. Lei, M. Xu, H. Fang, S. Ming, Preparation of TiO2 thin films from autoclaved sol containing needle-like anatase crystals, Appl. Surf. Sci. 2 (2006) 720-725.
[3].A. A. Assadi, A. Bouzaza, D. Wolbert, Study of synergetic effect by surface discharge plasma/TiO2 combination for indoor air treatment: Sequential and continuous configurations at pilot scale, J. Photochem. Photobiol. A Chem. 6 (2015) 148-154.
[4].W. X, M. K, T. A, T. K, X. G, C. JM, D. K, A. M, A metal-free polymeric photocatalyst for hydrogen production from water under visible light, Nat. Mater. 1 (2009) 76-80.
[5] M. M. Li, L. X. Zhang, M. Y. Wu, Y. Y. Du, X. Q. Fan, M. Wang, L. L. Zhang, Q. L. Kong and J. L. Shi. Mesostructured CeO2/g-C3N4 nanocomposites: Remarkably enhanced photocatalytic activity for CO2 reduction by mutual component activations, Nano Energy, 2016, 19, 145-155.
[6] Q. L. Tay, P. Kanhere, C. F. Ng, S Chen, S. Chakraborty, A. C. H. Huan, T. C. Sum, R. Ahuja and Z. Chen. Defect Engineered g-C3N4 for Efficient Visible Light Photocatalytic Hydrogen Production, Chem. Mater., 2015, 27 (14), 4930–4933.
[7] Q. Han, B. Wang, J. Gao, Z. H. Cheng, Y. Zhao, Z. P. Zhang and L. T. Qu. Atomically Thin Mesoporous Nanomesh of Graphitic C3N4 for High-Efficiency Photocatalytic Hydrogen Evolution, ACS Nano, 2016, 10 (2), 2745–2751.
[8].J. Ran, J. Yu, M. Jaroniec, Ni(OH)2 modified CdS nanorods for highly efficient visible-light-driven photocatalytic H2 generation, Green Chem. 10 (2011) 2708-2713
[9].M. Lu, Z. Pei, S. Weng, W. Feng, Z. Fang, Z. Zheng, M. Huang, P. Liu, Constructing atomic layer g-C3N4–CdS nanoheterojunctions with efficiently enhanced visible light photocatalytic activity, Phys. Chem. Chem. Phys. 39 (2014) 21280-8。
Disclosure of Invention
The invention aims to solve the following two technical problems: (1) at present pure g-C3N4The photocatalyst has the technical problems of high photoproduction electron-hole recombination rate, low visible light utilization rate and poor recovery capability; (2) the CdS photocatalyst has the technical problems of high photoproduction electron-hole recombination rate and poor stability and recycling property, and provides a preparation method of a visible photocatalyst with tight connection.
The invention is realized by adopting the following technical scheme: a preparation method of a visible light photocatalyst with tight connection comprises the following steps:
(1) preparation of g-C3N4Nanosheet (high temperature thermal polymerization):
putting melamine serving as a precursor into a crucible with a cover, and feeding the crucible into a muffle furnace; heating to 550 deg.C at a rapid heating rate of 55 deg.C/min from room temperature, maintaining at the temperature for 4 h, naturally cooling to room temperature, and grinding to obtain light yellow powder g-C3N4Nanosheets for use;
(2) preparation of CdS hollow microspheres (hydrothermal method):
adding cadmium nitrate tetrahydrate, thiourea and glutathione into distilled water according to the mass ratio of 1.67:1.24:1, mixing, wherein the mass concentration of the thiourea is 0.016 g/ml after mixing, and stirring for 1 h; then transferring the mixture into a polytetrafluoroethylene-lined stainless steel autoclave, and heating for 3 h at 250 ℃; then, taking out the obtained dark yellow product, centrifuging, washing with ultrapure water for several times, finally drying in an oven at 80 ℃ for 12 h, and grinding to obtain CdS hollow microspheres for later use;
(3) preparation of CdS/g-C3N4Composite photocatalyst (low-temperature calcination method):
g to C3N4Dispersing the nano sheet and the CdS hollow microsphere into distilled water, and mixing g-C3N4The mass ratio of the nanosheet to the CdS hollow microsphere is 1: 0.001-1: 0.0075, g-C3N4The mass concentration is 0.0067 g/ml, the mixture is continuously stirred for 12 hours at the room temperature and then dried for 12 hours in an oven at the temperature of 80 ℃; then, putting the dried mixture into a crucible with a cover, sending the crucible into a muffle furnace, roasting the mixture for 1 h at 150 ℃, and grinding the mixture after natural cooling to obtain CdS/g-C3N4A composite photocatalyst is provided.
The CdS/g-C with tight connection of the invention3N4The preparation of the composite photocatalyst can solve the problem of pure g-C3N4And CdS presents some practical problems. CdS/g-C constructed by the invention3N4In the composite photocatalyst, CdS and g-C3N4The two are closely connected, and the main functions are as follows: g-C3N4An energy band structure well matched with CdS exists between the CdS and the CdS, interaction at a connecting interface is enhanced, and g-C is enabled3N4The photo-generated electrons on the Conduction Band (CB) are easily injected to the CB of CdS through an interface, and meanwhile, the photo-generated holes on the CdS Valence Band (VB) can be spontaneously transferred to g-C through the interface3N4On VB of (c). The photoproduction electrons and the holes move in opposite directions, so that the separation and the migration of photoproduction charges are realized, and the photocatalytic activity of the photoproduction electrons and the holes is enhanced; meanwhile, the hole oxidation of the CdS is prevented, and the photo-corrosion problem of the CdS is solved, so that the circulation stability of the composite photocatalyst is improved; in addition, CdS/g-C3N4The composite photocatalyst has good settling property and is beneficial to separation and recovery.
CdS/g-C with tight connection constructed by the invention3N4The CdS hollow microsphere constituting the composite photocatalyst mainly has the following functions: the CdS hollow microsphere structure has higher light refraction efficiency, and meanwhile, the CdS belongs to a hexagonal wurtzite structure, so that the visible light absorption capacity of the composite photocatalyst can be enhanced, the visible light absorption range is widened, and more electrons and holes can be generated.
By adopting the method, the CdS/g-C with tight connection can be effectively prepared3N4Composite photocatalystThe CdS and g-C can be fully utilized3N4The two are closely connected and have the characteristic of a CdS hollow microsphere structure.
The invention has the beneficial effects that: (1) the invention provides CdS/g-C3N4The composite photocatalyst has good photocatalytic activity and circulation stability for photocatalytic degradation of organic pollutants; (2) CdS/g-C3N4The composite photocatalyst has good settling separation effect, and can be repeatedly recycled; (3) the CdS hollow microspheres can enhance the visible light absorption capacity of the composite photocatalyst, expand the visible light absorption range and improve the photocatalytic activity of the composite photocatalyst.
Drawings
FIG. 1 shows g-C3N4CdS and CdS/g-C3N4XRD pattern of photocatalyst.
FIG. 2 shows g-C3N4CdS and CdS/g-C3N4FT-IR diagram of photocatalyst.
FIG. 3 is CdS/g-C3N4XPS map of composite photocatalyst (a) full spectrum; c1 s, (C) N1 s and (d) Cd 3 d.
In FIG. 4, a is pure g-C3N4A TEM image of (B); FIGS. b-c are TEM images of CdS as hollow microspheres; FIG. d-e is CdS/g-C3N4TEM images of the photocatalyst; FIG. f is CdS/g-C3N4Selective area electron diffraction pattern of photocatalyst.
FIG. 5 is g-C3N4CdS and CdS/g-C3N4UV-vis diffuse reflectance pattern of photocatalyst.
FIG. 6 shows g-C3N4And CdS/g-C3N4PL diagram of the photocatalyst.
FIG. 7 is a view showing the graph a g-C3N4And CdS/g-C3N4Photodegradation curve of the RhB photodegradation under visible light; FIG. b is g-C3N4And CdS/g-C3N4Rate constant (K) of photodegradation for 20 minobs) (ii) a FIG. C is CdS/g-C3N4Ultraviolet-visible absorption of RhB solution at different times of photocatalytic reactionAnd (6) collecting the spectrum.
FIG. 8 is CdS/g-C3N4Cyclic experiments for degradation of RhB aqueous solutions under visible light irradiation.
FIG. 9 shows g-C3N4And CdS/g-C3N4And (5) standing and settling the photocatalyst after 5 hours to compare the effect graphs.
Detailed Description
A preparation method of a visible light photocatalyst with tight connection comprises the following steps:
(1) preparation of g-C3N4Nanosheet: putting melamine serving as a precursor into a crucible with a cover, and feeding the crucible into a muffle furnace; heating to 550 deg.C at a rapid heating rate of 55 deg.C/min from room temperature, maintaining at the temperature for 4 h, naturally cooling to room temperature, and grinding to obtain light yellow powder g-C3N4Nanosheets for use;
(2) preparing CdS hollow microspheres:
adding cadmium nitrate tetrahydrate, thiourea and glutathione into distilled water according to the mass ratio of 1.67:1.24:1, mixing, wherein the mass concentration of the thiourea is 0.016 g/ml after mixing, and stirring for 1 h; then transferring the mixture into a polytetrafluoroethylene-lined stainless steel autoclave, and heating for 3 h at 250 ℃; then, taking out the obtained dark yellow product, centrifuging, washing with ultrapure water for several times, finally drying in an oven at 80 ℃ for 12 h, and grinding to obtain CdS hollow microspheres for later use;
(3) preparation of CdS/g-C3N4The composite photocatalyst comprises:
g to C3N4Dispersing the nano sheet and the CdS hollow microsphere into distilled water, and mixing g-C3N4The mass ratio of the nanosheet to the CdS hollow microsphere is 1: 0.001-1: 0.0075 (1: 0.001; 1: 0.0025; 1: 0.005; 1:0.0075 can be selected), g-C3N4The mass concentration is 0.0067 g/ml, the mixture is continuously stirred for 12 hours at the room temperature and then dried for 12 hours in an oven at the temperature of 80 ℃; then, putting the dried mixture into a crucible with a cover, sending the crucible into a muffle furnace, roasting the mixture for 1 h at 150 ℃, and grinding the mixture after natural cooling to obtain CdS/g-C3N4A composite photocatalyst is provided.
FIG. 1 is an XRD pattern of the sample, showing that pure g-C3N4Two obvious characteristic peaks exist at the 2 theta of 12.8 degrees and 27.5 degrees, which respectively correspond to g-C3N4The (100) and (002) crystal faces of the graphite belong to a typical graphite-like hexagonal crystal phase structure; for pure CdS, an XRD spectrogram of the CdS has a series of characteristic diffraction peaks of CdS, the structure of the CdS is a hexagonal wurtzite structure, and the structure has a wider absorption range in a visible region; while for CdS/g-C3N4XRD spectrogram of composite photocatalyst with CdS and g-C simultaneously3N4Characteristic diffraction peak shows that the CdS/g-C can be successfully prepared by the preparation method3N4A composite photocatalyst is provided.
FIG. 2 is the FTIR results of the samples, from which it can be seen that 3420 cm for oven dried pure CdS-1The absorption peak of (a) corresponds to the vibration of O-H on the surface thereof; for oven dried g-C3N4At about 3200 cm-1The broad peak at (A) corresponds to NH2And NH stretching vibration; for CdS/g-C3N4A composite photocatalyst is positioned at 3000-3600 cm-1The absorption peak of (A) is further widened due to C3N4And CdS, indicating a tight bond between the two.
FIG. 3 is an XPS spectrum of a sample, and the result shows that Cd 3d in the composite photocatalyst5/2The binding energy (400.3 eV) of the CdS is lower than that of Cd 3d in pure CdS5/2Due to CdS with g-C (407.5 eV)3N4Have strong electronic interaction between them, which is beneficial to the tight connection between them.
FIG. 4 is a TEM image of the sample, and the result shows that g-C3N4Is a two-dimensional lamellar structure nano-sheet; the CdS microsphere has obvious hollow structure with diameter of 28 nm and inner diameter of 6 nm, and is well fixed in g-C3N4Surface, again indicating the presence of a tight junction between the two.
FIG. 5 is a graph of UV-vis DRS of the sample, showing CdS/g-C3N4Composite lightAbsorption edge of catalyst with pure g-C3N4Compared with slight red shift, the visible light absorption range is expanded. This is due to the narrow band gap, high optical refractive index and hexagonal wurtzite structure of the CdS hollow microspheres.
FIG. 6 is a PL spectrum of the sample, and the result shows CdS/g-C3N4The recombination of photogenerated electron hole pairs in the composite photocatalyst is effectively inhibited, and the separation capability of carriers is obviously enhanced due to the fact that the separation and migration of the carriers can be accelerated by the existence of close connection between the photogenerated electron hole pairs and the photogenerated electron hole pairs.
FIGS. 7 and 8 are graphs of degradation profiles and cycle test results, respectively, for samples showing CdS/g-C with tight junctions3N4The composite photocatalyst has good photocatalytic degradation performance on RhB under the irradiation of visible light, and the optimal mass ratio of the composite photocatalyst is 0.25 wt% for 20 min photodegradation KobsAbout pure g-C3N42.1 times of the total weight of the powder. After 4 cycles CdS (0.25%)/g-C3N4The composite photocatalyst still keeps higher photocatalytic activity, the RhB degradation rate is 95%, and the composite photocatalyst has good stability.
FIG. 9 is a standing sedimentation diagram of the composite photocatalyst, and the result shows that CdS/g-C are formed after the suspended aqueous solution is subjected to standing sedimentation for 5 hours after the photodegradation reaction is completed3N4The composite photocatalyst is well separated from the aqueous solution, and can be repeatedly recycled.
Claims (2)
1. A preparation method of a visible light photocatalyst with tight connection is characterized by comprising the following steps:
(1) preparation of g-C3N4Nanosheet:
putting melamine serving as a precursor into a crucible with a cover, and feeding the crucible into a muffle furnace; heating to 550 deg.C at a rapid heating rate of 55 deg.C/min from room temperature, maintaining at the temperature for 4 h, naturally cooling to room temperature, and grinding to obtain light yellow powder g-C3N4Nanosheets for use;
(2) preparing CdS hollow microspheres:
adding cadmium nitrate tetrahydrate, thiourea and glutathione into distilled water according to the mass ratio of 1.67:1.24:1, mixing, wherein the mass concentration of the thiourea is 0.016 g/ml after mixing, and stirring for 1 h; then transferring the mixture into a polytetrafluoroethylene-lined stainless steel autoclave, and heating for 3 h at 250 ℃; then, taking out the obtained dark yellow product, centrifuging, washing with ultrapure water for several times, finally drying in an oven at 80 ℃ for 12 h, and grinding to obtain CdS hollow microspheres for later use;
(3) preparation of CdS/g-C3N4The composite photocatalyst comprises:
g-C prepared in the step (1)3N4Dispersing the nanosheets and the CdS hollow microspheres prepared in the step (2) into distilled water for mixing, and g-C3N4The mass ratio of the nanosheet to the CdS hollow microsphere is 1: 0.001-1: 0.0075, g-C3N4The mass concentration is 0.0067 g/ml, the mixture is continuously stirred for 12 hours at the room temperature and then dried for 12 hours in an oven at the temperature of 80 ℃; then, putting the dried mixture into a crucible with a cover, sending the crucible into a muffle furnace, roasting the mixture for 1 h at 150 ℃, and grinding the mixture after natural cooling to obtain CdS/g-C3N4A composite photocatalyst is provided.
2. The method for preparing a visible light photocatalyst having a tight junction according to claim 1, wherein g-C in the step (3)3N4The mass ratio of the nanosheet to the CdS hollow microsphere is 1:0.001 or 1:0.0025 or 1:0.005 or 1: 0.0075.
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