CN110449172B - Method for regulating and controlling activity of photoelectrocatalysis semiconductor material - Google Patents
Method for regulating and controlling activity of photoelectrocatalysis semiconductor material Download PDFInfo
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- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 31
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 30
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- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
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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
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/10—Chlorides
-
- 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
-
- B01J35/33—
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/50—Processes
- C25B1/55—Photoelectrolysis
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
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- 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 invention provides an activity regulation and control method of a photoelectrocatalysis semiconductor material, which adopts halide ions to carry out surface modification on an electrode material made of the semiconductor material. The method of the invention can obviously improve the catalytic activity of the semiconductor material and reduce the catalytic cost.
Description
Technical Field
The invention belongs to the technical field of photoelectrocatalysis semiconductors, and particularly relates to a regulation and control method for photoelectrocatalysis water decomposition semiconductor materials.
Background
Photocatalytic water splitting is a very potential technical means for solving the current energy and environmental problems, and semiconductors represented by bismuth vanadate, tungsten trioxide and graphene carbon nitride have wide application due to the fact that the semiconductors have narrow forbidden band widths, can absorb a large number of visible spectrums, and have the characteristics of high catalytic efficiency, good stability and the like. In addition to light absorption, carrier separation transfer and surface interface chemical reactions are key factors affecting photocatalytic performance. Previous studies have shown that the vanadate secret exposing the (040) crystal plane exhibits more excellent photocatalytic activity in water dissociation into oxygen and contaminant degradation, in part due to its improved carrier separation efficiency. On the other hand, the lifetime of the charge carriers is compared (approximately at 10)-6On the second scale), the time required for the surface reaction throughout the photocatalytic process is the longest (on the order of milliseconds), a kinetically slow step; the rate of this step is usually increased in photocatalysis by the introduction of a promoter. However, the complicated cocatalyst preparation process and its dependence on noble metals have limited their development and, moreover, the cocatalyst effect is not satisfactory at present.
In the photoelectrocatalysis, an external bias is applied to a semiconductor material while photocatalysis is carried out, and researchers think that the separation efficiency of photon-generated carriers can be improved under the action of voltage, so that the catalytic activity is improved. At the same time, there is a need to significantly increase the efficiency of the surface reaction to avoid recombination of carriers at the surface. On the other hand, because the semiconductor material is required to be made into an electrode in the photoelectrocatalysis process, the semiconductor material losing the free powder form often reduces the absorption efficiency of a light source; in addition, the preparation of the electrode changes the regulation and control effect of modified ions on crystal lattices, so that the photoelectrocatalysis often not capable of achieving the activity regulation and control effect.
Disclosure of Invention
The activity regulation and control method of the photoelectrocatalysis semiconductor material provided by the invention can break through the limitation of the existing photoelectrocatalysis effect, obviously improve the catalytic activity of the semiconductor material and reduce the catalytic cost.
The method for regulating and controlling the activity of the photoelectrocatalysis semiconductor material adopts halogen ions to carry out surface modification on an electrode material made of the semiconductor material.
Wherein the halide ions comprise chloride ions, bromide ions and iodide ions, and the chloride ions are preferred. The halide ion can be modified by the form of halide ion salt, including sodium halide, potassium halide, etc., preferably sodium chloride. The photoelectric catalytic semiconductor material comprises monoclinic phase and graphite phase semiconductor materials, and comprises bismuth vanadate, tungsten trioxide and carbon nitride; bismuth vanadate and tungsten trioxide are preferably monoclinic phase, carbon nitride is preferably graphitic phase, and most preferably monoclinic bismuth vanadate.
The operation steps of surface modification of the electrode material by adopting halide ions comprise: preparing the electrode material crystallized at the temperature of more than 350 ℃ into a conductive film (generally, the conductive film is attached to conductive glass in a coating, deposition and other modes), soaking the conductive film by adopting a (salt) solution containing halide ions, wherein the concentration of the halide ions in the solution is 0.5-5 mmol/L, preferably 1mmol/L, the soaking time is 4-15 h, and cleaning and drying to obtain a halide ion modified electrode material product.
Further, the conductive film can be attached to the conductive glass by adopting the modes of electrodeposition, hydrothermal deposition reaction, centrifugal sedimentation and spin coating, and a crystallized electrode material is formed; and drying the electrode material at 60 ℃ for 1-12 h after soaking.
Wherein the photoelectrocatalysis conditions of the electrode material are as follows: the 300W xenon lamp is used as a light source, and the voltage is 0.2-1.3V vs. Further, a typical three-electrode system is adopted, a 1M potassium borate solution is used as an electrolyte, a Pt wire is used as a counter electrode, an Ag/AgCl (saturated KCl) electrode is used as a reference electrode, and an electrode material is used as a working electrode.
Wherein the activity of the photoelectrocatalytic semiconductor material is mainly photoelectrocatalytic water decomposition to oxygen and hydrogen evolution.
The invention adopts halide ions to regulate and control the activity of the photoelectrocatalysis semiconductor material, the raw materials are easy to obtain, the cost is low, and the process is simple and easy to operate. The halogen ions are modified on the surface of the material in a soaking mode after the semiconductor material is crystallized, so that the generation speed of carriers on the surface of the semiconductor material is accelerated, and the concentration of the halogen ions is regulated and controlled to match with the conditions of proper photoelectrocatalysis and the like, so that the carriers are quickly and effectively separated after being generated, and the adverse effects of the reduction of the light source absorption efficiency and the reduction of the carrier density caused by the fact that the semiconductor material is made into an electrode material are effectively overcome. In addition, the modification of the halide ions can obviously reduce Gibbs free energy generated by the intermediate in the reaction process, further change the reaction path, and promote the accelerated generation of the intermediate through the surface-modified photoelectrocatalysis, thereby accelerating the whole catalysis process. The common photocatalytic powder material can be improved by more than 2 times in the photoelectric catalytic activity after being modified by chloride ions, and the electrode material can be improved by more than 3 times in the photoelectric catalytic activity compared with an unmodified semiconductor material.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate an embodiment of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is an XRD diffraction pattern of a bismuth vanadate electrode;
FIG. 2 is a diagram showing the change of photo-current of photoelectrocatalytic water decomposition of bismuth vanadate after sodium chloride modification;
FIG. 3 is a graph showing the change in the photo-response of sodium chloride-modified bismuth vanadate to photo-catalytic water decomposition;
FIG. 4 is an XRD diffraction pattern of tungsten trioxide before and after sodium chloride modification;
FIG. 5 is a linear scanning photocurrent-potential spectrum of tungsten trioxide before and after sodium chloride modification;
FIG. 6 is an XRD diffraction pattern of a carbon nitride electrode;
FIG. 7 is a graph showing the change in the photo-response of sodium chloride-modified carbon nitride after photo-electro catalytic water decomposition;
FIG. 8 is a graphical representation of a computational simulation of Gibbs free energy of intermediate species formation during bismuth vanadate catalysis before and after sodium chloride modification.
Detailed Description
For a better understanding of the present invention, reference is made to the following further description taken in conjunction with the accompanying drawings.
Regulation and control of bismuth vanadate oxygen generation activity of photoelectrocatalysis water decomposition catalyst by sodium chloride
1.1 Experimental part
3.88g of bismuth nitrate pentahydrate were weighed into 40mL of a solution containing 16mL of acetic acid and 1.6mL of concentrated nitric acid (70 wt%), dissolved and used for electrodeposition, conductive glass was used as an electrode, and the area was 1.0X 2.5cm2. The electrochemical workstation of Shanghai Chenghua CHI760E was used to perform electrodeposition on the electrodes, and a classical three-electrode system was used, in which Pt wire was used as the counter electrode, Ag/AgCl (saturated KCl) electrode was used as the reference electrode, and conductive glass was used as the working electrode. The electrodeposition conditions were that an externally applied voltage was 2.82V vs. rhe, the deposition time was 0.5h, and the obtained precursor conductive glass was immersed in distilled water and dried at room temperature. Then weighing 1.74g of vanadium acetylacetonate to dissolve in 100mL of acetylacetone, after dissolving, uniformly dripping 80 mu L of prepared vanadium acetylacetonate solution on the dried precursor conductive glass, after drying, putting the precursor conductive glass into a muffle furnace, and preserving the heat for 2 hours at the temperature of 500 ℃ in air with 350-. And finally, soaking the obtained conductive glass in 1mol/L sodium hydroxide solution, washing with distilled water, and drying to obtain the bismuth vanadate electrode material (bismuth vanadate precursor conductive glass).
Soaking the bismuth vanadate precursor conductive glass prepared by the electrodeposition method in a sodium chloride solution, wherein the concentration of the solution is 0.5-5 mmol/L, the soaking time is 4-15 h, and placing the bismuth vanadate precursor conductive glass into a 60 ℃ oven to be dried for 1-12 h to obtain the modified bismuth vanadate semiconductor conductive glass. The number of the finally obtained bismuth vanadate conductive glass is BVO-0.5h, which corresponds to the number of the bismuth vanadate electrode obtained after 0.5h of electrodeposition; Cl-BVO-0.5h corresponds to the bismuth vanadate electrode obtained after 0.5h of electrodeposition after sodium chloride modification.
1.2 evaluation method
1.2.1 the phase was characterized by XRD diffraction pattern.
1.2.2 adopt the electrochemical engineering of Shanghai Chenghua CHI760EAnd performing photoelectric catalytic water decomposition performance evaluation on the electrode material by taking a station as a station. The method comprises the following specific steps: A1M potassium borate solution is selected as an electrolyte, a typical three-electrode system is adopted, a Pt wire is used as a counter electrode, an Ag/AgCl (saturated KCl) electrode is used as a reference electrode, and the prepared electrode is used as a working electrode. A 300W xenon lamp was used as the light source. The scanning range of photocurrent intensity measurement is 0.2-1.3V vs. RHE, and the scanning speed is 50mV s-1. The time for the photoresponse measurement was 275 s.
1.3, evaluation results
FIG. 1 is an XRD pattern of a bismuth vanadate electrode obtained by an electrodeposition method, and the result shows that monoclinic phase bismuth vanadate is successfully obtained.
FIG. 2 is a diagram showing the change of photo-current in photoelectrocatalytic water decomposition of sodium chloride modified bismuth vanadate and unmodified bismuth vanadate. It can be seen that the photocurrent intensity of the electrode modified with sodium chloride was greater, and at 1.23vvs. rhe, the photocurrent intensity of the modified electrode was 5.51mA cm-2Whereas the photocurrent intensity of the unmodified electrode was only 1.46mA cm-2. The modification of sodium chloride has obvious enhancement effect on the water decomposition performance of bismuth vanadate photoelectrocatalysis.
FIG. 3 is a graph showing the change in the photocatalytic water splitting photoresponse of sodium chloride-modified bismuth vanadate and unmodified bismuth vanadate. Therefore, the bismuth vanadate electrode material is sensitive to switching of light, and the bismuth vanadate electrode modified by sodium chloride has stronger photocurrent.
Secondly, regulating and controlling oxygen generation activity of tungsten trioxide serving as photoelectrocatalysis water decomposition catalyst by sodium chloride
2.1 Experimental part
Weighing 0.46g of sodium tungstate dihydrate, adding the sodium tungstate dihydrate into 60mL of deionized water, and stirring for 30min to dissolve the sodium tungstate; adding 3M 12mL nitric acid, mixing and stirring for 3h to obtain a precursor solution. And (3) placing the mixed precursor solution into a 100mL high-pressure reaction kettle made of polytetrafluoroethylene, placing cleaned conductive glass into the reaction kettle, placing the hydrothermal kettle into an oven, and preserving heat at 160 ℃ for 12 hours. Washing the obtained electrode material with distilled water, drying, and carrying out annealing heat treatment for 1h at the temperature of 350-3。
Soaking the tungsten trioxide precursor conductive glass prepared by the hydrothermal method in a sodium chloride solution, wherein the concentration of the solution is 0.5-5 mmol/L, the soaking time is 4-15 h, and placing the tungsten trioxide precursor conductive glass in a 60 ℃ oven to be dried for 1-12 h to obtain the modified tungsten trioxide semiconductor conductive glass. The finally obtained tungsten trioxide conductive glass is numbered as Cl-WO3。
2.2 evaluation method
2.2.1 the phase is characterised by an XRD diffraction pattern.
2.2.2 the photoelectrocatalysis water splitting performance of the electrode material is evaluated by adopting a Shanghai Chenghua CHI760E electrochemical workstation. The method comprises the following specific steps: 0.1M potassium phosphate solution is selected as electrolyte, a typical three-electrode system is adopted, a Pt wire is used as a counter electrode, an Ag/AgCl (saturated KCl) electrode is used as a reference electrode, and the prepared electrode is used as a working electrode. A 300W xenon lamp was used as the light source. Linear sweep voltammetry measurements at 50mV s-1Is the scanning speed.
2.3, evaluation results
FIG. 4 is an XRD diffraction pattern of tungsten trioxide after sodium chloride modification. As can be seen from the figure, monoclinic phase tungsten trioxide was successfully synthesized, and the modification of sodium chloride did not affect the phase thereof.
FIG. 5 shows the photoelectrocatalytic water splitting performance of the tungsten trioxide electrode before and after sodium chloride modification, and it can be seen that the modified electrode has higher photocurrent intensity, i.e. the photocurrent at 1.23V vs. RHE is 2.6mA cm-2. While the photocurrent of the unmodified tungsten trioxide electrode is only 0.9mA cm-2。
Thirdly, regulating and controlling the carbon nitride hydrogen evolution activity of the photoelectrocatalysis water decomposition catalyst by sodium chloride
3.1, Experimental part
1.84g of melamine (15mmol) was weighed into 150mL of deionized water and mixed well, and the mixed solution was placed in an oil bath and refluxed at 95 ℃ for 2 h. And centrifugally settling the obtained precursor, washing with distilled water, drying and grinding to obtain the carbon nitride precursor. And (3) placing the carbon nitride precursor into a porcelain boat, coating the porcelain boat with tinfoil, placing the porcelain boat in a muffle furnace, and calcining the porcelain boat in air at 550 ℃ for 2 hours to finally obtain a carbon nitride sample.
Weighing 5mg of carbon nitride sample, dispersing in 3mL of ethanol, ultrasonically dispersing for 30min to prepare a suspension, coating the suspension on FTO conductive glass layer by using spin coating parameters of 10s at 200rpm and 30s at 800rpm, wherein the area of the film is 1 multiplied by 1cm2. After drying, the mixture is treated for 2 hours at 350 ℃ in Ar atmosphere. The obtained electrode was numbered C3N4。
And soaking the carbon nitride conductive glass obtained by the spin coating method in a sodium chloride solution, wherein the concentration of the solution is 0.5-5 mmol/L, the soaking time is 4-15 h, and placing the carbon nitride conductive glass in a 60 ℃ oven for drying for 1-12 h to obtain the modified carbon nitride semiconductor conductive glass. The finally obtained carbon nitride conductive glass is numbered Cl-C3N4。
3.2 evaluation method
3.2.1 the phase is characterized by XRD diffraction pattern.
3.2.2 the photoelectrocatalysis water splitting performance of the electrode material is evaluated by adopting a Shanghai Chenghua CHI760E electrochemical workstation. The method comprises the following specific steps: A0.1M sodium sulfate solution is selected as electrolyte, a typical three-electrode system is adopted, a Pt wire is used as a counter electrode, an Ag/AgCl (saturated KCl) electrode is used as a reference electrode, and the prepared electrode is used as a working electrode. A 300W xenon lamp was used as the light source. The time for measuring the photoresponse is 360s, and the scanning speed is 50mV s-1。
3.3 evaluation results
FIG. 6 is an XRD diffraction pattern of carbon nitride before and after modification with sodium chloride. As can be seen from the figure, the graphite phase carbon nitride was successfully synthesized, and the modification of sodium chloride did not affect the phase.
FIG. 7 shows a photocurrent response spectrum of sodium chloride-modified carbon nitride. Therefore, the carbon nitride electrode material is sensitive to the switching of light, and the carbon nitride electrode modified by the sodium chloride has stronger photocurrent.
Research on changing reflection path by sodium chloride modification
4.1 Experimental part
The specific experimental part is the same as 1.1.
The label of the bismuth vanadate before modification is BVO, and the label of the bismuth vanadate after modification is Cl-BVO.
4.2 evaluation method
4.2.1 Gibbs free energy required for the formation of all intermediates (OH, O, OOH) involved in the water splitting process was calculated based on the density functional theory using Vienna ab initio package (VASP). Use of
To eliminate the interaction between neighboring cells of the model, and a 2 x 1Monk-horst k-point grid is used for (110) the Brillouin zone integration of the surface model. The gibbs free energy for each intermediate species was calculated at 298.15K according to the following equation:
ΔG＝ΔEDFT+ΔEZPE-TΔS
wherein Δ EDFTIs the adsorption energy of the adsorbed species of the catalyst,. DELTA.EZPEAnd Δ S are the differences in zero energy and entropy between the adsorbed atom and the molecule, respectively.
4.3 evaluation results
FIG. 8 is a simulation diagram showing the calculation of Gibbs free energy for the intermediate species generated by the surface oxidation of bismuth vanadate before and after modification. The rate-determining step for the photoelectrocatalytic hydro-oxidation process of the BVO sample was that OH formation had 3.3eV, while OH formation for the sodium chloride modified bismuth vanadate Cl-BVO hydro-oxidation process had a smaller gibbs free energy (1.67eV), and in addition the rate-determining step was also changed, i.e. had a smaller gibbs free energy O formation (2.18 eV).
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (4)
1. The application of the photoelectrocatalysis water decomposition semiconductor material in photoelectrocatalysis water decomposition oxygen and hydrogen evolution is characterized in that halide ions are adopted to carry out surface modification on an electrode material made of the semiconductor material, wherein the halide ions comprise chloride ions, bromide ions and iodide ions; the halide ions are introduced into modification in the form of halide ion salts, including sodium halide and potassium halide; the photoelectrocatalysis water decomposition semiconductor material is bismuth vanadate and tungsten trioxide; the method is characterized in that bismuth vanadate and tungsten trioxide are monoclinic phases, and the operation steps of surface modification of the electrode material by adopting halide ions are as follows: preparing the electrode material crystallized at the temperature of more than 350 ℃ into a conductive film, soaking the conductive film by adopting a salt solution containing halide ions, wherein the concentration of the halide ions in the solution is 0.5-5 mmol/L, the soaking time is 4-15 h, and then drying to obtain a halide ion modified electrode material product.
2. The use of a photoelectrocatalytic water-splitting semiconductor material in photoelectrocatalytic water-splitting oxygen and hydrogen evolution according to claim 1, wherein the conductive thin film is soaked with a halide-containing salt solution having a halide ion concentration of 1 mmol/L.
3. The application of the photoelectrocatalytic water-splitting semiconductor material in photoelectrocatalytic water-splitting oxygen and hydrogen evolution according to claim 1, wherein the conductive film is attached to conductive glass by means of electrodeposition, hydrothermal deposition reaction, centrifugal sedimentation and spin coating to form a crystallized electrode material; and drying the electrode material at 60 ℃ for 1-12 h after soaking.
4. The use of a photoelectrocatalytic water-splitting semiconductor material as set forth in claim 1 for photoelectrocatalytic water-splitting oxygen and hydrogen evolution, wherein the photoelectrocatalytic conditions of the electrode material are: the 300W xenon lamp is used as a light source, and the voltage is 0.2-1.3 Vvs.
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