CN114988378B - N-doped black phosphazene photocatalyst, and preparation method and application thereof - Google Patents
N-doped black phosphazene photocatalyst, and preparation method and application thereof Download PDFInfo
- Publication number
- CN114988378B CN114988378B CN202110230501.9A CN202110230501A CN114988378B CN 114988378 B CN114988378 B CN 114988378B CN 202110230501 A CN202110230501 A CN 202110230501A CN 114988378 B CN114988378 B CN 114988378B
- Authority
- CN
- China
- Prior art keywords
- nitrogen
- phosphazene
- black
- doped black
- doped
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000005922 Phosphane Substances 0.000 claims abstract description 54
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910000064 phosphane Inorganic materials 0.000 claims abstract description 54
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 37
- 239000010941 cobalt Substances 0.000 claims abstract description 37
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 37
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000001257 hydrogen Substances 0.000 claims abstract description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 claims abstract description 25
- 238000011068 loading method Methods 0.000 claims abstract description 22
- -1 black phosphorus alkene Chemical class 0.000 claims abstract description 15
- 239000002135 nanosheet Substances 0.000 claims description 33
- 229910052723 transition metal Inorganic materials 0.000 claims description 22
- 239000002064 nanoplatelet Substances 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 17
- 238000001354 calcination Methods 0.000 claims description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 150000003624 transition metals Chemical class 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000003837 high-temperature calcination Methods 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000013032 photocatalytic reaction Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 238000004299 exfoliation Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 229910002001 transition metal nitrate Inorganic materials 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 26
- 229910052751 metal Inorganic materials 0.000 abstract description 25
- 239000002184 metal Substances 0.000 abstract description 25
- 239000013078 crystal Substances 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 10
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 7
- 238000004873 anchoring Methods 0.000 abstract description 5
- 230000003993 interaction Effects 0.000 abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 20
- 239000000843 powder Substances 0.000 description 20
- 238000012360 testing method Methods 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 229910052786 argon Inorganic materials 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 8
- 229910021529 ammonia Inorganic materials 0.000 description 7
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 7
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910021389 graphene Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000000227 grinding Methods 0.000 description 4
- 238000009616 inductively coupled plasma Methods 0.000 description 4
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 229910001429 cobalt ion Inorganic materials 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 240000001549 Ipomoea eriocarpa Species 0.000 description 1
- 235000005146 Ipomoea eriocarpa Nutrition 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002065 inelastic X-ray scattering Methods 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/003—Phosphorus
-
- 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
-
- B01J35/23—
-
- B01J35/33—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/02—Preparation of phosphorus
-
- 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
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Abstract
The invention discloses an N-doped black phosphane photocatalyst, a preparation method and application thereof. On the premise of keeping the crystal structure and photoelectric property of the black phosphorus, the interaction between the black phosphorus alkene and the metal is enhanced through N atom doping for the first time, so that more anchoring sites are provided for the metal cobalt, the loading capacity of the metal cobalt on the black phosphorus alkene is obviously improved, and the photocatalytic hydrogen production activity of the N-doped black phosphorus alkene is further enhanced. The experimental results show that: the loading of the metallic cobalt is obviously improved compared with that of the black phosphazene, and thus the photocatalytic hydrogen production activity is greatly improved.
Description
Technical Field
The invention belongs to the technical field of photocatalytic hydrogen production, relates to an N-doped black phosphazene photocatalyst, and a preparation method and application thereof, and particularly relates to a method for doping nitrogen into black phosphazene to improve metal cobalt loading capacity and using the nitrogen as a photocatalyst to drive photocatalytic reaction to produce hydrogen.
Background
Black phosphazene is a new member of a two-dimensional layered material family, and has unique characteristics of tunable direct band gap, ultrahigh charge mobility, strong optical absorption, large specific surface area, anisotropic structure and the like, so that the black phosphazene is rapidly developed into one of the two-dimensional materials which are most concerned after graphene. The band gap property (0.3 eV-2 eV) of the graphene with the change of the layer number makes up the defect of overlarge band gap of the graphene zero band gap and the metal chalcogenide band gap, so that the black phosphazene is a photocatalyst semiconductor material with great development potential (see adv. Mater.2018,30 (32), 1800295,Small.2019,1804565,Advanced Energy Materials 2018,8 (5), 1701832, adv. Funct. Mater.2020,30 (22), ACS nano 2014,8 (4), 4033-4041). However, the photocatalytic activity of the black phosphazene itself is severely limited by the defects that the photo-generated charges are easy to be compounded, the black phosphazene is easy to be oxidized and decomposed, and the like. Thus, black-phospholene-based photocatalytic systems often require the introduction of cocatalysts.
Transition metals have been attracting attention due to their high catalytic activity, and photocatalytic solar energy conversion systems based on transition metal/black phosphorus composite photocatalysts have been reported in succession through research and development in recent years (e.g., adv.Mater.2018,1803641, adv.Mater.2017,29 (42), adv.Sci.2018,5,1800575,Chem.Commun, 2017,53,10946-10949, adv. Mater.2018, 1803641). Among the transition metals, metallic cobalt and cobalt phosphide are used as cocatalysts, and the photocatalytic water splitting system shows excellent catalytic activity, and in addition, compared with noble metals, the metallic cobalt has the advantages of low cost, rich reserves and the like. Therefore, the metal cobalt is selected as the promoter of the black phosphazene photocatalytic system, and has a higher application prospect (such as Angew.chem.int.ed.2018,57,2600-2604,ACS Catal.2019,9,9,7801-7807). However, the weak interaction of the black phosphazene and cobalt metal ions leads to low loading of the black phosphazene to the metal cobalt, so that the photocatalytic water splitting hydrogen production activity is not satisfactory. Therefore, how to develop a photocatalyst capable of increasing the metal cobalt loading to improve the photocatalytic hydrogen production activity from the structure or property of the black phosphazene and a preparation method thereof are technical problems to be solved.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a black phosphazene with higher transition metal loading, so that the photocatalytic activity of the black phosphazene is greatly improved.
The invention aims at realizing the following technical scheme:
a modified black phosphane in which the black phosphane is N-doped and a transition metal is supported on the N-doped black phosphane.
According to an embodiment of the invention, the transition metal is preferably cobalt.
According to an embodiment of the present invention, the loading amount of the transition metal on the N-doped black phosphane is 0.002 to 0.15wt%, preferably 0.004 to 0.1wt%, and exemplified by 0.004wt%, 0.008wt%, 0.01wt%, 0.015wt%, 0.018wt%, 0.02wt%, 0.026wt%, 0.03wt%, 0.04wt%, 0.05wt%, 0.06wt%, 0.08wt%, 0.09wt%, 0.1wt%, based on the mass of the N-doped black phosphane.
According to an embodiment of the present invention, the doping amount of N in the N-doped black phosphane is 1 to 5%, preferably 2 to 4%, and exemplary is 1%, 2%, 3%, 3.64%, 4%, 5% of the total mass of the N-doped black phosphane.
According to an embodiment of the invention, the modified black phosphazene is a nanoplatelet.
According to an embodiment of the invention, the N-doped black phosphazene carrier has a morphology substantially as shown in fig. 5 (b).
The invention also provides a preparation method of the modified black phosphazene, which comprises the steps of taking N-doped black phosphazene and transition metal salt as raw materials, and loading transition metal ions by a solution impregnation method to prepare the photocatalyst.
According to the invention, the N-doped black phosphazene is a nano-sheet.
In one embodiment of the invention, the N-doped black phosphazene nanosheet dispersion is mixed with a transition metal salt, stirred and centrifuged to obtain the modified black phosphazene. For example, the stirring time is 0.5 to 2 hours. Further, the modified black phosphazene obtained is washed and dried.
According to the embodiment of the invention, the N-doped black phosphazene is prepared from raw materials comprising a phosphorus source and an N source by a high-temperature calcination method.
According to the invention, the phosphorus source is provided by black phosphorus. For example, the black phosphorus is preferably black phosphorus powder crystals. More preferably, the black phosphorus powder crystals further comprise a step of grinding before the reaction. For example, the grinding time is, for example, 0.5 to 2 hours. Illustratively, the milling time may be 0.5h, 1h, 2h.
According to the invention, the N source is provided by an ammonia atmosphere. For example, the flow rate of ammonia gas is 5 to 20mL/min, preferably 8 to 15mL/min.
According to the invention, the high temperature calcination is carried out under an inert atmosphere, for example under nitrogen, or argon atmosphere, preferably under argon atmosphere.
According to the invention, before the high-temperature calcination, inert gas is introduced to exhaust air, and then the high-temperature calcination is performed under the mixed atmosphere of the inert gas and ammonia.
According to the present invention, the high temperature calcination temperature is 200 to 400 ℃, preferably 250 to 350 ℃, and exemplary 200 ℃, 250 ℃, 300 ℃, 350 ℃, 400 ℃; the calcination time is 1 to 8 hours, preferably 2 to 6 hours, and exemplified by 1 hour, 2 hours, 3 hours, 4 hours, 6 hours, 8 hours.
According to the invention, the temperature rise rate of the high-temperature calcination is 2-8 ℃/min, and is exemplified by 2 ℃/min, 5 ℃/min and 8 ℃/min.
In one embodiment of the present invention, the N-doped black phosphazene nanoplatelets can be prepared by a liquid phase exfoliation method, comprising: and (3) carrying out ultrasonic stripping on the N-doped black phosphazene in water, and centrifuging. The time of the ultrasound is, for example, 6-10 hours. In one embodiment, the centrifugation may be performed at a different rotational speed, for example 4000-6000rpm for the first centrifugation and 8000-12000rpm for the second centrifugation. Preferably, the centrifuged N-doped black phosphazene nanoplatelets are dried.
According to an embodiment of the invention, the transition metal salt is used in an amount of 1 to 10%, preferably 2 to 8%, and exemplary 1%, 2%, 5%, 8%, 10% by mass of the N-doped black phosphazene.
According to an embodiment of the present invention, the transition metal salt may be selected from at least one of nitrate, hydrochloride and sulfate of a transition metal, for example, preferably from nitrate of a transition metal. Preferably, the transition metal has the meaning as described above.
According to an embodiment of the present invention, the method for preparing the modified black phosphazene comprises the following steps:
(1) Preparation of N-doped black phosphazene: grinding black phosphorus powder crystals, and then placing the black phosphorus powder crystals in a tube furnace; calcining at high temperature in a mixed atmosphere of argon and ammonia, naturally cooling to room temperature after the reaction is finished, ultrasonically stripping the obtained powder in a water phase, centrifuging, and taking supernatant fluid to obtain a dispersion liquid of the N-doped black phosphazene material;
(2) Mixing the N-doped black phosphazene dispersion liquid prepared in the step (1) with a transition metal salt solution, and carrying out metal ion loading by a solution impregnation method to prepare the photocatalyst.
The invention also provides the application of the modified black phosphazene in a photocatalyst. For example, in the production of hydrogen by photocatalytic reactions.
The invention also provides a method for preparing hydrogen by adopting the modified black phosphazene through photocatalysis reaction, which comprises the step of contacting the modified black phosphazene with an electronic sacrificial agent and carrying out reaction by illumination.
According to an embodiment of the present invention, the electron sacrificial agent may be methanol, triethanolamine, oxalic acid, aqueous lactic acid, na 2 S and Na 2 SO 3 At least one of them is preferably methanol.
According to an embodiment of the invention, the photocatalytic reaction is carried out in a solvent system. Preferably, the solvent may be water.
According to an embodiment of the invention, the photocatalytic reaction is carried out under an inert atmosphere, for example under nitrogen, or under argon, preferably under argon.
According to an embodiment of the invention, the illumination is for example illuminated with a white LED lamp. Preferably, the time of the photocatalytic reaction is 4 to 12 hours, preferably 5 to 10 hours.
The invention has the beneficial effects that:
(1) The N-doped black phosphane is prepared from the structure or property of the black phosphane, and nitrogen atoms are introduced as anchoring sites of metal for the first time on the premise of not changing the original crystal structure and photoelectric property of the black phosphane, so that the loading capacity of metal cobalt ions is increased, and the photocatalytic hydrogen production activity is enhanced.
(2) According to the invention, a method of calcining black phosphorus powder in an argon/ammonia mixed atmosphere is adopted, and a P-N covalent bond is formed by phosphorus atoms and nitrogen atoms in the black phosphorus structure, so that N with stronger electronegativity is successfully doped into a black phosphazene crystal structure for the first time. On the premise of keeping the crystal structure and photoelectric property of the black phosphorus, the interaction between the black phosphorus alkene and the metal is enhanced by doping N atoms, so that more anchoring sites are provided for the metal cobalt, the loading capacity of the metal cobalt on the black phosphorus alkene is remarkably improved, and the aim of enhancing the photocatalytic hydrogen production activity is fulfilled. The experimental results show that: the loading of the metallic cobalt is obviously improved compared with that of the black phosphazene, and thus the photocatalytic hydrogen production activity is greatly improved.
Drawings
Fig. 1 is a schematic diagram of the preparation of an N-doped black phosphorus material.
In fig. 2, (a) shows XRD patterns of the black phosphorus crystals before and after calcination, and (b) shows Raman (Raman) spectra of the black phosphorus crystals before and after calcination.
FIG. 3 is an infrared spectrum of black phosphorus before and after calcination.
FIG. 4 shows XPS (a) full spectrum, (b) N1s high-resolution spectrum, (c) and (d) P2P high-resolution spectrum of the N-BP material obtained by calcining for 2h.
In FIG. 5, (a), (b), (c) and (d) are undoped black phosphazene nanoplatelet powder (BP), calcined for 2h (BP-NH) 3 -2 h), calcination 4h (BP-NH 3 -4 h), calcination for 6h (BP-NH 3 -6 h) TEM image of the black phosphane nanoplatelets.
FIG. 6 is a photocatalytic hydrogen production test result of N-BP, wherein: (a) And (b) testing the change of the photocatalytic hydrogen production amount with time of N-BP-2 h.
FIG. 7 is an ICP test of BP, and N-BP loading to Co.
FIG. 8 is a high resolution spectrum of Co 2p from XPS test of BP-Co and N-BP-Co.
Fig. 9 electrochemical activity test of black phosphane nanoplatelets, (a) electrical impedance test, (b) photocurrent response test.
Detailed Description
The technical scheme of the invention will be further described in detail below with reference to specific embodiments. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
Example 1: preparation of N-doped black phosphazene nanosheet photocatalyst
(1) Preparing N-doped block black phosphorus: grinding 50mg of a block black phosphorus powder crystal (purchased from Xianfeng nanometer (south Beijing of Jiangsu)) purchased for 1h until the particles are fine and uniform, transferring the powder crystal into a tube furnace, and introducing argon (flow rate: 50 mL/min) for 30min to exhaust the air although inside;
(2) Calcining at high temperature in a mixed atmosphere of argon and ammonia (argon flow rate: 50mL/min, ammonia flow rate: 10 mL/min), heating to 300 ℃ from room temperature at 5 ℃/min, and then respectively preserving heat for 2h, 4h and 6h; naturally cooling to room temperature after the reaction is finished to obtain N-doped block black phosphorus;
(3) Preparing N-doped black phosphane nanometer sheets by a liquid phase stripping method: placing 30mg of N-doped block black phosphorus prepared in the step (2) into a 50mL sharp-bottomed centrifuge tube, adding 45mL of ultrapure water, introducing argon gas to remove air and dissolved oxygen in the tube so as to prevent black phosphorus materials from oxidizing, sealing the centrifuge tube, then performing ultrasonic stripping for 6-10h under ice water bath (0 ℃), centrifuging the obtained N-doped black phosphorus nano-sheet suspension (5000 rpm for 20 min), collecting supernatant, centrifuging (10000 rpm for 30 min), collecting solids, drying in a vacuum oven (40 ℃ for 12 h) to obtain N-doped black phosphorus nano-sheet powder (wherein N-doped black phosphorus nano-sheets obtained by heat preservation for 2h, 4h and 6h are respectively named as BP-NH) 3 -2h、BP-NH 3 -4h、BP-NH 3 -6h)。
Comparative example 1: preparation of photocatalyst of undoped black phosphazene nanosheet
The difference from example 1 is that: the purchased 30mg of bulk black phosphorus powder crystals were directly subjected to the liquid phase exfoliation step of step (3), to obtain undoped black phosphorus nano-sheet powder (named BP).
Preserving heat for 2h, 4h and 6h to obtain the N-doped black phosphane nanometer sheet BP-NH 3 -2h、BP-NH 3 -4h、BP-NH 3 -6h and undoped black phosphazene nano-sheet powderThe last BP was subjected to X-ray diffraction (XRD) and Raman spectroscopy (Raman) characterization, and the results are shown in FIG. 2 (a) and FIG. 2 (b), respectively. As can be seen from the figure, the black phosphorus crystal structure was not changed before and after the N doping.
Preserving heat for 2h, 4h and 6h to obtain the N-doped black phosphane nanometer sheet BP-NH 3 -2h、BP-NH 3 -4h、BP-NH 3 The infrared spectrum (FTIR) characterization was performed for 6h and undoped black phosphane nanoplatelet powder BP, respectively, and the results are shown in FIG. 3. From the results in the figures, it can be seen that: after N doping the black phosphazene nano-sheet, the nano-sheet is positioned at 902.4cm -1 Characteristic peaks of P-N appear. This shows that: in the mixed atmosphere of argon and ammonia, the phosphorus atoms and nitrogen atoms in the black phosphorus structure form P-N covalent bonds through high-temperature calcination, so that the N-doped black phosphazene nano-sheet is realized.
FIG. 4 shows XPS (a) full spectrum, (b) N1s high-resolution spectrum, (c) and (d) P2P high-resolution spectrum of the N-BP material obtained by calcining for 2h.
In FIG. 5, (a), (b), (c) and (d) are respectively undoped black phosphane nano-sheet powder (BP), N-doped black phosphane nano-sheet powder (BP-NH) obtained by calcining for 2 hours 3 -2 h), calcining for 4h to obtain N-doped black phosphazene nano-sheet powder (BP-NH) 3 -4 h), calcining for 6h to obtain N-doped black phosphazene nano-sheet powder (BP-NH) 3 -6 h).
Example 2: preparation of N-doped black phosphane nanosheet supported metal cobalt photocatalyst
The N-doped black phosphazene nano-sheet prepared in the embodiment 1 realizes the loading of metal cobalt ions by a solution impregnation method, and the specific method is as follows:
n-doped black phosphane nanoplatelets (BP-NH) at 0.5mg/mL 3 -2 h) adding a cobalt nitrate solution (cobalt nitrate mass: N-doped black phosphane nanoplatelet mass = 5:100 Stirring for 1 hour until the reaction is complete, centrifuging, washing with water for 3 times (the centrifuging speed is 10000 r/min, the time is 30 min), collecting solid, and putting into a vacuum oven for drying (40 ℃ for 12 h), thus obtaining the N-doped black phosphazene nano-sheet material (N-BP-Co) loaded with metallic cobalt.
Comparative example 2: preparation of photocatalyst with undoped black phosphane nano-sheet loaded with metallic cobalt
The undoped black phosphane nanoplatelets prepared in comparative example 1 were prepared into a photocatalyst of undoped black phosphane nanoplatelet supported metal cobalt (BP-Co) in the same preparation method as in example 2.
Inductively coupled plasma emission spectrometry (ICP) was performed on the N-BP-Co prepared in example 2 and the BP-Co material prepared in comparative example 2 to obtain the loading amount of metallic cobalt, and the results are shown in Table 1 below.
TABLE 1 ICP test of BP-Co and N-BP-Co
Note that: the adding amount of the cobalt nitrate is 5wt%, and the mass of the cobalt nitrate is that the mass of the N-doped black phosphane nanometer sheet is=5: 100.
the results are plotted in FIG. 7. As can be seen from the figures: the N-doped black phosphane nanometer sheet can obviously improve the loading capacity of the metal cobalt.
FIG. 8 is XPS test of N-BP-Co prepared in example 2 and BP-Co material prepared in comparative example 2, co 2p Is a high resolution spectrogram of (c). As can be seen from the figures: the characteristic peak of Co is not detected in the elemental analysis map of the N-undoped black phosphane loaded metal cobalt, which indicates that the loading amount of the N-undoped black phosphane to the metal cobalt is too low; and a characteristic peak of Co appears in an XPS spectrum of N-doped black phosphane loaded metal cobalt, so that the characteristic peak shows that after N-doped black phosphane, the doped N atoms in the black phosphane can be used as anchoring sites of metal, thereby obviously improving the loading capacity of the metal cobalt.
The preparation method of the working electrode comprises the following steps:
respectively adding 2mg BP, BP-Co, BP-NH 3 -2h、BP-NH 3 Dispersing a 2h-Co sample in 150 mu L of ethanol and 350 mu L of ultrapure water, performing ultrasonic treatment for 30min to form a homogeneous solution, then dripping the homogeneous solution on the surface of a pre-cleaned 1cm multiplied by 2cm ITO glass electrode, and air-drying to obtain a working electrode, and performing electrochemical performance test.
Electrochemical performance testing was performed on a CHI660e electrochemical workstation (Shanghai morning glory instrument), using standardThree electrode system: the working electrode, platinum sheet (1 cm) 2 ) As a counter electrode, ag/AgCl was used as a reference electrode. Na of electrolyte 0.5M 2 SO 4 A solution. The test results are shown in fig. 9, and the results in the graph show that after the N-doped black phosphane nano-sheet is further loaded with metallic cobalt, the photoelectrocatalytic activity of the black phosphane nano-sheet can be remarkably improved. Therefore, after N is doped with the black phosphane, the doped N atom in the black phosphane can be used as an anchoring site of metal, so that the loading amount of the metal cobalt is obviously improved, and the electrochemical performance of the black phosphane is improved.
Example 3: hydrogen production test of N-doped black phosphane supported metallic cobalt photocatalyst
The reaction steps are as follows: 5wt% metallic cobalt loaded (cobalt nitrate mass: N-doped black phosphane nanoplatelet mass=5:100) N-doped black phosphane nanoplatelets (2 mg) were added to a reaction tube with magnetite and 6mL methanol-water (V Alcohols ：V Water and its preparation method =1:5) mixed solvent. After the air is exhausted by inert gas (nitrogen or argon and the like), the reaction tube is irradiated by a 100W white light LED lamp for reaction for 8 hours, and the system is cooled by a water cooling mode. After the reaction was completed, the product hydrogen was quantified by gas chromatography equipped with a thermal conductivity detector.
Fig. 6 (a) shows the results of the photocatalytic hydrogen production test of the black phosphazene nanoplatelets calcined for different times, and the results can be seen from the graph: the N-doped graphene nano-sheet has little influence on the photocatalytic hydrogen production performance of the graphene nano-sheet, but after the N-doped graphene nano-sheet is further loaded with 5wt% of metallic cobalt, the photocatalytic hydrogen production performance of the graphene nano-sheet can be remarkably improved, and the N-doped graphene nano-sheet (BP-NH 3 2 h) after 5 weight percent of metallic cobalt is loaded, the prepared N-doped black phosphane nanometer sheet has the best photocatalytic hydrogen production performance.
In FIG. 6 (b), the N-doped black phosphane nanometer sheet powder (BP-NH) obtained by calcining undoped black phosphane nanometer sheet powder (BP) for 2h 3 -2 h), undoped black phosphane nanoplatelet powder (BP) loaded with 5% metallic cobalt (cobalt nitrate mass: undoped black phosphane nanoplatelet mass = 5:100 5% metallic cobalt loaded on N-BP-2h (cobalt nitrate mass: N-doped black phosphane nanoplatelet mass=5: 100 Measurement of photocatalytic hydrogen production over timeResults were tested. As can be seen from the figures: with the time extension, the N doping has little influence on the photocatalytic hydrogen production performance of the black phosphane nano-sheet, but after the N doping black phosphane nano-sheet is further loaded with 5 weight percent of metallic cobalt, the photocatalytic hydrogen production performance of the black phosphane nano-sheet can be obviously improved, and the N doping black phosphane nano-sheet (BP-NH 3 2 h) after 5 weight percent of metallic cobalt is loaded, the prepared N-doped black phosphane nanometer sheet has the best photocatalytic hydrogen production performance.
In conclusion, the N-doped black phosphazene nano-sheet can remarkably improve the loading capacity of the metal cobalt so as to realize high-efficiency photocatalytic hydrogen production activity.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (13)
1. The preparation method of the nitrogen-doped black phosphane photocatalyst is characterized by comprising the steps of mixing a nitrogen-doped black phosphane nanosheet dispersion liquid with transition metal salt, stirring and centrifuging to obtain the nitrogen-doped black phosphane photocatalyst;
the transition metal is cobalt;
the nitrogen-doped black phosphazene is prepared from raw materials including a phosphorus source and a nitrogen source by a high-temperature calcination method; the phosphorus source is black phosphorus; the nitrogen source is ammonia gas; the high-temperature calcination temperature is 200-400 ℃, and the calcination time is 1-8 hours.
2. The nitrogen-doped black phosphazene photocatalyst of claim 1, wherein the loading of transition metal on the nitrogen-doped black phosphazene is 0.002-0.15 wt% based on the mass of the nitrogen-doped black phosphazene.
3. The nitrogen-doped black phosphazene photocatalyst of claim 2, wherein the loading of the transition metal on the nitrogen-doped black phosphazene is 0.004-0.1wt% based on the mass of the nitrogen-doped black phosphazene.
4. The nitrogen-doped black phosphazene photocatalyst of claim 1, wherein the doping amount of nitrogen in the nitrogen-doped black phosphazene is 1-5% of the total mass of the nitrogen-doped black phosphazene.
5. The nitrogen-doped black phosphazene photocatalyst of claim 1, wherein the doping amount of nitrogen in the nitrogen-doped black phosphazene is 2-4% of the total mass of the nitrogen-doped black phosphazene.
6. The nitrogen-doped black-phosphazene photocatalyst of claim 1, wherein the high temperature calcination is performed under an inert atmosphere;
the high-temperature calcination temperature is 250-350 ℃; the calcination time is 2-6 hours.
7. The nitrogen-doped black phosphazene photocatalyst of claim 1, wherein the nitrogen-doped black phosphazene nanoplatelets are prepared by a liquid phase exfoliation method, comprising: and (3) carrying out ultrasonic stripping on the nitrogen-doped black phosphazene in water, and centrifuging.
8. The nitrogen-doped black-phosphorus alkene photocatalyst of claim 1, wherein the transition metal salt is selected from at least one of a nitrate, a hydrochloride, and a sulfate of a transition metal.
9. The nitrogen-doped black-phosphazene photocatalyst of claim 1, wherein the transition metal salt is selected from the group consisting of transition metal nitrates.
10. The nitrogen-doped black-phosphorus alkene photocatalyst of any of claims 1-9, wherein the nitrogen-doped black-phosphorus alkene photocatalyst is used in photocatalytic reaction hydrogen production.
11. A method for producing hydrogen by photocatalytic reaction, comprising contacting the nitrogen-doped black phosphazene of any one of claims 1 to 9 with an electron sacrificial agent, and reacting by irradiation with light.
12. The method for producing hydrogen by photocatalytic reaction as claimed in claim 11, wherein said electron sacrificial agent is methanol, triethanolamine, oxalic acid, aqueous lactic acid, na 2 S and Na 2 SO 3 At least one of them.
13. The method for producing hydrogen by photocatalytic reaction as claimed in claim 12, wherein said electron sacrificial agent is methanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110230501.9A CN114988378B (en) | 2021-03-02 | 2021-03-02 | N-doped black phosphazene photocatalyst, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110230501.9A CN114988378B (en) | 2021-03-02 | 2021-03-02 | N-doped black phosphazene photocatalyst, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114988378A CN114988378A (en) | 2022-09-02 |
| CN114988378B true CN114988378B (en) | 2023-07-28 |
Family
ID=83018551
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110230501.9A Active CN114988378B (en) | 2021-03-02 | 2021-03-02 | N-doped black phosphazene photocatalyst, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114988378B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105977311A (en) * | 2016-07-13 | 2016-09-28 | 东南大学 | Resonant tunneling diode realized by use of different stacking structures of few-layer black phosphorene, and realization method |
| CN111646439A (en) * | 2020-06-19 | 2020-09-11 | 昆明理工大学 | Method for doping nano black phosphorus or black phosphorus-based mixed material |
| CN112047313A (en) * | 2020-09-21 | 2020-12-08 | 东北大学 | Preparation and hydrogen storage method of calcium-doped modified two-dimensional black phosphorus nanosheet |
-
2021
- 2021-03-02 CN CN202110230501.9A patent/CN114988378B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105977311A (en) * | 2016-07-13 | 2016-09-28 | 东南大学 | Resonant tunneling diode realized by use of different stacking structures of few-layer black phosphorene, and realization method |
| CN111646439A (en) * | 2020-06-19 | 2020-09-11 | 昆明理工大学 | Method for doping nano black phosphorus or black phosphorus-based mixed material |
| CN112047313A (en) * | 2020-09-21 | 2020-12-08 | 东北大学 | Preparation and hydrogen storage method of calcium-doped modified two-dimensional black phosphorus nanosheet |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114988378A (en) | 2022-09-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105413730B (en) | A kind of preparation method of nitrogen-doped carbon nanometer pipe parcel cobalt electrocatalytic oxidation reducing material | |
| Liao et al. | Hierarchical porous NiO as a noble-metal-free cocatalyst for enhanced photocatalytic H 2 production of nitrogen-deficient gC 3 N 4 | |
| CN113270595B (en) | Nitrogen-doped carbon-supported non-noble metal nano catalyst prepared based on MOF | |
| CN109908959B (en) | Core-shell ZnO/precious metal @ ZIF-8 photocatalytic material and preparation method and application thereof | |
| Zhang et al. | Mechanism investigation of PtPd decorated Zn0. 5Cd0. 5S nanorods with efficient photocatalytic hydrogen production combining with kinetics and thermodynamics | |
| CN112619710A (en) | Triazine-based covalent network loaded metal monoatomic composite material and preparation method and application thereof | |
| CN110975912B (en) | Preparation and application of cobalt-nitrogen doped catalyst derived from bimetallic MOFs (metal-organic frameworks) | |
| CN102500360B (en) | Method for preparing mesoporous tungsten oxide/carbon composite conductive materials | |
| CN113881965B (en) | Metal nanoparticle supported catalyst with biomass carbon source as template and preparation method and application thereof | |
| Bai et al. | A facile one-step preparation of a Pd–Co bimetallic hollow nanosphere electrocatalyst for ethanol oxidation | |
| CN112725819A (en) | Tungsten-molybdenum-based nitrogen carbide nano material and preparation method and application thereof | |
| CN106492863A (en) | The method that base metal molybdenum carbide catalyst is prepared using cold plasma | |
| An et al. | 0D ultrafine ruthenium quantum dot decorated 3D porous graphitic carbon nitride with efficient charge separation and appropriate hydrogen adsorption capacity for superior photocatalytic hydrogen evolution | |
| CN116083949B (en) | MXene-loaded Ag-ZnO electrocatalyst and preparation method, application and test method thereof | |
| CN114988378B (en) | N-doped black phosphazene photocatalyst, and preparation method and application thereof | |
| CN112952119B (en) | Transition metal doped two-dimensional carbon nanosheet and preparation method and application thereof | |
| CN112023937B (en) | Nano copper oxide coated palladium nanowire heterogeneous catalyst, preparation method thereof and application thereof in methanol electrocatalytic oxidation | |
| CN114606527A (en) | One-dimensional defective iron oxide nanorod visible light anode and preparation method and application thereof | |
| CN112871165A (en) | Two-dimensional WO modified by noble metal loading3Preparation method of nanosheet photocatalyst | |
| CN113697783B (en) | Porous g-C 3 N 4 Preparation method and application of nano-sheet | |
| CN112044456B (en) | Ag3PO4/α-Fe2O3Preparation method and application of composite material | |
| CN113941331B (en) | Stabilizing Ni on surface of catalyst 3+ Method for active site and application | |
| CN114797932B (en) | Bimetallic 3D unique honeycomb-shaped carbon dioxide reduction catalyst and preparation method and application thereof | |
| CN112958124B (en) | Indium-doped molybdenum carbide nanoflower core-shell structure photocatalyst and preparation and application thereof | |
| CN114100656B (en) | Preparation method of S-CN-D homogeneous nano heterojunction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |