CN117160509A - Ruthenium-loaded crystalline carbon nitride/doped nano diamond composite material and preparation method and application thereof - Google Patents
Ruthenium-loaded crystalline carbon nitride/doped nano diamond composite material and preparation method and application thereof Download PDFInfo
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000002131 composite material Substances 0.000 title claims abstract description 57
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 42
- 239000002113 nanodiamond Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000002135 nanosheet Substances 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 22
- 238000000137 annealing Methods 0.000 claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000227 grinding Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 16
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- 230000001681 protective effect Effects 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 56
- 229910052757 nitrogen Inorganic materials 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 12
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 238000005286 illumination Methods 0.000 claims description 5
- 239000002064 nanoplatelet Substances 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000010335 hydrothermal treatment Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- 235000014380 magnesium carbonate Nutrition 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 19
- 238000007146 photocatalysis Methods 0.000 abstract description 5
- 238000005336 cracking Methods 0.000 abstract 1
- 238000007781 pre-processing Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 30
- 229910003460 diamond Inorganic materials 0.000 description 16
- 239000010432 diamond Substances 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
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- 239000007787 solid Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
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- 239000013078 crystal Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
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- 238000000926 separation method Methods 0.000 description 3
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
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- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
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- 238000001291 vacuum drying Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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 belongs to the technical field of photocatalysis, and discloses a ruthenium-loaded crystalline carbon nitride/doped nano diamond composite material, and a preparation method and application thereof. The composite material is Ru/CCN/XDND. The preparation method comprises the following steps: (1) preparing a crystalline carbon nitride nanosheet, namely a CCN nanosheet; (2) Preparing a ruthenium-loaded crystalline carbon nitride nanosheet, namely a Ru/CCN nanosheet; (3) preprocessing the doped nano diamond, namely XDND; (4) And (3) grinding and uniformly mixing the Ru/CCN nano-sheet obtained in the step (2) and the XDND obtained in the step (3) according to the mass ratio of (80-95) to (5-20) and the sum of the Ru/CCN nano-sheet and the XDND being 100, and annealing at 150-250 ℃ for 0.5-1.5 h under a protective atmosphere to obtain the Ru/CCN/XDND composite material. The application of the ruthenium-loaded crystalline carbon nitride/doped nano-diamond composite material as a photocatalyst in hydrogen production by water splitting. The Ru/CCN/XDND photocatalysis water cracking hydrogen production rate prepared by the invention is obviously improved compared with that of a single CCN and a single massive CN.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, and particularly relates to a ruthenium-loaded crystalline carbon nitride/doped nano diamond composite material, and a preparation method and application thereof.
Background
The search for clean and sustainable energy is a hot topic of current research. Among them, photocatalytic water splitting hydrogen production is considered as an economical and environment-friendly technology. In the photochemical conversion process, enhancing the charge separation and transfer capability is a key to improving the photocatalytic activity. In particular, the construction of heterojunction structures and the modification design at the interface are critical to further enhance charge separation and migration. At present, many metal semiconductors have been reported to have good photocatalytic activity, such as CdS, znIn 2 S 4 、BiVO 4 Etc., but the high cost and environmental problems thereof have attracted considerable attention.
In contrast, graphite carbon nitride (g-C 3 N 4 CN) is a nonmetallic two-dimensional semiconductor material, which has proven to be an ideal semiconductor photocatalyst due to its excellent physicochemical stability, non-toxicity, low cost, and suitable energy band structure. However, the single CN as a photocatalyst has extremely low hydrogen production efficiency by decomposing water, is unsatisfactory in practical application, and is mainly due to poor conductivity of CN, rapid combination of photo-generated electrons and holes in a bulk phase, relatively low specific surface area and the like, and in addition, poor crystallinity of the CN leads to-NH in an amorphous structure 2 CN containing a large number of structural defects inside, which act as trap sites for charge recombination, greatly inhibiting the kinetics of the hydrogen production reaction, so that modification and structural design of the catalyst are required. The ultrathin CN nano-plate with high crystallinity can effectively eliminate internal defects and improve the utilization rate of photo-generated carriers, thereby efficiently producing hydrogen. In addition, the construction of heterojunction is also one of effective strategies for improving the photocatalytic activity of CN, and particularly, the construction of composite materials with compact electron coupling effect and efficient charge transfer channels is realized.
Disclosure of Invention
The invention aims to solve the problem of low hydrogen production efficiency of CN through photocatalytic water splitting in the prior art, and aims to provide a ruthenium-loaded crystalline carbon nitride/doped nano-diamond composite material, and a preparation method and application thereof.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the ruthenium-loaded crystalline carbon nitride/doped nano diamond composite material is Ru/CCN/XDND, ru represents ruthenium, CCN represents crystalline carbon nitride, XDND represents doped nano diamond, X represents a doping element, and the doping element is a nonmetallic element; the loading amount of ruthenium in the ruthenium-loaded crystalline carbon nitride is 0.5-2 wt%, the doping amount of doping element X in the doped nano diamond is 0.1-2 wt%, and the mass ratio of the doped nano diamond in the whole catalyst is 5-20 wt%.
Preferably, the nonmetallic element is boron or nitrogen.
The preparation process of ruthenium loaded crystallized carbon nitride/doped nanometer diamond composite material includes the following steps:
(1) Preparing a crystalline carbon nitride nano-sheet, namely a CCN nano-sheet;
(2) Preparing ruthenium-supported crystalline carbon nitride nanoplatelets, namely Ru/CCN nanoplatelets, in the following manner (i) or (ii);
(i) Dispersing the CCN nano-sheets obtained in the step (1) in water, adding a ruthenium trichloride aqueous solution according to the load of ruthenium, uniformly stirring, reducing by illumination or reducing agent, centrifuging, and drying to obtain Ru/CCN nano-sheets;
(ii) Dispersing the CCN nanosheets obtained in the step (1) in water, adding a ruthenium trichloride aqueous solution according to the load of ruthenium, uniformly stirring, evaporating to dryness, and then utilizing H 2 Or H 2 /N 2 Reducing the mixed gas to obtain Ru/CCN nano-sheets;
(3) Pretreating the doped nano diamond, namely XDND;
annealing XDND for 0.5-1.5 hours at 400-500 ℃ in an air atmosphere;
(4) And (3) grinding and uniformly mixing the Ru/CCN nano-sheet obtained in the step (2) and the XDND obtained in the step (3) according to the mass ratio of (80-95) to (5-20) and the sum of the Ru/CCN nano-sheet and the XDND being 100, and annealing at 150-250 ℃ for 0.5-1.5 h under a protective atmosphere to obtain the Ru/CCN/XDND composite material.
Preferably, the preparation process of the step (1) is as follows: dissolving a nitrogen-rich precursor and a template agent in No. 1 water, uniformly stirring, drying, and calcining for 2-6 hours at 400-650 ℃ in a reaction atmosphere; dispersing the calcined sample in No. 2 water, uniformly stirring, performing hydrothermal treatment at 100-180 ℃ for 0.5-2 h, cooling, washing, and drying to obtain the CCN nanosheets.
Preferably, in the step (1), the mass ratio of the nitrogen-rich precursor to the template agent is 1:0-0.2, the use amount of the template agent does not comprise 0, and the mass ratio of the nitrogen-rich precursor to the 1# water to the 2# water is 5: 5 g:5-30 mL:20-60 mL.
Preferably, in the step (1), the nitrogen-rich precursor is one or more of urea, melamine, dicyandiamide, cyanamide and thiourea; the template agent is one or more of sodium bicarbonate, sodium carbonate, magnesium carbonate, ammonium chloride, ammonium persulfate and potassium chloride.
Preferably, the reaction atmosphere is air, nitrogen or nitrogen-hydrogen mixture.
Preferably, in the modes (i) and (ii) of the step (2), the dosage ratio of raw materials is CCN nano-sheets to water=0.5 g:10-50 mL; the concentration of the ruthenium trichloride aqueous solution is 2-20 mM.
Preferably, in the step (2), the light in the light reduction is visible light or simulated sunlight; the reducing agent is sodium borohydride or hydrazine hydrate, and the consumption of the reducing agent is excessive relative to ruthenium; the time of illumination reduction or reducing agent reduction is 0.5-2 h; h 2 Or H 2 /N 2 The temperature of the mixed gas for reduction is 150-200 ℃, H 2 /N 2 H in the mixed gas 2 The proportion is 5-20 v%.
Preferably, in the step (3), XDND is soaked in concentrated acid oxidizing solution, heated and stirred for 0.5-2 hours at 30-60 ℃, washed to be neutral by water, dried in vacuum and then annealed; the concentrated acid oxidizing solution is one or a mixture of more of concentrated nitric acid, concentrated sulfuric acid and concentrated hydrochloric acid.
The application of ruthenium-loaded crystalline carbon nitride/doped nano diamond composite material as a photocatalyst in hydrogen production by water splitting is provided.
In the present invention, the doped nanodiamond may be obtained commercially or prepared with reference to the prior art.
The beneficial effects are that: the book is provided withThe invention prepares the Ru/CCN/XDND composite material by utilizing a template method to cooperate with a simple autoloading strategy, the photocatalysis water splitting hydrogen production rate of Ru/CCN/XDND is obviously improved compared with that of single CCN and single massive CN (the photocatalysis hydrogen evolution rate of the Ru/CCN/BDND composite material is up to 8.12 mmol g at maximum) -1 h -1 ) Provides a new solution for realizing industrial production in the early days; meanwhile, the preparation method has the advantages of simple preparation process, low cost, high light utilization rate, high charge separation and transfer efficiency and the like, and has important application prospect in the field of green energy. Therefore, the invention is a very significant technology for efficiently acquiring clean energy.
Drawings
Fig. 1: x-ray diffraction (XRD) patterns of CCN and CN prepared in example 1 and comparative example 1.
Fig. 2: scanning electron microscopy of CCN prepared in example 1.
Fig. 3: x-ray photoelectron spectroscopy of CCN prepared in example 1.
Fig. 4: ru prepared in example 1 1.0 /CCN/BDND 10.0 Composite material, ru 1.0 And (3) XRD pattern of BDND obtained after pretreatment in step (3).
Detailed Description
The present invention is described in detail below with reference to specific embodiments, wherein numerous specific details are set forth in order to provide a thorough understanding of the objects, features, and advantages of the present invention. These examples are provided only for illustrating the present invention and are not intended to limit the actual scope of the present invention in any way, and those skilled in the art may implement any modification and variation of the present invention without departing from the spirit of the present invention, and thus the present invention is not limited to the specific examples disclosed below.
Example 1
The preparation process of ruthenium loaded crystallized carbon nitride/doped nanometer diamond composite material includes the following steps:
(1) Dissolving 5 g dicyandiamide and 0.25 g sodium bicarbonate in 15 mL deionized water, uniformly stirring, freeze-drying to remove the solvent to obtain white powder, then placing the white powder into a crucible with a cover, placing the crucible in a muffle furnace, heating to 550 ℃ in air at a heating rate of 2 ℃/min, and calcining 4 h; dispersing the calcined sample in 60 mL deionized water, stirring at room temperature for 1 h, transferring to a high-pressure reaction kettle, performing hydrothermal treatment at 180 ℃ for 1 h, cooling, centrifuging, washing, and drying to obtain high-crystallinity carbon nitride ultrathin nanosheets, and marking the carbon nitride ultrathin nanosheets as CCN nanosheets;
(2) Dispersing 0.5 g CCN nano-sheet in 20 mL deionized water, adding 5 mL ruthenium trichloride aqueous solution (10 mM), stirring 0.5 h, reducing 1 h by illumination, centrifuging, washing and drying to obtain ruthenium-loaded crystalline carbon nitride nano-sheet (Ru load of 1.0 wt%), and marking as Ru 1.0 /CCN；
(3) Soaking BDND (boron doped nano diamond with boron doping amount of 0.7 wt% and purchased from Changsha Sanbika superhard materials Co., ltd.) powder in concentrated sulfuric acid/concentrated nitric acid (volume ratio of 3:1) oxidation solution, heating and stirring at 40deg.C for 1 h, repeatedly centrifuging with deionized water to neutral pH, vacuum drying at 60deg.C, placing the obtained solid into muffle furnace, annealing at 450deg.C in air atmosphere for 0.5 h, removing sp covered on surface 2 Carbon;
(4) The product obtained in step (2) (0.45 g Ru) 1.0 Grinding (1.05 g BDND) of the product obtained in the step (3) in a ball mill for 1 h, uniformly mixing, adding into a crucible, heating to 200 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen in a tube furnace, and annealing for 1 h to obtain Ru containing 10.0 wt% BDND 1.0 /CCN/BDND 10.0 A composite material.
Example 2
The preparation process of ruthenium loaded crystallized carbon nitride/doped nanometer diamond composite material includes the following steps:
(1) Step (1) is the same as in example 1;
(2) Dispersing 0.5 g of CCN nano-sheets in 20 mL deionized water, performing ultrasonic dispersion, adding 1 mL ruthenium trichloride aqueous solution (10 mM), stirring for 0.5 h, and performing light irradiation reduction for 1 h to obtain ruthenium-loaded crystalline carbon nitride nano-sheets (Ru load amount is 0.2 wt%), wherein the ruthenium-loaded crystalline carbon nitride nano-sheets are marked as Ru 0.2 /CCN；
(3) Step (3) as in example 1;
(4) The product obtained in step (2) (0.45 g Ru) 0.2 Grinding (1.05 g BDND) of the product obtained in the step (3) in a ball mill for 1 h, uniformly mixing, adding into a crucible, heating to 200 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen in a tube furnace, and annealing for 1 h to obtain Ru containing 10.0 wt% BDND 0.2 /CCN/BDND 10.0 A composite material.
Example 3
The preparation process of ruthenium loaded crystallized carbon nitride/doped nanometer diamond composite material includes the following steps:
(1) Step (1) is the same as in example 1;
(2) Dispersing 0.5 g CCN nano-sheet in 20 mL deionized water, then adding 2.5 mL ruthenium trichloride aqueous solution (10 mM), stirring 0.5 h, and reducing 1 h by illumination to obtain ruthenium-loaded crystalline carbon nitride nano-sheet (Ru load amount is 0.5 wt%), marked as Ru 0.5 /CCN；
(3) Step (3) as in example 1;
(4) The product obtained in step (2) (0.45 g Ru) 0.5 Grinding (1.05 g BDND) of the product obtained in the step (3) in a ball mill for 1 h, uniformly mixing, adding into a crucible, heating to 200 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen in a tube furnace, and annealing for 1 h to obtain Ru containing 10.0 wt% BDND 0.5 /CCN/BDND 10.0 A composite material.
Example 4
The preparation process of ruthenium loaded crystallized carbon nitride/doped nanometer diamond composite material includes the following steps:
(1) Step (1) is the same as in example 1;
(2) Dispersing 0.5 g of CCN nano-sheets in 20 mL deionized water, performing ultrasonic dispersion, adding 10 mL ruthenium trichloride aqueous solution (10 mM), stirring for 0.5 h, and performing light irradiation reduction for 1 h to obtain ruthenium-loaded crystalline carbon nitride nano-sheets (Ru load amount is 2.0 wt%), wherein the ruthenium-loaded crystalline carbon nitride nano-sheets are marked as Ru 2.0 /CCN；
(3) Step (3) as in example 1;
(4) The product obtained in step (2) (0.45 g Ru) 2.0 Grinding (1.05 g BDND) of the product obtained in the step (3) in a ball mill for 1 h, uniformly mixing, adding into a crucible, heating to 200 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen in a tube furnace, and annealing for 1 h to obtain Ru containing 10.0 wt% BDND 2.0 /CCN/BDND 10.0 A composite material.
Example 5
The preparation process of ruthenium loaded crystallized carbon nitride/doped nanometer diamond composite material includes the following steps:
(1) Step (1) is the same as in example 1;
(2) Step (2) as in example 1;
(3) Step (3) as in example 1;
(4) The product obtained in step (2) (0.495 g Ru) 1.0 Grinding (1) h) the product obtained in the step (3) (0.005 g BDND) in a ball mill, mixing uniformly, adding into a crucible, heating to 200 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen in a tube furnace, and annealing for 1 h to obtain Ru containing 1.0 wt% BDND 1.0 /CCN/BDND 1.0 A composite material.
Example 6
The preparation process of ruthenium loaded crystallized carbon nitride/doped nanometer diamond composite material includes the following steps:
(1) Step (1) is the same as in example 1;
(2) Step (2) as in example 1;
(3) Step (3) as in example 1;
(4) The product obtained in step (2) (0.49 g Ru) 1.0 Grinding (1.01 g BDND) of the product obtained in the step (3) in a ball mill for 1 h, uniformly mixing, adding into a crucible, heating to 200 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen in a tube furnace, and annealing for 1 h to obtain Ru containing 2.0 wt% BDND 1.0 /CCN/BDND 2.0 A composite material.
Example 7
The preparation process of ruthenium loaded crystallized carbon nitride/doped nanometer diamond composite material includes the following steps:
(1) Step (1) is the same as in example 1;
(2) Step (2) as in example 1;
(3) Step (3) as in example 1;
(4) The product obtained in step (2) (0.475 g Ru) 1.0 Grinding (1.025 g BDND) of the product obtained in the step (3) in a ball mill for 1 h, uniformly mixing, adding the mixture into a crucible, heating to 200 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen in a tube furnace, and carrying out annealing treatment for 1 h to obtain Ru containing 5.0 wt% BDND 1.0 /CCN/BDND 5.0 A composite material.
Example 8
The preparation process of ruthenium loaded crystallized carbon nitride/doped nanometer diamond composite material includes the following steps:
(1) Step (1) is the same as in example 1;
(2) Step (2) as in example 1;
(3) Step (3) as in example 1;
(4) The product obtained in step (2) (0.425 g Ru) 1.0 Grinding the product (0.075 g BDND) obtained in the step (3) in a ball mill to 1 h, uniformly mixing, adding into a crucible, heating to 200 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen in a tube furnace, and annealing for 1 h to obtain Ru containing 15.0 wt% BDND 1.0 /CCN/BDND 15.0 A composite material.
Example 9
The preparation process of ruthenium loaded crystallized carbon nitride/doped nanometer diamond composite material includes the following steps:
(1) Step (1) is the same as in example 1;
(2) Step (2) as in example 1;
(3) Step (3) as in example 1;
(4) The product obtained in step (2) (0.4 g Ru) 1.0 CCN) and step (3)Grinding the product (0.1 g BDND) in a ball mill for 1 h, mixing, adding into a crucible, heating to 200deg.C at a heating rate of 5deg.C/min under nitrogen protection in a tube furnace, and annealing for 1 h to obtain Ru containing 20.0 wt% BDND 1.0 /CCN/BDND 20.0 A composite material.
Example 10
The preparation process of ruthenium loaded crystallized carbon nitride/doped nanometer diamond composite material includes the following steps:
(1) Step (1) is the same as in example 1;
(2) Step (2) as in example 1;
(3) Step (3) as in example 1;
(4) The product obtained in step (2) (0.35 g Ru 1.0 Grinding (1.15 g BDND) of the product obtained in the step (3) in a ball mill for 1 h, uniformly mixing, adding into a crucible, heating to 200 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen in a tube furnace, and annealing for 1 h to obtain Ru containing 30.0 wt% BDND 1.0 /CCN/BDND 30.0 A composite material.
Example 11
The preparation process of ruthenium loaded crystallized carbon nitride/doped nanometer diamond composite material includes the following steps:
(1) Step (1) is the same as in example 1;
(2) Step (2) as in example 1;
(3) Putting 100 mg nitrogen-doped graphene powder (the content of nitrogen element is 0.9 wt%) into 20 mL absolute ethyl alcohol, continuously irradiating with 532 nm laser beams under vigorous stirring after ultrasonic dispersion for 0.5 h, stopping irradiation until no obvious black solid powder is suspended, centrifuging, drying, putting the obtained solid into a muffle furnace, annealing at 400 ℃ in an air atmosphere for 0.5 h, and removing sp2 carbon covered on the surface to obtain NDND (nitrogen-doped nano diamond), wherein the content of nitrogen element is 0.9 wt%;
(4) The product obtained in step (2) (0.45 g Ru) 1.0 CCN) and the product from step (3) (0.05 g NDND)Grinding 1. 1 h in a ball mill, mixing, adding into a crucible, heating to 200deg.C at a heating rate of 5deg.C/min under nitrogen protection in a tube furnace, and annealing for 1. 1 h to obtain Ru containing 10.0 wt% NDND 1.0 /CCN/NDND 10.0 A composite material.
Example 12
The preparation process of ruthenium loaded crystallized carbon nitride/doped nanometer diamond composite material includes the following steps:
(1) Step (1) is the same as in example 1;
(2) Step (2) as in example 1;
(3) Placing 100 mg graphite powder and 4 mg cobalt acetate into 20 mL absolute ethyl alcohol, continuously irradiating with 532 nm laser beams under intense stirring after ultrasonic dispersion of 0.5 h, stopping irradiation after pulse power is 200 mJ until no obvious black solid powder is suspended, centrifuging, drying, placing the obtained solid into a muffle furnace, annealing at 450 ℃ in an air atmosphere for 0.5 h, and removing sp2 carbon covered on the surface to obtain CDND (cobalt doped nano diamond), wherein the content of Co is about 0.5 wt%;
(4) The product obtained in step (2) (0.45 g Ru) 1.0 Grinding (1.05 g CDND) product obtained in step (3) in ball mill for 1 h, mixing, adding into crucible, heating to 200deg.C at 5 ℃/min under nitrogen protection, and annealing for 1 h to obtain Ru containing 10.0 wt% CDND 1.0 /CCN/CDND 10.0 A composite material.
Comparative example 1
The preparation process of ruthenium loaded composite material with common carbon nitride and doped nanometer diamond includes the following steps:
(1) Placing 5 g dicyandiamide into a crucible with a cover and placing the crucible into a muffle furnace, heating to 550 ℃ in air at a heating rate of 2 ℃/min, and calcining 4 h to obtain common block Carbon Nitride (CN);
(2) Dispersing 0.5 g block CN in 20 mL deionized water, ultrasonic dispersing, adding 5 mL ruthenium trichloride aqueous solution (10 mM), stirring 0.5 h, and reducing 1 h by light irradiation to obtain ruthenium-loaded common carbon nitride nanosheets (R)u-loading 1.0. 1.0 wt%), labeled Ru 1.0 /CN；
(3) Step (3) as in example 1;
(4) The product obtained in step (2) (0.45 g Ru) 1.0 Grinding (CN) and the product obtained in the step (3) (0.05 g BDND) in a ball mill to obtain 1 h, mixing uniformly, adding into a crucible, heating to 200 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen in a tube furnace, and annealing for 1 h to obtain Ru containing 10.0 wt% BDND 1.0 /CN/BDND 10.0 A composite material.
Characterization of product Structure
FIG. 1 is an X-ray diffraction (XRD) pattern of CCN and CN prepared in example 1 and comparative example 1. As can be seen from fig. 1: CN and CCN have two peaks at 12.9 ° and 27.4 °, respectively corresponding to the in-plane repeating triazine units of the (100) crystal plane and the interlayer stack of the planar conjugated system of the (002) crystal plane, wherein the diffraction peak of CCN is significantly enhanced, indicating that CCN has a higher crystallinity.
FIG. 2 is a scanning electron microscope image of CCN prepared in example 1. As can be seen from fig. 2: CCN exhibits a typical two-dimensional nanoplatelet morphology.
FIG. 3 is an X-ray photoelectron spectrum of CCN prepared in example 1. As can be seen from fig. 3: C-NH appears in the high resolution C1 s spectrum x And a characteristic peak of N-c=n, c=n-C, N-C appearing in the N1 s spectrum 3 、C-N-H x And characteristic peaks of charging effects, confirm the surface chemical state and element composition of CCN.
FIG. 4 shows Ru prepared according to example 1 1.0 /CCN/BDND 10.0 Composite material, ru 1.0 And (3) XRD pattern of BDND obtained after pretreatment in step (3). As can be seen from fig. 4: two peaks at 43.9 ° and 75.2 ° in the BDND sample correspond to the (111) and (220) crystal planes of diamond, respectively; the two peaks at 12.9 ° and 27.4 ° in the CCN sample are due to the characteristic peaks of CCN, which are difficult to see for Ru in the composite, possibly due to its lower loading; in Ru 1.0 /CCN/BDND 10.0 Peaks of CCN and BDND were observed in the composite, confirming the compositeSuccessful synthesis.
Performance testing
Selecting any one of the products prepared in examples 1-12, the product prepared in comparative example 1, CCN prepared in step (1) in example 1 and CN prepared in step (1) in comparative example 1 as a catalyst, adding a 25 mg catalyst into a 100 mL aqueous solution containing 10 v% triethanolamine, ultrasonically dispersing for 10 min, adding into a 250 mL Beijing pofivelie photocatalytic reactor, vacuumizing to remove air, using a 300W xenon lamp as a light source to provide full spectrum light irradiation reaction liquid, sampling after a certain time interval, detecting the generated hydrogen by using a Japanese island body fluid GC-81 type chromatograph, and quantitatively analyzing.
The results of the photocatalytic hydrogen evolution rate are shown in table 1. As can be seen from table 1:
(1) BDND and Ru have important influence on improving the photocatalytic hydrogen production activity of Ru/CCN/BDND, the optimal mass fraction of BDND is 5-20 wt%, the optimal mass fraction of Ru is 0.5-2 wt%, and the photocatalytic hydrogen production effect is not best in the range lower or higher than the optimal range;
(2) The doped elements have good promotion effect on the photocatalytic performance, and boron is optimal and nitrogen is secondary, because the band gaps and the energy band structure positions of the diamond doped with different elements are greatly different, and the photocatalytic activity of the catalyst is greatly influenced;
(3) Ru prepared by the invention 1.0 /CCN/BDND 10.0 The photocatalytic hydrogen evolution rate of the catalyst is 8.12 mmol g -1 h -1 The method comprises the steps of carrying out a first treatment on the surface of the The photocatalytic hydrogen evolution rate of CCN was 0.63 mmol g -1 h -1 The photocatalytic hydrogen evolution rate of the common block CN is 0.12 mmol g -1 h -1 ，Ru 1.0 /CCN/BDND 10.0 The hydrogen evolution rate of (2) is improved by 13.5 times compared with CCN, and is improved by 67.7 times compared with common CN.
Claims (10)
1. A ruthenium-loaded crystalline carbon nitride/doped nanodiamond composite, characterized in that: the composite material is Ru/CCN/XDND, ru represents ruthenium, CCN represents crystalline carbon nitride, XDND represents doped nano diamond, X represents a doping element, and the doping element is a nonmetallic element; the loading amount of ruthenium in the ruthenium-loaded crystalline carbon nitride is 0.5-2 wt%, the doping amount of doping element X in the doped nano diamond is 0.1-2 wt%, and the mass ratio of the doped nano diamond in the whole catalyst is 5-20 wt%.
2. The ruthenium-supported crystalline carbon nitride/doped nanodiamond composite of claim 1, wherein: the nonmetallic element is boron or nitrogen.
3. A method for preparing the ruthenium-supported crystalline carbon nitride/doped nanodiamond composite material as claimed in claim 1, comprising the steps of:
(1) Preparing a crystalline carbon nitride nano-sheet, namely a CCN nano-sheet;
(2) Preparing ruthenium-supported crystalline carbon nitride nanoplatelets, namely Ru/CCN nanoplatelets, in the following manner (i) or (ii);
(i) Dispersing the CCN nano-sheets obtained in the step (1) in water, adding a ruthenium trichloride aqueous solution according to the load of ruthenium, uniformly stirring, reducing by illumination or reducing agent, centrifuging, and drying to obtain Ru/CCN nano-sheets;
(ii) Dispersing the CCN nanosheets obtained in the step (1) in water, adding a ruthenium trichloride aqueous solution according to the load of ruthenium, uniformly stirring, evaporating to dryness, and then utilizing H 2 Or H 2 / N 2 Reducing the mixed gas to obtain Ru/CCN nano-sheets;
(3) Pretreating the doped nano diamond, namely XDND;
annealing XDND for 0.5-1.5 hours at 400-500 ℃ in an air atmosphere;
(4) And (3) grinding and uniformly mixing the Ru/CCN nano-sheet obtained in the step (2) and the XDND obtained in the step (3) according to the mass ratio of (80-95) to (5-20) and the sum of the Ru/CCN nano-sheet and the XDND being 100, and annealing at 150-250 ℃ for 0.5-1.5 h under a protective atmosphere to obtain the Ru/CCN/XDND composite material.
4. The method of preparing a ruthenium-supported crystalline carbon nitride/doped nanodiamond composite according to claim 3, wherein the preparation process of step (1) is as follows: dissolving a nitrogen-rich precursor and a template agent in No. 1 water, uniformly stirring, drying, and calcining for 2-6 hours at 400-650 ℃ in a reaction atmosphere; dispersing the calcined sample in No. 2 water, uniformly stirring, performing hydrothermal treatment at 100-180 ℃ for 0.5-2 h, cooling, washing, and drying to obtain the CCN nanosheets.
5. The method for preparing the ruthenium-supported crystalline carbon nitride/doped nano-diamond composite material according to claim 4, wherein the method comprises the following steps: in the step (1), the mass ratio of the nitrogen-rich precursor to the template agent is 1:0-0.2, the use amount of the template agent does not comprise 0, and the mass ratio of the nitrogen-rich precursor to the 1# water to the 2# water is 5 g:5-30 mL:20-60 mL.
6. The method for preparing the ruthenium-supported crystalline carbon nitride/doped nano-diamond composite material according to claim 4 or 5, wherein the method comprises the following steps: in the step (1), the nitrogen-rich precursor is one or more of urea, melamine, dicyandiamide, cyanamide and thiourea; the template agent is one or more of sodium bicarbonate, sodium carbonate, magnesium carbonate, ammonium chloride, ammonium persulfate and potassium chloride.
7. The method for preparing the ruthenium-supported crystalline carbon nitride/doped nano-diamond composite material according to claim 4 or 5, wherein the method comprises the following steps: in the step (1), the reaction atmosphere is air, nitrogen or nitrogen-hydrogen mixture.
8. The method for preparing the ruthenium-supported crystalline carbon nitride/doped nanodiamond composite material according to claim 3, wherein: in the step (2), the dosage ratio of raw materials is CCN nano-sheets to water=0.5: 0.5 g:10-50 mL; the concentration of the ruthenium trichloride aqueous solution is 2-20 mM.
9. The method for preparing the ruthenium-supported crystalline carbon nitride/doped nanodiamond composite material according to claim 3, wherein: in the step (3), firstly, XDND is soaked in concentrated acid oxidation solution, heated and stirred for 0.5-2 h at 30-60 ℃, washed to be neutral by water, dried in vacuum, and then annealed; the concentrated acid oxidizing solution is one or a mixture of more of concentrated nitric acid, concentrated sulfuric acid and concentrated hydrochloric acid.
10. Use of the ruthenium-supported crystalline carbon nitride/doped nanodiamond composite material according to claim 1 as a photocatalyst in hydrogen production by water splitting.
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