CN112121836A - Preparation method of palladium-cobalt/carbon nitride composite material, product and application thereof - Google Patents
Preparation method of palladium-cobalt/carbon nitride composite material, product 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 77
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 55
- 239000010941 cobalt Substances 0.000 title claims abstract description 55
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 62
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 23
- 239000010439 graphite Substances 0.000 claims abstract description 23
- 239000002105 nanoparticle Substances 0.000 claims abstract description 22
- 230000009467 reduction Effects 0.000 claims abstract description 17
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 235000019253 formic acid Nutrition 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011148 porous material Substances 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 6
- 230000001699 photocatalysis Effects 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000007598 dipping method Methods 0.000 claims abstract description 4
- 238000005286 illumination Methods 0.000 claims abstract description 4
- 239000007787 solid Substances 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000002082 metal nanoparticle Substances 0.000 claims description 10
- 238000011068 loading method Methods 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 8
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 150000002940 palladium Chemical class 0.000 claims description 6
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 239000012279 sodium borohydride Substances 0.000 claims description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 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
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- 229910020676 Co—N Inorganic materials 0.000 claims 2
- 230000008020 evaporation Effects 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000006356 dehydrogenation reaction Methods 0.000 description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 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
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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Abstract
The invention discloses a preparation method of a palladium-cobalt/carbon nitride composite material, a product and application thereof, wherein the preparation method of the palladium-cobalt/carbon nitride composite material with a heterojunction structure is realized by a hard template method and a step-by-step dipping reduction method, and the obtained palladium-cobalt nano particles are ultrafine nano particles and are attached to the pore channel and the surface of a carbon nitride material by virtue of rich pore channel structures of mesoporous graphite phase carbon nitride. The product obtained by the method is a palladium-cobalt/carbon nitride composite material, and due to the existence of a heterojunction structure between the palladium-cobalt nano particles and the carbon nitride, the surface of the palladium particles has higher electron density, and photoelectrons generated by the carbon nitride under illumination can be captured, so that the prepared composite material shows excellent photocatalytic hydrogen production performance, and has great application potential in the field of hydrogen production from formic acid and other raw materials.
Description
Technical Field
The invention belongs to the field of preparation of nano metal-semiconductor composite materials, and particularly relates to a preparation method of a palladium-cobalt/carbon nitride composite material, and a product and application thereof.
Background
As an ideal clean energy source, hydrogen has higher energy density and lower environmental burden, and has wide application prospect, such as hydrogen fuel cells and hydrogen fuel engines. Hydrogen gas is expected to play an important role in future energy structures. Water, organic matters and biomass raw materials can be used for preparing hydrogen, wherein formic acid is an ideal hydrogen preparation raw material and has the advantages of no toxicity, stability, high hydrogen storage density and the like. The decomposition of formic acid may take place in two reactions, one being a dehydrogenation reaction, generating carbon dioxide and hydrogen; the other is a dehydration reaction, which produces water and carbon monoxide. Therefore, when the catalyst is selected, the catalyst which only catalyzes the dehydrogenation reaction and does not generate the dehydration reaction is selected for the hydrogen production by the decomposition of the formic acid.
Recent literature and theoretical studies have shown that palladium nanoparticles have a better effect in catalyzing the dehydrogenation of formic acid, since palladium catalyzes the dehydrogenation of formic acid with a minimal effective barrier (0.76 eV), followed by nickel (1.03 eV) and platinum (1.56 eV). And the palladium nanoparticles catalyze the dehydrogenation of the formic acid to have better selectivity, and products are all carbon dioxide and hydrogen, so that a dehydration side reaction cannot occur.
Much research has been devoted to improving the activity of palladium nanometals in catalyzing the dehydrogenation of formic acid, and since the mechanism of palladium participation in the reaction is to provide electrons for the reduction of hydrogen, all catalyst optimization schemes are centered around the rationale of increasing the electron density around the palladium nanoparticles. The higher electron density will make the palladium nanoparticles a stronger electron donor with stronger reducing power.
One of the catalytic methods of palladium nanoparticles is to select a suitable semiconductor as a carrier to form a metal-semiconductor supported catalyst. Commonly used carriers are metal oxides, non-metal oxides, activated carbon, carbon nitride, and the like. Mesoporous graphite phase carbon nitride is an ideal support for noble metal nanoparticles because it has a band gap of 2.7eV and the work function of palladium is between its valence and conduction bands. Palladium can thus form rectifying contact with it, and the difference in fermi levels causes electrons at the interface to flow from the carbon nitride to the palladium nanoparticles until they reach the fermi level equilibrium, and the palladium nanoparticles acquire a higher electron density, which is the so-called Mott-Schottky effect.
Another strategy for enhancing the catalytic activity of the single-component palladium nano-particles is to add gold, silver, copper and other elements to construct a bimetallic catalyst. The additional metal element serves as an electron donor to further increase the electron density of the palladium nanoparticle. However, at present, several noble metal element nanoparticles are mostly used to construct a multi-metal catalyst in related reports, which increases the cost of the catalyst and greatly limits the application of the catalyst. Co as a transition metal element is widely researched and used for catalyzing various important reactions due to good activity and relatively low cost, and at present, no report about the application of a bimetallic catalyst formed by Co and Pd in photocatalytic formic acid decomposition is provided. Therefore, there is a need to develop a controllable and reproducible method for preparing palladium-cobalt/carbon nitride composite materials; meanwhile, the prepared composite material can keep a good nano-configuration.
Disclosure of Invention
The invention aims to: provides a preparation method of a palladium-cobalt/carbon nitride composite material.
Another object of the present invention is to: a palladium-cobalt/carbon nitride composite material product prepared by the method is provided.
Yet another object of the present invention is to: applications of the above products are provided.
The purpose of the invention is realized by the following scheme: a preparation method of a palladium-cobalt/carbon nitride composite material utilizes a hard template method and a step-by-step dipping reduction method to prepare the palladium-cobalt/carbon nitride composite material with a heterojunction structure, and comprises the following steps:
a. preparing mesoporous graphite phase carbon nitride: 50% aqueous cyanamide solution was added dropwise to silica sol (mSiO) with vigorous stirring2·nH2O), fully stirring the silica sol and cyanamide according to the mass ratio of 10: 1-1: 10, evaporating to dryness in a water bath, calcining the obtained solid for 4 hours under the protection of nitrogen, and naturally cooling to obtain a yellow solid; the resulting yellow solid was ground and added to a solution of ammonium bifluoride and stirred for 48 hours to remove Si02A template, washing and drying the obtained solid to obtain light yellow mesoporous graphite phase carbon nitride as a matrix;
b. loading of palladium-cobalt metal nanoparticles: and (2) ultrasonically dispersing 100mg of prepared mesoporous graphite phase carbon nitride in 25mL of deionized water, dropwise adding a certain amount of palladium salt solution under vigorous stirring, stirring overnight, then dropwise adding a reducing agent for reduction, centrifugally separating and washing the obtained mixture, retaining the solid, adding deionized water again for dispersion, adding a certain amount of cobalt chloride solution, repeating the operation for reduction, and finally obtaining the solid, and centrifugally separating, washing and drying the obtained solid to obtain the palladium-cobalt/carbon nitride composite material.
The invention provides a novel preparation method of a palladium-cobalt/carbon nitride composite material, which utilizes Si02Preparing mesoporous graphite-phase carbon nitride as a hard template, and then loading palladium and cobalt nanoparticles on the pore channels of the mesoporous graphite-phase carbon nitride by using a continuous oxidation-reduction method, wherein in the prepared material, a specific heterojunction structure is formed between the palladium-cobalt nanoparticles and the carbon nitride.
On the basis of the scheme, in the preparation process of the mesoporous graphite phase carbon nitride, the cyanamide is one of raw materials of cyanamide, dicyandiamide, melamine or cyanuric acid, and the palladium salt solution used in the process of loading the palladium/cobalt metal nanoparticles is one of palladium chloride, palladium nitrate or palladium sulfate solutions.
On the basis of the scheme, the concentration of the palladium salt solution is 0.1-10 mol/L.
The concentration of the cobalt chloride solution is 0.1-1 mol/L.
The reducing agent is one of sodium borohydride solution, dicyandiamide solution or sodium sulfite solution.
The drying temperature is 50-80 ℃.
The preferable calcination temperature is 500 to 650 ℃.
The invention also provides a palladium-cobalt/carbon nitride composite material which is prepared by any one of the methods, wherein the obtained palladium-cobalt nanoparticles are formed by means of rich pore channel structures of mesoporous graphite phase carbon nitride and are attached to pore channels and the surface of the carbon nitride material, and due to the existence of a heterojunction structure between the palladium-cobalt nanoparticles and the carbon nitride, the surface of the palladium particles has higher electron density and photoelectrons generated by the carbon nitride under illumination can be captured.
Preferably, the palladium-cobalt/carbon nitride composite material is (5-10)% Pd- (1-8)% Co/g-C3N4A catalyst.
The invention also provides application of the palladium-cobalt/carbon nitride composite material as a catalyst material for photocatalytic hydrogen production from formic acid.
Activity evaluation of palladium cobalt/carbon nitride catalyst:
20.0 mg of palladium-cobalt/carbon nitride catalyst was added to a round flask (reaction volume 10 cm)3) The reaction solution was kept at a constant temperature with a constant water temperature, and stirred with a 78-1 type magnetic stirrer. 5ml of deionized water and 5ml of 2M aqueous formic acid were simultaneously added, and the reaction flask was purged with nitrogen gas while stirring, and the operation was repeated 3 times to evacuate the air in the reactor. A150W xenon lamp was turned on to carry out the decomposition reaction of formic acid, and the reaction was carried out for 60 minutes under visible light excitation. Generated gas (CO + H)2) The volume of (b) is determined by the drainage method. After the reaction, the reaction solution was filtered to remove the catalyst.
The invention has the advantages that: the composite material prepared by the method can generate a heterojunction structure between the metal nanoparticles and the carbon nitride, and the unique structure can enhance the electron density of the palladium nanoparticles, and particularly can improve the aggregation degree of photoelectrons under the illumination condition, so that the prepared composite material shows excellent photocatalytic hydrogen production performance.
Drawings
FIG. 1 is a graph of the catalytic formic acid dehydrogenation reaction rate of a palladium-cobalt/carbon nitride composite synthesized by the method of the present invention;
fig. 2 is an XPS chart of the palladium-cobalt/carbon nitride composite synthesized in example 1 of the present invention.
Detailed Description
The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following embodiments.
Example 1:
a palladium-cobalt/carbon nitride composite material is prepared by a hard template method and a step-by-step dipping reduction method, and is prepared by the following steps:
a. preparing mesoporous graphite phase carbon nitride: dropwise adding 5g of cyanamide 50% aqueous solution into 7.5g of Ludox HS40 silica sol under vigorous stirring, fully stirring and evaporating to dryness in a water bath at 65 ℃, calcining the obtained solid in a tubular furnace under the protection of nitrogen at the temperature rising speed of 2.3 ℃/min, preserving heat at 550 ℃ for 4 hours, and naturally cooling to obtain a yellow solid; the resulting solid was ground and added with an excess of 4mol/L ammonium bifluoride solution and stirred for 48 hours to remove Si02Washing and drying the obtained solid to obtain light yellow mesoporous graphite phase carbon nitride;
b. loading of palladium-cobalt metal nanoparticles: ultrasonically dispersing 100mg of prepared mesoporous graphite-phase carbon nitride in 25mL of deionized water, dropwise adding 1.07mL of 1mol/L palladium chloride solution under vigorous stirring, stirring overnight, then dropwise adding 2mL of 0.5mol/L sodium borohydride solution for reduction, centrifugally separating and washing the obtained mixture, and retaining solids; adding the solid into deionized water again for dispersion; 0.39mL of a 0.1mol/L cobalt chloride solution was added, and the above-mentioned operation was repeated to conduct reduction. Centrifugally separating, washing and drying the finally obtained solid to obtain the carbon nitride matrix composite material containing 10 percent of palladium and 2 percent of cobalt, 10 percent of Pd-2 percent of Co/g-C3N4。
As can be seen from FIG. 2, 10% Pd/g-C3N4The Pd nano-particles of the catalyst are mainly the zero-valent metal Pd0In the form of a small amount of Pd2+Ions. When the Co additive is added, the mixture becomes 10 percent Pd-2 percent Co/g-C3N4In the case of the catalyst, the binding energy position of the Pd nano-particles gradually moves to a high-energy direction and shifts by 0.09 eV and 0.51 eV respectively, which shows that the Pd particles play a role as an active center in the reaction. When the Co component is added, more electrons are transferred to the surface of the Pd particles, so that the reactivity of the Pd particles is increased, and the reaction can be shownShowing better photocatalytic activity.
FIG. 1 is a graph showing the catalytic formic acid dehydrogenation reaction rate of the palladium-cobalt/carbon nitride composite material synthesized by the method of the present invention when the ratio of 10% Pd-2% Co/g-C is used3N4When the catalyst is used, the volume of gas generated by formic acid dehydrogenation after 60min of light excitation reaches 56 ml, which is far higher than that of the catalyst formed by other proportions, and good reaction activity is shown.
Example 2:
a palladium-cobalt/carbon nitride composite material, similar to example 1, prepared by the following steps:
a. preparing mesoporous graphite phase carbon nitride: dropwise adding 5g of cyanamide 50% aqueous solution into 7.5g of Ludox HS40 silica sol under vigorous stirring, fully stirring and evaporating the mixture to dryness in a water bath at 65 ℃, calcining the obtained solid in a tubular furnace under the protection of nitrogen at the temperature rising speed of 2.3 ℃/min, preserving the heat at 600 ℃ for 4 hours, and naturally cooling to obtain a dark yellow solid; the resulting solid was ground and added with an excess of 4mol/L ammonium bifluoride solution and stirred for 48 hours to remove Si02Washing and drying the obtained solid to obtain yellow mesoporous graphite phase carbon nitride;
b. loading of palladium-cobalt metal nanoparticles: taking 100mg of prepared mesoporous graphite phase carbon nitride, ultrasonically dispersing in 25mL of deionized water, dropwise adding 1.07mL of 1mol/L palladium chloride solution under vigorous stirring, stirring overnight, then dropwise adding 2mL of 0.5mol/L sodium borohydride solution for reduction, centrifugally separating and washing the obtained mixture, retaining solids, adding deionized water again for dispersion, adding 0.39mL of 0.1mol/L cobalt chloride solution, and repeating the operation for reduction. Centrifugally separating, washing and drying the finally obtained solid to obtain the carbon nitride matrix composite material containing 10 percent of palladium and 2 percent of cobalt, 10 percent of Pd-2 percent of Co/g-C3N4。
Example 3
A palladium-cobalt/carbon nitride composite material, similar to example 1, prepared by the following steps:
a. preparing mesoporous graphite phase carbon nitride: 5g of a 50% aqueous solution of cyanamide are added dropwise with vigorous stirring to 7.5g of Ludox HS40 silica sol, stirred well andevaporating the water bath to dryness at 65 ℃, calcining the obtained solid in a tubular furnace under the protection of nitrogen at the heating speed of 2.3 ℃/min, preserving the heat at 550 ℃ for 4 hours, and naturally cooling to obtain a yellow solid; the resulting solid was ground and added with an excess of 4mol/L ammonium bifluoride solution and stirred for 48 hours to remove Si02Washing and drying the obtained solid to obtain light yellow mesoporous graphite phase carbon nitride;
b. loading of palladium-cobalt metal nanoparticles: taking 100mg of prepared mesoporous graphite phase carbon nitride, ultrasonically dispersing in 25mL of deionized water, dropwise adding 0.86mL of 1mol/L palladium chloride solution under vigorous stirring, stirring overnight, then dropwise adding 2mL of 0.5mol/L sodium borohydride solution for reduction, centrifugally separating and washing the obtained mixture, retaining solids, adding deionized water again for dispersion, adding 0.98mL of 0.1mol/L cobalt chloride solution, and repeating the operation for reduction. Centrifugally separating, washing and drying the finally obtained solid to obtain the carbon nitride matrix composite material 8% Pd-5% Co/g-C containing 8% Pd and 5% Co3N4。
Example 4:
a palladium-cobalt/carbon nitride composite material, similar to example 1, prepared by the following steps:
a. preparing mesoporous graphite phase carbon nitride: dropwise adding 5g of cyanamide 50% aqueous solution into 7.5g of Ludox HS40 silica sol under vigorous stirring, fully stirring and evaporating to dryness in a water bath at 65 ℃, calcining the obtained solid in a tubular furnace under the protection of nitrogen at the temperature rising speed of 2.3 ℃/min, preserving heat at 550 ℃ for 4 hours, and naturally cooling to obtain a yellow solid; the resulting solid was ground and added with an excess of 4mol/L ammonium bifluoride solution and stirred for 48 hours to remove Si02Washing and drying the obtained solid to obtain light yellow mesoporous graphite phase carbon nitride;
b. loading of palladium-cobalt metal nanoparticles: taking 100mg of prepared mesoporous graphite phase carbon nitride, ultrasonically dispersing in 25mL of deionized water, dropwise adding 0.52mL of 1mol/L palladium chloride solution under vigorous stirring, stirring overnight, then dropwise adding 2mL of 0.5mol/L sodium borohydride solution for reduction, centrifugally separating and washing the obtained mixture, retaining the solid, adding again the solid, and then adding againDeionized water was dispersed, and 0.94mL of a 0.1mol/L cobalt chloride solution was added to conduct reduction by repeating the above-mentioned operation. Centrifugally separating, washing and drying the finally obtained solid to obtain the carbon nitride matrix composite material containing 5 percent of palladium and 5 percent of cobalt, 5 percent of Pd and 5 percent of Co/g-C3N4。
Claims (10)
1. A preparation method of a palladium-cobalt/carbon nitride composite material is characterized in that a palladium-cobalt/carbon nitride composite material with a heterojunction structure is prepared by a hard template method and a step-by-step dipping reduction method, and comprises the following steps:
a. preparing mesoporous graphite phase carbon nitride: dropwise adding 50% cyanamide aqueous solution into silica sol under vigorous stirring, wherein the mass ratio of the silica sol to the cyanamide is 10: 1-1: 10, fully stirring and evaporating to dryness in a water bath, calcining the obtained solid for 4 hours under the protection of nitrogen, and naturally cooling to obtain a yellow solid; the resulting solid was ground and added to a solution of ammonium bifluoride and stirred for 48 hours to remove Si02A template, washing and drying the obtained solid to obtain light yellow mesoporous graphite phase carbon nitride as a matrix;
b. loading of palladium-cobalt metal nanoparticles: and (2) ultrasonically dispersing 100mg of prepared mesoporous graphite phase carbon nitride in 25mL of deionized water, dropwise adding a certain amount of palladium salt solution under vigorous stirring, stirring overnight, then dropwise adding a reducing agent for reduction, centrifugally separating and washing the obtained mixture, retaining the solid, adding deionized water again for dispersion, adding a certain amount of cobalt chloride solution, repeating the operation for reduction, and finally obtaining the solid, and centrifugally separating, washing and drying the obtained solid to obtain the palladium-cobalt/carbon nitride composite material.
2. The method of claim 1, wherein the cyanamide used in the preparation of the mesoporous graphite phase carbon nitride is one of raw materials of cyanamide, dicyandiamide, melamine or cyanuric acid, and the palladium salt solution used in the loading of the palladium-cobalt metal nanoparticles is one of palladium chloride, palladium nitrate or palladium sulfate solutions.
3. The method for preparing a palladium-cobalt/carbon nitride composite material according to claim 1 or 2, wherein the concentration of the palladium salt solution is 0.1-10 mol/L.
4. The method for preparing a palladium-cobalt/carbon nitride composite material according to claim 1, wherein the concentration of the cobalt chloride solution is 0.1-1 mol/L.
5. The method of claim 1, wherein the reducing agent is one of a sodium borohydride solution, a dicyandiamide solution, or a sodium sulfite solution.
6. The method for preparing a palladium-cobalt/carbon nitride composite material according to claim 1, wherein the evaporation temperature is 50-80 ℃.
7. The method for preparing a palladium-cobalt/carbon nitride composite material according to claim 1, wherein the calcination temperature is 500-650 ℃.
8. A palladium-cobalt/carbon nitride composite material is characterized in that the palladium-cobalt composite material is prepared according to the method of any one of claims 1 to 7, the obtained palladium-cobalt nanoparticles are formed by means of a rich pore channel structure of mesoporous graphite phase carbon nitride and are attached to the pore channels and the surface of the carbon nitride material, wherein due to the existence of a heterojunction structure between the palladium-cobalt nanoparticles and the carbon nitride, the palladium-cobalt composite material can enable the surface of the palladium particles to have higher electron density and can capture photoelectrons generated by the carbon nitride under illumination.
9. The Pd-Co-N composite material according to claim 8, wherein the Pd-Co-N composite material is (5-10)% Pd- (1-8)% Co/g-C3N4。
10. Use of the palladium-cobalt/carbon nitride composite material according to claim 8 or 9 as a catalyst material for photocatalytic hydrogen production from formic acid.
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