CN113600185A - Amino-functionalized h-BN supported AuPd nano-catalyst and preparation method and application thereof - Google Patents
Amino-functionalized h-BN supported AuPd nano-catalyst and preparation method and application thereof Download PDFInfo
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- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 54
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 49
- 235000019253 formic acid Nutrition 0.000 claims abstract description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 25
- 239000001257 hydrogen Substances 0.000 claims abstract description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 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 23
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- 229910052582 BN Inorganic materials 0.000 claims abstract description 16
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 13
- 239000002105 nanoparticle Substances 0.000 claims abstract description 10
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 5
- 239000000956 alloy Substances 0.000 claims abstract description 5
- 238000007306 functionalization reaction Methods 0.000 claims abstract description 4
- 238000011068 loading method Methods 0.000 claims abstract description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 35
- 239000007864 aqueous solution Substances 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 26
- 239000011259 mixed solution Substances 0.000 claims description 23
- 239000002135 nanosheet Substances 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910004042 HAuCl4 Inorganic materials 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 229910003244 Na2PdCl4 Inorganic materials 0.000 claims description 7
- 101150003085 Pdcl gene Proteins 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- -1 citric acid modified boron nitride Chemical class 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 27
- 230000003197 catalytic effect Effects 0.000 abstract description 16
- 238000006356 dehydrogenation reaction Methods 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 7
- 239000000446 fuel Substances 0.000 abstract description 4
- 230000001737 promoting effect Effects 0.000 abstract description 4
- 239000011232 storage material Substances 0.000 abstract description 3
- 239000011949 solid catalyst Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 21
- 239000007789 gas Substances 0.000 description 11
- 239000012279 sodium borohydride Substances 0.000 description 8
- 229910000033 sodium borohydride Inorganic materials 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 230000007547 defect Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 229910018557 Si O Inorganic materials 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 230000037361 pathway Effects 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- TZHYBRCGYCPGBQ-UHFFFAOYSA-N [B].[N] Chemical compound [B].[N] TZHYBRCGYCPGBQ-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
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- B01J23/48—Silver or gold
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Abstract
The invention belongs to the field of catalysts for formic acid dehydrogenation reactions, and particularly discloses an amino-functionalized h-BN supported AuPd nano catalyst and a preparation method and application thereof, wherein firstly, citric acid is used for modifying hexagonal boron nitride h-BN to prepare ca-BNNS; secondly, performing amino functionalization by using the prepared cA-BNNS to prepare A cA-BNNS-A solution; and finally, loading the AuPd nano-particles in A cA-BNNS-A carrier to prepare the amino functionalized h-BN loaded AuPd alloy nano-catalyst AuPd/cA-BNNS-A. The invention can be used as a simple, convenient and efficient method to synthesize a high-performance supported catalyst, and the synthesized catalyst can obtain excellent catalytic activity when being applied to the hydrogen production reaction by formic acid decomposition, thereby providing a new way for developing a safe and efficient solid catalyst and further promoting the application of FA as a hydrogen storage material in a vehicle-mounted fuel cell.
Description
Technical Field
The invention relates to the field of catalysts for formic acid dehydrogenation reactions, in particular to an amino functionalized h-BN supported AuPd nano catalyst and a preparation method and application thereof.
Background
With the development of science and technology, the use of energy is increasing day by day, but fossil fuel belongs to non-renewable energy, and the environmental problems brought by the energy crisis and the combustion products thereof which are reduced continuously bring a severe test to the social development. The search for new energy sources to replace traditional fossil energy sources is urgent. The hydrogen energy is regarded as one of clean energy sources in the world because the combustion heat value is high and the product is water without pollution, and the hydrogen energy and fuel cell industry also raises the commercial hot tide in the world and has wide application prospect. Formic acid (HCOOH, FA) is a safe, convenient H2Vector due to its H2High bulk density (53g L)-1) Easy to charge and excellent in stability under normal conditions, is considered as a chemical hydrogen storage material with great application prospects. H stored in FA2Can be via the dehydrogenation pathway (HCOOH → H)2+CO2) Released on a suitable catalyst and possibly also subjected to dehydration to form water and carbon monoxide (HCOOH → H)2O + CO). In which the formic acid dehydrogenation reaction is a desirable route, and at the same time, the dehydration reaction should be avoided, and since CO produced by the dehydration reaction is a harmful component of the catalyst in the fuel cell, the formic acid dehydration reaction must be strictly controlled, and the reaction pathway largely depends on the catalyst.
At present, the catalysts used for the formic acid dehydrogenation mainly include homogeneous catalysts and heterogeneous catalysts, and among them, heterogeneous catalysts are widely studied because of their advantages of easy control and easy recovery. The research finds that Pd and Au are effective elements for dehydrogenating formic acid in the formic acid dehydrogenation reaction, and the catalytic performance of the formed AuPd alloy shows obvious enhancement due to the synergistic action between Au and Pd.
Nanoparticles (NPs) having an ultra-fine size generally undergo severe agglomeration due to their high surface free energy, resulting in a decrease in reactive active sites, which greatly inhibits catalyst activity. Researches find that the carrier can effectively avoid the agglomeration of NP, and the interaction between metal NP and the carrier can improve the catalytic activity of the supported nanoparticles. Among a plurality of carrier materials, hexagonal boron nitride (h-BN) has good thermal stability, chemical stability and mechanical strength, and has high surface area and nitrogen-boron polar bonds capable of adsorbing various substances from an aqueous solution, but the unmodified h-BN belongs to hydrophobic substances, citric acid is helpful for improving the hydrophilicity of the substances, and then the h-BN is modified by the citric acid. The modified h-BN can further improve the water solubility of the h-BN and the dispersity of the metal nano-catalyst through the interaction of the functional group and the metal nano-catalyst, and simultaneously improve the electronic structure of the h-BN, thereby improving the catalytic performance of the functional h-BN based composite.
Therefore, it is highly desirable to search a simple and convenient strategy for preparing an amino-functionalized h-BN supported AuPd nanocatalyst to achieve ultra-fine size and excellent dispersibility as a high performance catalyst for formic acid dehydrogenation.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides an amino-functionalized h-BN supported AuPd nano-catalyst, and a preparation method and application thereof.
In order to achieve the purpose, the invention is implemented according to the following technical scheme:
the invention aims to provide a preparation method of an amino functionalized h-BN supported AuPd nano catalyst, which comprises the following steps:
s1, modifying the hexagonal boron nitride h-BN by using citric acid to obtain a citric acid modified boron nitride nanosheet ca-BNNS;
s2, performing amino functionalization on the citric acid modified boron nitride nanosheet cA-BNNS to prepare an amino functionalized boron nitride nanosheet cA-BNNS-A solution;
s3, loading AuPd alloy nanoparticles on A cA-BNNS-A carrier to prepare the amino-functionalized h-BN supported AuPd nano catalyst AuPd/cA-BNNS-A.
As a further technical solution of the present invention, the step S1 specifically comprises:
s11, uniformly grinding 3.33g of citric acid and 50mg of hexagonal boron nitride h-BN in N2Heating to 170 ℃ at the speed of 2 ℃/min in the atmosphere, preserving heat for 8h, and cooling to room temperature along with the furnace;
s12, washing the obtained product with ethanol and deionized water for several times, and then drying in vacuum at 40 ℃ to obtain the tan amino functionalized boron nitride nanosheet ca-BNNS.
As a further technical solution of the present invention, the step S2 specifically comprises:
s21, adding 0.4mL of 3-aminopropyltriethoxysilane APTES into 10mL of deionized water to prepare an aqueous solution of the 3-aminopropyltriethoxysilane APTES;
s22, mixing the aqueous solution of 3-aminopropyltriethoxysilane APTES and 15.0mg of amino-functionalized boron nitride nanosheet cA-BNNS, and carrying out ultrasonic treatment for 40min to obtain an amino-functionalized boron nitride nanosheet cA-BNNS-A solution.
As a further technical solution of the present invention, the step S3 specifically comprises:
s31 PdCl with the molar ratio of 1:22Dissolving NaCl in distilled water, and stirring to obtain brown yellow Na with concentration of 0.025M2PdCl4An aqueous solution;
s32, taking 0.07mmol of Na2PdCl4Aqueous solution and 0.03mmol of HAuCl4·4H2Adding O into the cA-BNNS-A solution, and stirring for 3h at room temperature to obtain A mixed solution A;
s33, mixing 40mg NaBH at room temperature4Adding the reducing agent into the mixed solution A, and continuously stirring and reducing for 10-30min to obtain a mixed solution B;
s34, magnetically stirring and reducing the mixed solution B in the air at room temperature, centrifuging at 8000-12000rpm for 3-10min when no bubbles exist, and washing for multiple times to obtain the amino functionalized h-BN supported AuPd nano catalyst AuPd/cA-BNNS-A.
The invention also provides A preparation method of the amino-functionalized h-BN supported AuPd nano-catalyst, and the amino-functionalized h-BN supported AuPd nano-catalyst is AuPd/cA-BNNS-A prepared by the preparation method.
As A further technical scheme of the invention, the particle size of the amino-functionalized h-BN supported AuPd nano-catalyst AuPd/cA-BNNS-A is 2.0 nm.
The third purpose of the invention is to provide an application of the amino-functionalized h-BN supported AuPd nano-catalyst, wherein the amino-functionalized h-BN supported AuPd nano-catalyst AuPd/cA-BNNS-A is used for catalyzing the formic acid aqueous solution to decompose and produce hydrogen, and the application specifically comprises the following steps: mixing the AuPd/cA-BNNS-A nano catalyst and formic acid according to the molar ratio of 0.02, and catalyzing the decomposition of formic acid aqueous solution to prepare hydrogen; wherein the concentration of the formic acid aqueous solution is 1M.
Compared with the prior art, the invention firstly adopts A wet chemical method to successfully synthesize the amino-functionalized h-BN supported AuPd nano-catalyst which can be completed at room temperature, has the advantages of rapid and efficient synthesis process, simple and convenient operation and the like, obviously improves the dispersibility of AuPd nano-particles on A cA-BNNS-A carrier and reduces the size of metal nano-particles; the synthesized AuPd/cA-BNNS-A nano catalyst is applied to the hydrogen production reaction by decomposing the catalytic formic acid aqueous solution, the catalyst still shows excellent catalytic performance under the condition of no existence of any additive, 225mL of gas can be generated within 1.35 minutes under 323K, and the initial conversion frequency (TOF) is 7046mol H2 mol catalyst-1h-1(ii) a The conversion rate is 100%; the hydrogen selectivity was 100%. The excellent catalytic activity is attributed to the modification of h-BN by citric acid greatly improving the hydrophilicity on the one hand and the electronic effect caused by the strong interaction between the cA-BNNS-A carrier and the AuPd NPs on the other hand.
In conclusion, the invention explores a simple wet chemical method for preparing the AuPd nano-catalyst loaded on the amino-functionalized h-BN, so as to realize good hydrophilicity and excellent dispersibility, and the AuPd nano-catalyst is used as a high-performance catalyst for formic acid dehydrogenation, thereby providing a new idea for developing a safe and efficient catalyst and further promoting the application of formic acid as a hydrogen storage material in a vehicle-mounted fuel cell.
Drawings
FIG. 1(A) changes in color of solutions of (1) h-BN-A, (2) cA-BNNS-A, (3) AuPd/h-BN-A in comparative example 1, (4) AuPd/cA-BNNS-A in example 1 left to stand at room temperature for 0min and 60min, respectively; 1(b) Scanning Electron Microscope (SEM) image of AuPd/cA-BNNS-A nanocatalyst of example 1;
FIG. 2(A) is A Fourier transform infrared (FT-IR) spectrum of AuPd/h-BN, AuPd/h-BN-A, AuPd/cA-BNNS in comparative example 1 and AuPd/cA-BNNS-A in example 1; 2(b) is the X-ray powder diffraction (XRD) pattern of AuPd/cA-BNNS-A in example 1 and AuPd/h-BN-A, AuPd/h-BN, AuPd in comparative example 1;
FIG. 3(A) is the X-ray photoelectron (XPS) total spectrA of AuPd/cA-BNNS-A in example 1 and AuPd in comparative example 1; 3(b) is the XPS spectrum of N1s of AuPd/cA-BNNS-A in example 1; 3(c) is the XPS spectrA of the AuPd/cA-BNNS-A in example 1, and the Pd 3d of AuPd/h-BN-A and AuPd in comparative example 1; 3(d) is the XPS spectrA of Au 4f of AuPd/cA-BNNS-A in example 1 and AuPd/h-BN-A and AuPd in comparative example 1;
FIG. 4(A) is A graph showing the hydrogen production by catalytic FA decomposition in AuPd/cA-BNNS-A of example 1 and AuPd/h-BN-A, AuPd/h-BN, AuPd at 323K in comparative example 1, 4(b) is an initial conversion frequency (TOF) of the hydrogen production by catalytic FA decomposition in AuPd/cA-BNNS-A of example 1 and AuPd/h-BN-A, AuPd/h-BN, AuPd at 323K in comparative example 1, 4(c) is A graph showing the hydrogen production by catalytic FA decomposition in AuPd/cA-BNNS-A at different temperatures in comparative example 2, and 4(d) is an Arrhenius curve of the hydrogen production by catalytic FA decomposition in AuPd/cA-BNNS-A catalyst obtained by fitting the datA in 4 (c).
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. The specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
Example 1
3.33g of citric acid (ca) was uniformly ground with 50mg of h-BN in N2Heating to 170 ℃ (2 ℃/min) in the atmosphere, preserving heat for 8h, and cooling to room temperature along with the furnace;
washing the obtained product with ethanol and deionized water for several times, and vacuum drying at 40 deg.C overnight to obtain brown ca-BNNS;
adding 0.4mL of 3-aminopropyltriethoxysilane APTES into 10mL of deionized water to prepare an aqueous solution of the 3-aminopropyltriethoxysilane APTES;
mixing the aqueous solution of 3-aminopropyltriethoxysilane APTES and 15.0mg cA-BNNS, and performing ultrasonic treatment for 40min to obtain A cA-BNNS-A solution;
PdCl with a molar ratio of 1:22Dissolving NaCl in distilled water, and stirring to obtain brown yellow Na with concentration of 0.025M2PdCl4An aqueous solution;
0.07mmol of Na is taken2PdCl4Aqueous solution and 0.03mmol of HAuCl4·4H2Adding O into the solution cA-BNNS-A, and stirring for 3h at room temperature to obtain A mixed solution A;
40mg of NaBH4Adding the reducing agent into the mixed solution A, and continuously stirring and reducing for 10min to obtain a mixed solution B;
at room temperature, the mixed solution B is magnetically stirred and reduced in the air, when no air bubbles exist, the mixed solution B is centrifuged at 8000rpm for 3min and washed with water for 3 times to obtain the amino functionalized h-BN supported AuPd nano-catalyst Au0.3Pd0.7/ca-BNNS-A。
Example 2
3.33g of citric acid (ca) was uniformly ground with 50mg of h-BN in N2Heating to 170 ℃ (2 ℃/min) in the atmosphere, preserving heat for 8h, and cooling to room temperature along with the furnace;
washing the obtained product with ethanol and deionized water for several times, and vacuum drying at 40 deg.C overnight to obtain brown ca-BNNS;
adding 0.4mL of 3-aminopropyltriethoxysilane APTES into 10mL of deionized water to prepare an aqueous solution of the 3-aminopropyltriethoxysilane APTES;
mixing the aqueous solution of 3-aminopropyltriethoxysilane APTES and 15.0mg cA-BNNS, and performing ultrasonic treatment for 40min to obtain A cA-BNNS-A solution;
PdCl with a molar ratio of 1:22Dissolving NaCl in distilled water, and stirring to obtain brown yellow Na with concentration of 0.025M2PdCl4An aqueous solution;
0.07mmol of Na is taken2PdCl4Aqueous solution and 0.03mmol of HAuCl4·4H2Adding O into the solution cA-BNNS-A, and stirring for 3h at room temperature to obtain A mixed solution A;
40mg of NaBH4Adding the reducing agent into the mixed solution A, and continuously stirring and reducing for 30min to obtain a mixed solution B;
at room temperature, the mixed solution B is magnetically stirred and reduced in the air, when no air bubbles exist, the mixed solution B is centrifuged at 12000rpm for 10min and washed for 3 times to obtain the amino functionalized h-BN supported AuPd nano-catalyst Au0.3Pd0.7/ca-BNNS-A。
Example 3
3.33g of citric acid (ca) was uniformly ground with 50mg of h-BN in N2Heating to 170 ℃ (2 ℃/min) in the atmosphere, preserving heat for 8h, and cooling to room temperature along with the furnace;
washing the obtained product with ethanol and deionized water for several times, and vacuum drying at 40 deg.C overnight to obtain brown ca-BNNS;
adding 0.4mL of 3-aminopropyltriethoxysilane APTES into 10mL of deionized water to prepare an aqueous solution of the 3-aminopropyltriethoxysilane APTES;
mixing the aqueous solution of 3-aminopropyltriethoxysilane APTES and 15.0mg cA-BNNS, and performing ultrasonic treatment for 40min to obtain A cA-BNNS-A solution;
PdCl with a molar ratio of 1:22Dissolving NaCl in distilled water, and stirring to obtain brown yellow Na with concentration of 0.025M2PdCl4An aqueous solution;
0.07mmol of Na is taken2PdCl4Aqueous solution and 0.03mmol of HAuCl4·4H2Adding O into the solution cA-BNNS-A, and stirring for 3h at room temperature to obtain A mixed solution A;
40mg of NaBH4Adding the reducing agent into the mixed solution A, and continuously stirring and reducing for 20min to obtain a mixed solution B;
at room temperature, the mixed solution B is magnetically stirred and reduced in the air, when no air bubbles exist, the mixed solution B is centrifuged at 10000rpm for 8min and washed for 3 times to obtain the amino functionalized h-BN supported AuPd nano catalyst Au0.3Pd0.7/ca-BNNS-A。
Further, for comparison with example 1, example 2 and example 3, the following comparative examples were made.
Comparative example 1
0.03mmol of HAuCl4·4H2O and 0.07mmol of Na2PdCl4Dissolving in water solution containing 15mg h-BN and 0.4mL 3-aminopropyltriethoxysilane APTES, and stirring; 40mg of NaBH4Adding into the above solution, and magnetically stirring at 25 deg.C to completely reduce; centrifuging, washing to obtain Au0.3Pd0.7the/h-BN-A nano catalyst. 0.03mmol of HAuCl4·4H2O and 0.07mmol of Na2PdCl4Dissolving in water solution containing 15mg h-BN, and stirring uniformly; 40mg of NaBH4Adding into the above solution, and magnetically stirring at 25 deg.C to completely reduce; centrifuging, washing to obtain Au0.3Pd0.7the/h-BN nano catalyst. 0.03mmol of HAuCl4·4H2O and 0.07mmol of Na2PdCl4Dissolved in an appropriate amount of deionized water, 40mg of NaBH4Adding into the above solution, and magnetically stirring at 25 deg.C to completely reduce; centrifuging, washing to obtain Au0.3Pd0.7A catalyst. 0.03mmol of HAuCl4·4H2O and 0.07mmol of Na2PdCl4Dissolving in water solution containing 15mg ca-BNNS, and stirring; 40mg of NaBH4Adding into the above solution, and magnetically stirring at 25 deg.C to completely reduce; washing with centrifugal water to obtain Au0.3Pd0.7the/ca-BNNS nano catalyst.
Comparative example 2
After preparation of ca-BNNS, 0.03mmol of HAuCl4·4H2O and 0.07mmol of Na2PdCl4Dissolving in water solution containing 15mg ca-BNNS and 0.4mL 3-aminopropyl triethoxy silane APTES, and stirring uniformly; 40mg of NaBH4Adding into the above solution, and magnetically stirring at 25 deg.C to completely reduce; centrifuging, washing to obtain Au0.3Pd0.7A/cA-BNNS-A nano catalyst.
Sample detection
Dried Au obtained in example 10.3Pd0.7the/cA-BNNS-A was uniformly ground with the dried AuPd/h-BN, AuPd/h-BN-A, AuPd/cA-BNNS prepared in comparative example 1 and dried potassium bromide at A mass ratio of 1:200, respectively, and subjected to Fourier transform infrared (FT-IR) spectroscopic analysis, referring to FIG. 1(A), at 1374cm for the AuPd/h-BN sample in comparative example 1-1The nearby peak corresponds to the stretching vibration of B-N, and 810cm-1The peak at (A) is the bending vibration of B-N-B, which demonstrates the presence of h-BN. In comparative example 1, AuPd/ca-BNNS showed a peak value of 3415cm in addition to the two peaks-1And 918cm-1Two peaks appear, corresponding to the stretching vibration of-OH and the C-H bond respectively, which shows that the citric acid (cA) molecule is not directly modified on the BN surface, but generates-OH and C-H modification on BN defects and edge positions by destroying part of B-N bonds, and 1633cm is generated after the AuPd/cA-BNNS-A in example 1 is added with APTES-1、1576cm-1、1127cm-1And 1035cm-1Peaks corresponding to N-H stretching vibration, Si-O-C, Si-O, respectively, at 2930cm-1The peak of (a) belongs to ca molecules, but is almost negligible due to the small content. This indicates that the broken B-N bond due to ca modification provides more defects to BN, and these defect sites are more favorable for-NH in APTES2And introduction of Si-O and the like. For the above reasons, the hydrophilicity of AuPd/cA-BNNS-A was greatly improved as compared with h-BN-A, see FIG. 1 (b).
The AuPd/cA-BNNS-A nano catalyst prepared in example 1 is dissolved in A proper amount of deionized water for dilution, ultrasonic dispersion is uniform, A plurality of drops of the diluted solution are dropped on A silicon wafer for observation and analysis by A Scanning Electron Microscope (SEM), and the result shows that after citric acid and APTES are introduced, the amino functionalized h-BN is successfully stripped from the boron nitride nano sheet (cA-BNNS-A), and refer to fig. 2 (A). The AuPd/cA-BNNS-A prepared in example 1 and the AuPd/h-BN-A, AuPd/h-BN prepared in comparative example 1 are dried in vacuum, and subjected to X-ray powder diffraction (XRD) analysis, referring to fig. 2(b), the analysis result shows that the cA-BNNS-A functionalized by amino still maintains the phase of h-BN, and AuPd nano-particles have an alloy structure, thus the experimental method successfully synthesizes the cA-BNNS-A supported AuPd binary alloy catalyst.
Further, the AuPd/cA-BNNS-A nano-catalyst obtained in example 1 was dried in vacuum, and an appropriate amount of the dried powder was subjected to X-ray photoelectron spectroscopy (XPS) detection, referring to FIG. 3. The results of the examination showed that the presence of B and N was detected in the total spectrum of AuPd/cA-BNNS-A as compared with the XPS total spectrum of AuPd prepared in comparative example 1, referring to FIG. 3(A), and the results of the spectral peak separation of N1s showed that 397.9eV corresponds to the N peak of h-BN and 399.6eV corresponds to C-NH2Referring to FIG. 3(b), the successful synthesis of AuPd/cA-BNNS-A is illustrated; compared with the Pd 3d and Au 4f spectrograms of AuPd prepared in the comparative example 1, the peak positions of AuPd/cA-BNNS-A are both shifted in the negative direction, and referring to fig. 3(c-d), the electron synergistic effect exists between the amino group serving as an electron donor and the AuPd metal active sites, which plays an important promoting role in promoting the activity of the catalyst.
AuPd/cA-BNNS-A prepared in example 1 is used for catalyzing FA decomposition hydrogen production reaction: mixing an AuPd/cA-BNNS-A catalyst and FA at A molar ratio of 0.02, wherein the concentration of formic acid aqueous solution is 1M, measuring the generated gas by A gas burette, and catalyzing the gas production (mL) of the FA aqueous solution hydrogen production process by the AuPd/cA-BNNS-A nanocatalyst at 323K and the relation of time (min) as shown in (A) in FIG. 4, the gas production of the catalytic FA hydrogen production by decomposition can reach 225mL within 1.35min, and the initial conversion frequency (TOF) is 7046mol H2 mol catalyst-1h-1Referring to FIG. 4(b), the catalytic activity of AuPd/cA-BNNS-A catalyst at different temperatures was investigated using temperature as A variable as shown in (c) of FIG. 4, and as the temperature increased, the catalytic activity of the catalyst increased, and the activation energy of the reaction (E)a) It was 29.7 kJ/mol.
Comparative example 1The AuPd/h-BN-A, AuPd/h-BN and AuPd catalyst prepared in (1) were dispersed in water, and a 5mmol, 1M aqueous solution of FA was further added, and the amount of gas generated was measured by a gas burette. The relationship between gas production (mL) and time (min) in the process of producing hydrogen by catalyzing FA aqueous solution with AuPd/H-BN-A, AuPd/H-BN and AuPd catalyst prepared in comparative example 1 under 323K is shown in (a) of FIG. 4, and the initial conversion frequency (TOF) of hydrogen production by catalyzing FA decomposition is 2602mol of H2 mol catalyst-1h-1，127mol H2 mol catalyst-1h-1，108mol H2 mol catalyst-1h-1Refer to 4 (b).
The AuPd/cA-BNNS-A nanocatalyst prepared in comparative example 2 was dispersed in water, and A5 mmol, 1M aqueous solution of FA was added, and the generated hydrogen gas was measured by A gas burette. The reaction temperature was changed, the gas yield (mL) of the hydrogen production process by catalyzing FA aqueous solution with AuPd/cA-BNNS-A nanocatalyst at 293, 303, 313 and 323K was recorded as A function of time (min), as shown in FIG. 4(c), and the activation energy of the AuPd/cA-BNNS-A catalytic FA decomposition hydrogen production reaction was found to be 29.7kJ/mol by fitting the datA in FIG. 4(c) (as shown in FIG. 4 (d)).
In summary, the invention develops A method for modifying the surface of h-BN by using citric acid, achieves the purposes of stripping the h-BN and improving the hydrophilicity of the h-BN through further amino functionalization, and finally synthesizes the supported catalyst taking cA-BNNS-A as A carrier and carrying AuPd NPs through A wet chemical method. The prepared AuPd/cA-BNNS-A nano catalyst is applied to the hydrogen production reaction by catalyzing the decomposition of FA aqueous solution, the catalyst still shows excellent catalytic performance under the condition of no existence of any additive, 225mL of gas can be generated within 1.35 minutes under 323K, and the initial conversion frequency (TOF) is 7046mol H2mol catalyst-1h-1。
The h-BN functionalized by amino groups is used as A carrier, so that on one hand, the hydrophilicity of the h-BN is effectively improved, and the water solubility of the obtained cA-BNNS-A is greatly enhanced; on the other hand, a functional group- (NH-) -2Can provide more electrons for the active sites of the catalyst as an electron donor, thereby obtaining catalyst active atoms with high electron density and further showingThe activity of the catalyst is obviously improved.
The technical solution of the present invention is not limited to the limitations of the above specific embodiments, and all technical modifications made according to the technical solution of the present invention fall within the protection scope of the present invention.
Claims (8)
1. A preparation method of an amino functionalized h-BN supported AuPd nano catalyst is characterized by comprising the following steps:
s1, modifying the hexagonal boron nitride h-BN by using citric acid to obtain a citric acid modified boron nitride nanosheet ca-BNNS;
s2, performing amino functionalization on the citric acid modified boron nitride nanosheet cA-BNNS to prepare an amino functionalized boron nitride nanosheet cA-BNNS-A solution;
s3, loading AuPd alloy nanoparticles on A cA-BNNS-A carrier to prepare the amino-functionalized h-BN supported AuPd nano catalyst AuPd/cA-BNNS-A.
2. The preparation method of the amino-functionalized h-BN supported AuPd nano-catalyst according to claim 1, wherein the S1 comprises the following specific steps:
s11, uniformly grinding 3.33g of citric acid and 50mg of hexagonal boron nitride h-BN in N2Heating to 170 ℃ at the speed of 2 ℃/min in the atmosphere, preserving heat for 8h, and cooling to room temperature along with the furnace;
s12, washing the obtained product with ethanol and deionized water for several times, and then drying in vacuum at 40 ℃ to obtain the tan amino functionalized boron nitride nanosheet ca-BNNS.
3. The preparation method of the amino-functionalized h-BN supported AuPd nano-catalyst according to claim 1, wherein the S2 comprises the following specific steps:
s21, adding 0.4mL of 3-aminopropyltriethoxysilane APTES into 10mL of deionized water to prepare an aqueous solution of the 3-aminopropyltriethoxysilane APTES;
s22, mixing the aqueous solution of 3-aminopropyltriethoxysilane APTES and 15.0mg of amino-functionalized boron nitride nanosheet cA-BNNS, and carrying out ultrasonic treatment for 40min to obtain an amino-functionalized boron nitride nanosheet cA-BNNS-A solution.
4. The preparation method of the amino-functionalized h-BN supported AuPd nano-catalyst according to claim 1, wherein the S3 comprises the following specific steps:
s31 PdCl with the molar ratio of 1:22Dissolving NaCl in distilled water, and stirring to obtain brown yellow Na with concentration of 0.025M2PdCl4An aqueous solution;
s32, taking 0.07mmol of Na2PdCl4Aqueous solution and 0.03mmol of HAuCl4·4H2Adding O into the amino-functionalized boron nitride nanosheet cA-BNNS-A solution, and stirring for 3h at room temperature to obtain A mixed solution A;
s33, mixing 40mg NaBH at room temperature4Adding the reducing agent into the mixed solution A, and continuously stirring and reducing for 10-30min to obtain a mixed solution B;
s34, magnetically stirring and reducing the mixed solution B in the air at room temperature, centrifuging at 8000-12000rpm for 3-10min when no bubbles exist, and washing for multiple times to obtain the amino functionalized h-BN supported AuPd nano catalyst AuPd/cA-BNNS-A.
5. The AuPd/cA-BNNS-A as the amino-functionalized h-BN supported AuPd nano-catalyst prepared by the preparation method of the amino-functionalized h-BN supported AuPd nano-catalyst as claimed in any one of claims 1 to 4.
6. The amino-functionalized h-BN supported AuPd nanocatalyst of claim 5, wherein: the particle size of the amino functionalized h-BN supported AuPd nano catalyst AuPd/cA-BNNS-A is 2.0 nm.
7. The application of the amino-functionalized h-BN supported AuPd nano-catalyst according to claim 6, wherein the application comprises the following steps: the amino-functionalized h-BN supported AuPd nano catalyst AuPd/cA-BNNS-A is used for catalyzing the formic acid aqueous solution to decompose and produce hydrogen.
8. The application of the amino-functionalized h-BN supported AuPd nano-catalyst as claimed in claim 7, wherein the amino-functionalized h-BN supported AuPd nano-catalyst AuPd/cA-BNNS-A is used for catalyzing the hydrogen production reaction by the decomposition of formic acid aqueous solution, and comprises the following specific steps: mixing the AuPd/cA-BNNS-A nano catalyst and formic acid according to the molar ratio of 0.02, and catalyzing the decomposition of formic acid solution to prepare hydrogen; wherein the concentration of the formic acid aqueous solution is 1M.
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