AU2021101809A4 - A Method For Catalyzing The Dehydrogenation of Formic Acid With Visible Light With PdAu Nanosheet Catalyst - Google Patents
A Method For Catalyzing The Dehydrogenation of Formic Acid With Visible Light With PdAu Nanosheet Catalyst Download PDFInfo
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- 239000002135 nanosheet Substances 0.000 title claims abstract description 77
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 235000019253 formic acid Nutrition 0.000 title claims abstract description 38
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000203 mixture Substances 0.000 claims abstract description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- 239000004280 Sodium formate Substances 0.000 claims abstract description 13
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims abstract description 13
- 235000019254 sodium formate Nutrition 0.000 claims abstract description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 5
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 28
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 24
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 18
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 15
- 229920000877 Melamine resin Polymers 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 14
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 14
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 14
- 230000009467 reduction Effects 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 10
- 239000008098 formaldehyde solution Substances 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 238000004108 freeze drying Methods 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- -1 of which Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 9
- 238000004064 recycling Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 2
- 238000003889 chemical engineering Methods 0.000 abstract 1
- 230000001699 photocatalysis Effects 0.000 abstract 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000012495 reaction gas Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000002638 heterogeneous catalyst Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01J23/48—Silver or gold
- B01J23/52—Gold
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a method for catalyzing the dehydrogenation of formic acid with
visible light with PdAu nanosheet catalyst, which belongs to the technical field of chemistry
and chemical engineering. In the invention, place the prepared PdAu nanosheet catalyst in a
jacketed reactor, control the reaction to proceed at a certain temperature through a constant
temperature circulation tank, irradiate the reaction solution with visible light from the top of
the jacketed reactor, and then add a mixture of formic acid and sodium formate into the reactor
for reaction, and the generated hydrogen is collected by drainage method. The difference with
the traditional supported catalyst is: According to the invention, the supported PdAu nanosheet
catalyst with high activity and high selectivity for photocatalytic dehydrogenation of formic
acid to hydrogen can be prepared by adjusting the content of metal palladium and metal in the
catalyst and the content of Mxene-TiO2. The catalyst is used for dehydrogenation reaction of
formic acid with visible light, the conversion rate and selectivity of dehydrogenation are both
100%, the TOF value of the reaction is greater than 850h- 1, and the TOF value of the reaction
is still greater than 834h-1 after recycling for 8h.
Description
Descriptions
A Method for Catalyzing the Dehydrogenation of Formic Acid with Visible Light with PdAu Nanosheet Catalyst
Technical Field
[0001] The invention belongs to the technical field of chemistry and chemical
engineering, in particular to a method for catalyzing the dehydrogenation of
formic acid with visible light with PdAu/TiO2@g-C3N4 nanosheet catalyst.
Background Technology
[0002] Hydrogen is an efficient, clean and green energy source. However,
hydrogen has very low volume energy density and mass energy density. Efficient
and safe storage and transportation of hydrogen has become a major challenge for
hydrogen energy utilization. In order to solve this problem, researchers have
developed and explored a variety of different types of hydrogen storage materials.
Of which, formic acid has attracted extensive attention from researchers due to its
non-toxic, high mass energy density, safe storage and transportation as well as
other advantages.
[0003] Currently, the key to the application of formic acid as a hydrogen storage
material lies in the development of efficient dehydrogenation catalysts. For the time
being, the catalysts researched by the researchers mainly focus on homogeneous
catalysts and heterogeneous catalysts. Of which, the homogeneous catalysts are
mainly metal complexes of ruthenium, rhodium, iridium, iron and cobalt. Can Li et
al. (CN105772090B) reported a type of computational dehydrogenation catalyst
that can be used in aqueous system. The catalyst comprises metals and ligands. The
metals are iridium, rhodium, ruthenium, iron, copper, cobalt, palladium and
platinum, etc. The ligands are heterocyclic compounds containing C=N double bonds in the structure; the highest TOF can reach 375*10 4 h-1 at 90°C under the condition of alkali free. Although homogeneous catalysts show excellent catalytic performance, their difficulty in separation and recycling largely limits their large-scale applications. Liu et al. designed the AuxPdy/CNS catalyst and applied it to the dehydrogenation of formic acid with visible light with a TOF value of up to
10178h-I(Applied Catalysis B: Environmental 252(2019)24-32). Therefore, the
research on heterogeneous catalysts, especially the heterogeneous catalysts that
achieve the efficient dehydrogenation of formic acid under the action of visible
light, is one of the current research hotspots.
Summary of the Invention
[0004] The purpose of the invention is to provide a method for catalyzing the
dehydrogenation of formic acid with visible light with
PdAu/Mxene-TiO2@g-C3N4 nanosheet catalyst in view of the shortcomings of the
existing technology, so that the PdAu/Mxene-TiO2@g-C3N4 nanosheet catalyst
can achieve the complete dehydrogenation of formic acid under mild conditions,
and the catalyst has good catalytic activity, selectivity and stability.
[0005] The technical solutions adopted by the invention to solve its technical
problems are as follows.
[0006] A method for catalyzing the dehydrogenation of formic acid with visible
light with PdAu nanosheet catalyst. Place the PdAu nanosheet catalyst in a
jacketed reactor, control the reaction to proceed at 10-40°C through a constant
temperature circulation tank, irradiate the reaction solution with visible light with
a wavelength of X>400nm from the top of the jacketed reactor, and then add a
mixture of formic acid and sodium formate with a molar ratio of 1: (0.2-0.6) into
the reactor for reaction, and finally obtain the product hydrogen.
[0007] The mass ratio of the catalyst to the mixture of formic acid and sodium
formate is 1: (30~50).
[0008] The PdAu nanosheet catalyst comprises Pd, Au, Mxene-TiO2 and
g-C3N4 nanosheet, of which, Pd is derived from palladium chloride, Au is derived
from aurichlorohydric acid, Mxene-TiO2 is derived from Mxene-Ti2AlC, and
g-C3N4 nanosheet is prepared by calcination of melamine and lithium chloride.
[0009] The PdAu nanosheet catalyst is prepared by the following steps:
[0010] (1) After calcinating the melamine and lithium chloride in a certain ratio
under certain calcination conditions and atmosphere, then wash them with water
for a period of time at a certain temperature, filter and obtain the g-C3N4
nanosheet;
[0011] The mass ratio of melamine to lithium chloride is 1: (4 8), the
calcination temperature is 520 550°C, the calcination time is 4 7h, the
atmosphere is nitrogen, the washing temperature is 20~45°C, and the washing
time is 40~50h;
[0012] (2) Take a certain amount of Ti2AlC, add it to a certain concentration of
hydrofluoric acid solution, treat it for a period of time, freeze-dry and obtain the
Ti2C;
[0013] The mass concentration of HF is 30~50wt%, and the treatment time is
4.0~6.0h;
[0014] (3) Place the Ti2C and g-C3N4 nanosheets in a hydrothermal synthesis
reactor containing 40ml of deionized water at a certain molar ratio, add a certain
concentration of NaHSO3 solution, ultrasonically disperse for a period of time,
and place them at a certain temperature for hydrothermal synthesis for a period of
time, after filtering and washing with water, freeze-dry and obtain the
Mxene-TiO2@g-C3N4 nanosheet support;
[0015] The molar ratio of Ti2C to g-C3N4 nanosheet is 1: (20 35), the
concentration of NaHSO3 is 0.03 ~ 0.05mol/l, the hydrothermal synthesis
temperature is 120-150°C, and the hydrothermal synthesis time is 8-12h;
[0016] (4) Place the porous Mxene-TiO2@g-C3N4 nanosheet support obtained by freeze-drying in a certain composition of palladium chloride and aurichlorohydric acid solution, reduce it with formaldehyde solution for a period of time, centrifuge and dry, and then obtain the PdAu/Mxene-TiO2@ g-C3N4 nanosheet catalyst;
[0017] The molar ratio of palladium chloride, aurichlorohydric acid to
Mxene-TiO2@g-C3N4 nanosheet is 1: (0.1~0.3): (20~25), the concentration of
formaldehyde is 0.05~0.09mol/L, the reduction temperature is 10~25°C, and the
reduction time is 5~8h.
[0018] Further, the mass ratio of melamine to lithium chloride is 1: 8, the
calcination temperature is 550°C, the calcination time is 4h, the atmosphere is
nitrogen, the washing temperature is 20°C, and the washing time is 50h; the mass
concentration of HF is 50wt%, and the treatment time is 4.0h; the molar ratio of
Ti2C to g-C3N4 nanosheet is 1: 35, the concentration of NaHSO3 is 0.05mol/l, the
hydrothermal synthesis temperature is 150°C, and the hydrothermal synthesis time
is 8h; the molar ratio of palladium chloride, aurichlorohydric acid to
Mxene-TiO2@g-C3N4 nanosheet is 1: 0.3: 25, the concentration of formaldehyde is
0.09mol/L, the reduction temperature is 10C, and the reduction time is 5h; the
mass ratio of the catalyst to the mixture of formic acid and sodium formate is 1: 50,
and the reaction temperature is 40°C; the molar ratio of formic acid to sodium
formate is 1:0.6. At this time, the selectivity of hydrogen is 100%, the conversion
rate of formic acid is 100%, and the TOF value of the reaction is 1360h-1 .
[0019] Compared with the existing technology, the beneficial effects of the
invention are:
[0020] 1. The patent of the invention uses Mxene-Ti2AlC as a precursor to
synthesize the Mxene-TiO2 rich in oxygen vacancy, and then synthesize the
highly dispersible Mxene-TiO 2@g-C3N4 nanosheet support material. The
Mxene-TiO2@g-C3N4 nanosheet support material has good electron transfer
performance and light induction performance. Further, it adopts the impregnation
reduction method to synthesize the PdAu/Mxene-TiO 2@g-C3N4 nanosheet catalyst, which is a kind of supported PdAu alloy synthesized by formaldehyde reduction under mild conditions. The reductant can adjust the structure of PdAu alloy and uniformly load on the support. By adjusting the ratio of metal components, the concentration of reductant and the reaction conditions, it can change the charge distribution of metal valence band orbits, so as to adjust the stability of catalytic reaction. In addition, due to the influence of multi-component metal composition and multi-functional groups on the surface of support, the
Strong Metal-Support Interactions (SMSI) between metal and support are
significantly enhanced, and the catalytic activity is effectively improved.
[0021] 2. The invention adopts the impregnation reduction method. First, it uses
the salt fusion method to synthesize the g-C 3N 4 nanosheet, and then treat the
Ti2AlC (Mxene) with hydrofluoric acid to prepare the Ti 2C, heat treat the g-C 3N 4
nanosheet and Ti 2C to prepare the Mxene-TiO 2@g-C 3N4 nanosheet. Place the
obtained Mxene-TiO2@g-C3N4 nanosheet in a certain composition of palladium
chloride and chloroauric acid solution, reduce it with formaldehyde solution for a
period of time at a certain temperature, centrifuge and dry, and then obtain the
PdAu/Mxene-TiO 2 @g-C 3N 4 nanosheet catalyst, which has high activity and
selectivity under the action of visible light. The catalyst is used for
dehydrogenation reaction of formic acid with visible light, the conversion rate and
selectivity of dehydrogenation are both 100%, the TOF value of the reaction is
greater than 850h- 1, and the TOF value of the reaction is still greater than 834h-1
after recycling for 8h.
[0022] Detailed Description of the Presently Preferred Embodiments
[0023] The invention will be further described in detail by the embodiments
below. However, the embodiments do not constitute a limitation on the
invention.
[0024] Embodiment 1
[0025] The Preparation Process of Catalyst
[0026] Grind and mix 3g of melamine and 12g of lithium chloride uniformly,
calcinate for 7h at 520°C under nitrogen atmosphere, wash the calcined mixture
with water for 50h at 20°C, dry and obtain the g-C3N4 nanosheet; weigh lg of
Ti2AlC into 30wt% of HF solution, the treatment time is 6.0h, filter, wash with
water, dry and obtain the Ti2C; place 0.1mmol of Ti2C and 2mmol of g-C3N4
nanosheets in a 40ml of deionized water, add NaHSO3, adjust the concentration of
NaHSO3 to 0.03mol/L, the hydrothermal synthesis temperature is 120°C, the
hydrothermal synthesis time is 12h, and obtain the (Mxene-TiO2)1/20@g-C3N4
nanosheet. Weigh 20mmol of (Mxene-TiO2)1/20@g-C3N4 nanosheet, place it in a
solution containing Immol of palladium chloride and 0.1mmol of aurichlorohydric
acid, reduce it with 0.05mol/L of formaldehyde solution for 8h at 10°C, obtain the
catalyst, which is denoted as the PdAuo /(Mxene-TiO2)1/20@g-C3N4 nanosheet
catalyst, and then store it in an airtight space.
[0027] The Reaction Process of Dehydrogenation
[0028] Place 50mg of the above catalyst into a jacketed reactor, control the reaction
to proceed at 20°C through a constant temperature circulation tank, irradiate the
reaction solution with visible light with a certain power wavelength (X > 400nm)
from the top of the jacketed reactor, and then add a 1.5g of mixture of formic acid
and sodium formate with a molar ratio of 1: 0.2, and collect the reaction gas. After
the reaction, the selectivity of hydrogen is 100%, the conversion rate of formic acid
is 100%, the TOF value of the reaction is 920h- 1, and the TOF value of the reaction
is still greater than 912h-1 after recycling for 8h.
[0029] Embodiment 2
[0030] The Preparation Process of Catalyst
[0031] Grind and mix 3g of melamine and 24g of lithium chloride uniformly,
calcinate for 4h at 550°C under nitrogen atmosphere, wash the calcined mixture
with water for 50h at 20°C, dry and obtain the g-C3N4 nanosheet; weigh lg of
Ti2AlC into 50wt% of HF solution, the treatment time is 4.0h, filter, wash with water, dry and obtain the Ti2C; place 0.1mmol of Ti2C and 3.5mmol of g-C3N4 nanosheets in a 40ml of deionized water, add NaHSO3, adjust the concentration of
NaHSO3 to 0.05mol/L, the hydrothermal synthesis temperature is 150°C, the hydrothermal synthesis time is 8h, and obtain the Mxene-TiO2)1/35@g-C3N4
nanosheet. Weigh 25mmol of (Mxene-TiO2)1/35@g-C3N4 nanosheet, place it in a
solution containing Immol of palladium chloride and 0.3mmol of aurichlorohydric
acid, reduce it with 0.09mol/L of formaldehyde solution for 5h at 10°C, obtain the
catalyst, which is denoted as the PdAu3/(Mxene-TiO2)1/35@g-C3N4 nanosheet
catalyst, and then store it in an airtight space.
[0032] The Reaction Process of Dehydrogenation
[0033] Place 50mg of the above catalyst into a jacketed reactor, control the reaction
to proceed at 40°C through a constant temperature circulation tank, irradiate the
reaction solution with visible light with a certain power wavelength (X > 400nm)
from the top of the jacketed reactor, and then add a 2.5g of mixture of formic acid
and sodium formate with a molar ratio of 1: 0.6, and collect the reaction gas. After
the reaction, the selectivity of hydrogen is 100%, the conversion rate of formic acid
is 100%, the TOF value of the reaction is 1360h-1, and the TOF value of the
reaction is still greater than 1352h-1 after recycling for 8h.
[0034] Embodiment 3
[0035] The Preparation Process of Catalyst
[0036] Grind and mix 3g of melamine and 21g of lithium chloride uniformly, calcinate for 6h at 540°C under nitrogen atmosphere, wash the calcined mixture
with water for 43h at 30°C, dry and obtain the g-C3N4 nanosheet; weigh lg of
Ti2AlC into 45wt% of HF solution, the treatment time is 4.5h, filter, wash with water, dry and obtain the Ti2C; place 0.1mmol of Ti2C and 2.5mmol of g-C3N4
nanosheets in a 40ml of deionized water, add NaHSO3, adjust the concentration of
NaHSO3 to 0.04mol/L, the hydrothermal synthesis temperature is 140°C, the hydrothermal synthesis time is 10h, and obtain the Mxene-TiO2)1/2@g-C3N4 nanosheet. Weigh 23mmol of (Mxene-TiO2)1/25@g-C3N4 nanosheet, place it in a solution containing Immol of palladium chloride and 0.2mmol of aurichlorohydric acid, reduce it with 0.05mol/L of formaldehyde solution for 6h at 25°C, obtain the catalyst, which is denoted as the PdAu2/(Mxene-TiO2)1/25@g-C3N4 nanosheet catalyst, and then store it in an airtight space.
[0037] The Reaction Process of Dehydrogenation
[0038] Place 50mg of the above catalyst into a jacketed reactor, control the reaction
to proceed at 30°C through a constant temperature circulation tank, irradiate the
reaction solution with visible light with a certain power wavelength (X > 400nm)
from the top of the jacketed reactor, and then add a 2.0g of mixture of formic acid
and sodium formate with a molar ratio of 1: 0.5, and collect the reaction gas. After
the reaction, the selectivity of hydrogen is 100%, the conversion rate of formic acid
is 100%, the TOF value of the reaction is 1130h-1, and the TOF value of the
reaction is still greater than 1122h-a fter recycling for 8h.
[0039] Embodiment 4
[0040] The Preparation Process of Catalyst
[0041] Grind and mix 3g of melamine and 18g of lithium chloride uniformly,
calcinate for 6h at 540°C under nitrogen atmosphere, wash the calcined mixture
with water for 43h at 30°C, dry and obtain the g-C3N4 nanosheet; weigh lg of
Ti2AlC into 45wt% of HF solution, the treatment time is 4.5h, filter, wash with
water, dry and obtain the Ti2C; place 0.1mmol of Ti2C and 3.mmol of g-C3N4
nanosheets in a 40ml of deionized water, add NaHSO3, adjust the concentration of
NaHSO3 to 0.03mol/L, the hydrothermal synthesis temperature is 130°C, the
hydrothermal synthesis time is 9h, and obtain the Mxene-TiO2)1/30@g-C3N4
nanosheet. Weigh 22mmol of (Mxene-TiO2)1/3o@g-C3N4 nanosheet, place it in a
solution containing Immol of palladium chloride and 0.25mmol of
aurichlorohydric acid, reduce it with 0.06mol/L of formaldehyde solution for 8h at
°C, obtain the catalyst, which is denoted as the
PdAuo25/(Mxene-TiO2)1/3@g-C3N4 nanosheet catalyst, and then store it in an
airtight space.
[0042] The Reaction Process of Dehydrogenation
[0043] Place 50mg of the above catalyst into a jacketed reactor, control the reaction
to proceed at 35°C through a constant temperature circulation tank, irradiate the
reaction solution with visible light with a certain power wavelength (X > 400nm)
from the top of the jacketed reactor, and then add a 2.3g of mixture of formic acid
and sodium formate with a molar ratio of 1: 0.4, and collect the reaction gas. After
the reaction, the selectivity of hydrogen is 100%, the conversion rate of formic acid
is 100%, the TOF value of the reaction is 1270h-1, and the TOF value of the
reaction is still greater than 1262h-1 after recycling for 8h.
[0044] Embodiment 5
[0045] The Preparation Process of Catalyst
[0046] Grind and mix 3g of melamine and 17g of lithium chloride uniformly,
calcinate for 5h at 530°C under nitrogen atmosphere, wash the calcined mixture
with water for 47h at 45°C, dry and obtain the g-C3N4 nanosheet; weigh lg of
Ti2AlC into 35wt% of HF solution, the treatment time is 5.5h, filter, wash with
water, dry and obtain the Ti2C; place 0.1mmol of Ti2C and 2.8mmol of g-C3N4
nanosheets in a 40ml of deionized water, add NaHSO3, adjust the concentration of
NaHSO3 to 0.04mol/L, the hydrothermal synthesis temperature is 150°C, the
hydrothermal synthesis time is 8h, and obtain the Mxene-TiO2)1/28@g-C3N4
nanosheet. Weigh 20mmol of (Mxene-TiO2)1/28@g-C3N4 nanosheet, place it in a
solution containing Immol of palladium chloride and 0.15mmol of
aurichlorohydric acid, reduce it with 0.09mol/L of formaldehyde solution for 8h at
°C, obtain the catalyst, which is denoted as the
PdAuol5/(Mxene-TiO2)1/28@g-C3N4 nanosheet catalyst, and then store it in an
airtight space.
[0047] The Reaction Process of Dehydrogenation
[0048] Place 50mg of the above catalyst into a jacketed reactor, control the reaction
to proceed at 25°C through a constant temperature circulation tank, irradiate the
reaction solution with visible light with a certain power wavelength (X > 400nm)
from the top of the jacketed reactor, and then add a 2.Og of mixture of formic acid
and sodium formate with a molar ratio of 1: 0.6, and collect the reaction gas. After
the reaction, the selectivity of hydrogen is 100%, the conversion rate of formic acid
is 100%, the TOF value of the reaction is 1194h-1, and the TOF value of the
reaction is still greater than 1185h-1 after recycling for 8h.
[0049] Embodiment 6
[0050] The Preparation Process of Catalyst
[0051] Grind and mix 3g of melamine and 22g of lithium chloride uniformly,
calcinate for 7h at 520°C under nitrogen atmosphere, wash the calcined mixture
with water for 40h at 45°C, dry and obtain the g-C3N4 nanosheet; weigh Ig of
Ti2AlC into 30wt% of HF solution, the treatment time is 6.0h, filter, wash with
water, dry and obtain the Ti2C; place 0.1mmol of Ti2C and 3.2mmol of g-C3N4
nanosheets in a 40ml of deionized water, add NaHSO3, adjust the concentration of
NaHSO3 to 0.05mol/L, the hydrothermal synthesis temperature is 130°C, the
hydrothermal synthesis time is 12h, and obtain the Mxene-TiO2)1/32@g-C3N4
nanosheet. Weigh 24mmol of (Mxene-TiO2)1/32@g-C3N4 nanosheet, place it in a
solution containing Immol of palladium chloride and 0.3mmol of aurichlorohydric
acid, reduce it with 0.08mol/L of formaldehyde solution for 7h at 15°C, obtain the
catalyst, which is denoted as the PdAu3/(Mxene-TiO2)1/32@g-C3N4 nanosheet
catalyst, and then store it in an airtight space.
[0052] The Reaction Process of Dehydrogenation
[0053] Place 50mg of the above catalyst into a jacketed reactor, control the reaction to proceed at 15°C through a constant temperature circulation tank, irradiate the reaction solution with visible light with a certain power wavelength (X > 400nm) from the top of the jacketed reactor, and then add a 1.8g of mixture of formic acid and sodium formate with a molar ratio of 1: 0.3, and collect the reaction gas. After the reaction, the selectivity of hydrogen is 100%, the conversion rate of formic acid is 100%, the TOF value of the reaction is 965h-1 , and the TOF value of the reaction is still greater than 987h-1 after recycling for 8h.
Claims (2)
- Claims 1. A method for catalyzing the dehydrogenation of formic acid with visible light with PdAu nanosheet catalyst, which is characterized in that: Place the PdAu nanosheet catalyst in a jacketed reactor, control the reaction to proceed at 10 40°C through a constant temperature circulation tank, irradiate the reaction solution with visible light with a wavelength of X>400nm from the top of the jacketed reactor, and then add a mixture of formic acid and sodium formate with a molar ratio of 1: (0.2~0.6) into the reactor for reaction, and finally obtain the product hydrogen; The mass ratio of the catalyst to the mixture of formic acid and sodium formate is 1: (30~50); The PdAu nanosheet catalyst comprises Pd, Au, Mxene-TiO2 and g-C3N4 nanosheet, of which, Pd is derived from palladium chloride, Au is derived from aurichlorohydric acid, Mxene-TiO2 is derived from Mxene-Ti2AlC, and g-C3N4 nanosheet is prepared by calcination of melamine and lithium chloride; The PdAu nanosheet catalyst is prepared by the following steps: (1) After calcinating the melamine and lithium chloride in a certain ratio under certain calcination conditions and atmosphere, then wash them with water for a period of time at a certain temperature, filter and obtain the g-C3N4 nanosheet; The mass ratio of melamine to lithium chloride is 1: (4~8), the calcination temperature is 520-55 0 °C, the calcination time is 4-7h, the atmosphere is nitrogen, the washing temperature is 20~45°C, and the washing time is 40~50h; (2) Take a certain amount of Ti2AlC, add it to a certain concentration of hydrofluoric acid solution, treat it for a period of time, freeze-dry and obtain the Ti2C; The mass concentration of HF is 30~50wt%, and the treatment time is 4.0~ 6.0h; (3) Place the Ti2C and g-C3N4 nanosheets in a hydrothermal synthesis reactor containing 40ml of deionized water at a certain molar ratio, add a certain concentration of NaHSO3 solution, ultrasonically disperse for a period of time, and place them at a certain temperature for hydrothermal synthesis for a period of time, after filtering and washing with water, freeze-dry and obtain the Mxene-TiO2@g-C3N4 nanosheet support; The molar ratio of Ti2C to g-C3N4 nanosheet is 1: (20 ~ 35), the concentration of NaHSO3 is 0.03 ~ 0.05mol/l, the hydrothermal synthesis temperature is 120-150°C, and the hydrothermal synthesis time is 8-12h;(4) Place the porous Mxene-TiO2@g-C3N4 nanosheet support obtained by freeze-drying in a certain composition of palladium chloride and aurichlorohydric acid solution, reduce it with formaldehyde solution for a period of time, centrifuge and dry, and then obtain the PdAu/Mxene-TiO2@ g-C3N4 nanosheet catalyst. The molar ratio of palladium chloride, aurichlorohydric acid to Mxene-TiO2@g-C3N4 nanosheet is 1: (0.1~0.3): (20~25), the concentration of formaldehyde is 0.05~0.09mol/L, the reduction temperature is 10~25°C, and the reduction time is 5~8h.
- 2. A method for catalyzing the dehydrogenation of formic acid with visible light with PdAu nanosheet catalyst as described in Claim 1, which is characterized in that: The mass ratio of melamine to lithium chloride is 1: 8, the calcination temperature is 550°C, the calcination time is 4h, the atmosphere is nitrogen, the washing temperature is 20°C, and the washing time is 50h; The mass concentration of HF is 50wt%, and the treatment time is 4.0h; The molar ratio of Ti2C to g-C3N4 nanosheet is 1: 35, the concentration of NaHSO3 is 0.05mol/, the hydrothermal synthesis temperature is 150°C, and the hydrothermal synthesis time is 8h; The molar ratio of palladium chloride, aurichlorohydric acid to Mxene-TiO2@g-C3N4 nanosheet is 1: 0.3: 25, the concentration of formaldehyde is 0.09mol/L, the reduction temperature is 10°C, and the reduction time is 5h; The mass ratio of the catalyst to the mixture of formic acid and sodium formate is 1: 50, and the reaction temperature is 40°C; the molar ratio of formic acid to sodium formate is 1:0.6.
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