CN113351210B - Cu-based catalyst and application thereof in photocatalytic water hydrogen production-5-HMF oxidation coupling reaction - Google Patents
Cu-based catalyst and application thereof in photocatalytic water hydrogen production-5-HMF oxidation coupling reaction Download PDFInfo
- Publication number
- CN113351210B CN113351210B CN202110684551.4A CN202110684551A CN113351210B CN 113351210 B CN113351210 B CN 113351210B CN 202110684551 A CN202110684551 A CN 202110684551A CN 113351210 B CN113351210 B CN 113351210B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- hmf
- hydrogen production
- based catalyst
- coalo
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 70
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 48
- 239000001257 hydrogen Substances 0.000 title claims abstract description 47
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 31
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 25
- 230000003647 oxidation Effects 0.000 title claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 19
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 claims abstract description 31
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- 229910016507 CuCo Inorganic materials 0.000 claims abstract description 6
- 239000011258 core-shell material Substances 0.000 claims abstract description 4
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 4
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 4
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 abstract description 9
- 239000002923 metal particle Substances 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 8
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 230000007935 neutral effect Effects 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 2
- 150000001768 cations Chemical class 0.000 abstract 1
- 238000010586 diagram Methods 0.000 description 8
- 238000005691 oxidative coupling reaction Methods 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000011941 photocatalyst Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 230000006872 improvement Effects 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- PXJJKVNIMAZHCB-UHFFFAOYSA-N 2,5-diformylfuran Chemical compound O=CC1=CC=C(C=O)O1 PXJJKVNIMAZHCB-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- -1 polyethylene furancarboxylate Polymers 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J35/396—Distribution of the active metal ingredient
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention provides a Cu-based catalyst and a method for using the Cu-based catalyst to carry out photocatalytic hydrogen production-5-HMF oxidation coupling reaction in water, wherein the chemical expression of the Cu-based catalyst is Cu/CoAlO, and the catalyst is prepared by using Cu 2+ 、Co 2+ And Al 3+ Hydrotalcite of a metal cation as precursor in H 2 /N 2 Or H 2 Roasting at 550-650 ℃ under the mixed atmosphere of/Ar to obtain the metal nano particles with a Co @ CuCo core-shell structure on the surface of the carrier by Cu and Co species, wherein the metal particles are uniformly distributed, and the average particle size of the metal particles is 2-10 nm; the valence band value VB = 1.7-2.0 eV, and the conduction band value CB is-0.8-1.0 eV. The catalyst is applied to the photocatalytic water hydrogen production-5-HMF oxidation coupling reaction under the condition of no additional alkali, not only improves the hydrogen production efficiency, but also realizes the efficient directional conversion from 5-hydroxymethylfurfural to 2, 5-furandicarboxylic acid under the neutral condition. The Cu-based catalyst has outstanding catalytic performance, simple preparation and environmental protection.
Description
Technical Field
The invention relates to the technical field of catalysis, in particular to a Cu-based catalyst and a method for preparing a high-added-value chemical by using the Cu-based catalyst in a photocatalytic water hydrogen production-5-HMF oxidation coupling reaction while improving the hydrogen production performance.
Background
With the rapid development of economy and the continuous improvement of the living standard of people, the demand on energy sources continuously increases. The development of clean, pollution-free, renewable, high energy density hydrogen energy is critical to solving current energy and environmental problems. The photocatalytic hydrogen production technology can utilize abundant and clean solar energy, and has the characteristics of environmental friendliness and low energy consumption, so that the photocatalytic hydrogen production technology is a hydrogen production mode with wide application prospect. In the traditional photocatalytic water splitting hydrogen production reaction, light excites electricityProton reduction to produce H 2 However, the oxidizing ability to excite holes is not fully utilized. Therefore, if a raw material (such as 5-HMF and its derivatives) which is abundant in source and is easily available is used to capture excited holes, and the photocatalytic hydrogen production from water and the oxidation reaction of 5-HMF are coupled, the improvement of the hydrogen production efficiency is promoted, and meanwhile, a downstream product with a high added value is obtained, so that the solar energy utilization efficiency can be effectively promoted, and the high-value conversion of renewable resources can be realized. In recent years, to alleviate the current energy crisis, there has been increasing interest in converting renewable 5-HMF resources to value-added chemicals. Through C 6 5-hydroxymethylfurfural (5-HMF) produced by dehydration of carbohydrates is classified as one of the 12 largest sustainable 5-HMF value-added chemicals by the U.S. department of energy, and its downstream product, 2, 5-furandicarboxylic acid (FDCA), is considered as an important monomer substitute for synthetic polymers, particularly polyethylene furancarboxylate (PEF), which is considered as a potential substitute for the polymer polyethylene terephthalate.
Reference 2Chen et al in P-dotted Zn x Cd 1-x P-doped Zn with S-rich vacancies is prepared in S-soluble vacancies for hydrogen evolution from water splitting with a phosphorus oxidation of 5-hydroxymethyiful, applied Catalysis B, environmental 233 (2018) 70-79 x Cd 1-x S(Zn x Cd 1-x S-P) is used as photocatalyst and is simultaneously used for hydrogen production and photocatalysis by water decompositionAnd (3) chemically oxidizing 5-HMF. After 8h of reaction, the selectivity of DFF in the product of 5-hydroxymethylfurfural conversion is 65%, and the maximum hydrogen production rate is 786 mu mol g -1 ·h -1 。
In the published literature of photocatalytic hydrohydrogen-5-hydroxymethylfurfural oxidative coupling, it can be found that under neutral conditions, the oxidation product of 5-HMF is substantially 2, 5-Diformylfuran (DFF). Only under strongly alkaline conditions will the aldehyde group be rapidly converted to 2, 5-furandicarboxylic acid (FDCA) due to its instability at high pH. Although the addition of an alkaline solution to the reaction system can improve the selectivity to FDCA, it does not meet the trend of green chemistry and is liable to cause corrosion of equipment. Therefore, the design and synthesis of the environment-friendly photocatalyst with high selectivity on FDCA in the coupling reaction under the non-strong alkaline condition has important significance.
In the document 3Feng et al, in Interfacial Structure-defined Reaction Pathway and selection for5- (Hydroxymethyl) furfull Hydrogenation Cu-Based catalysts ACS Cat. 2020,10,1353-1365, precursors such as CuMgAl-LDH and CuCoAl-LDH were synthesized by coprecipitation method, and the LDH precursor was adjusted to 10H 2 And reducing the mixture for 4 hours at the high temperature of 300 ℃ under the Ar atmosphere to prepare the Cu-based catalyst for the hydrogenation reaction of 5-hydroxymethylfurfural.
Document 4Zhao et al, in Layered Double Hydroxide Nanostructured pollutants for recycled Energy production, advanced Energy Materials,2016 (6): 1501974, demonstrate that Layered Double Hydroxides (LDHs), as typical two-dimensional Layered Materials, show great application prospects in the field of photocatalysis due to their excellent electronic properties and ability of fast transport of photo-generated electron-hole pairs. Based on the adjustability of the composition, specific photosensitive metal ions are introduced into the laminate, so that the energy band structure of the laminate can be adjusted and controlled. The coupling reaction has a great development prospect in the field of photocatalytic hydrogen production, and few reports are provided in the emerging field for preparing a photocatalytic material by using LDH. Therefore, LDH provides a strong structural platform for developing photocatalysts with high activity suitable for photocatalytic coupling reactions.
Therefore, our inventive idea is: with LDHs is a platform, and photosensitive ions Cu are added based on the topological effect and the composition adjustability 2+ And the hydrotalcite laminate is introduced to design and synthesize a photocatalyst which has strong photoresponse capability and high activity and is suitable for photocatalytic hydrogen-production-5-HMF oxidation coupling reaction, and the catalytic performance is enhanced under the condition of no additional alkali.
Disclosure of Invention
The invention aims to provide a Cu-based catalyst which is specially used for photocatalytic hydrogen production-5-HMF oxidation coupling reaction in water.
The chemical expression of the Cu-based catalyst is Cu/CoAlO, wherein the molar ratio of Cu to Co is 1-3 to 1, and the molar ratio of Co to Al is 1.5-2.5; the catalyst is structurally characterized in that Cu and Co species form metal nano particles with a Co @ CuCo core-shell structure on the surface of a carrier, the metal particles are uniformly distributed, and the average particle size of the metal particles is 2-10 nm; the valence band value VB = 1.7-2.0 eV, and the conduction band value CB is-0.8-1.0 eV.
The Cu/CoAlO catalyst is specially used for photocatalytic water hydrogen production-5-HMF oxidation coupling reaction, and the highest hydrogen production rate can reach 796.8-888.3 mu molh after 6h of reaction without adding alkali -1 g -1 The FDCA selectivity can reach 93.7-95.5%, which is much higher than the performances reported in the literature. The catalyst promotes the improvement of the hydrogen production efficiency and simultaneously realizes the efficient directional conversion from 5-HMF to FDCA under the neutral condition.
The Cu/CoAlO catalyst is prepared from Cu 2+ 、Co 2+ And Al 3+ Hydrotalcite of metal ions as precursor in H 2 /N 2 Or H 2 The catalyst is obtained by roasting at 550-650 ℃ in the mixed atmosphere of/Ar.
The specific application steps of the Cu/CoAlO catalyst are as follows:
adding reactants of 5-HMF, cu/CoAlO and deionized water into a sealable reactor, wherein the mass ratio of the 5-HMF to the Cu/CoAlO is 2-6, and the mass concentration of the 5-HMF is 1.0-3.3 g/L; fully replacing the air in the reaction flask with high-purity Ar under magnetic stirring, irradiating the reaction solution by using a 300W Xe lamp (lambda is more than 380 nm), and reacting for 1-8 h under full stirring to obtain the FDCA product.
The photocatalytic hydrogen production with water-5-HMF oxidation coupling reaction path is as follows:
as the Cu-based catalyst has proper valence band and conduction band position, the conduction band position meets the thermodynamic requirement of reducing H protons into hydrogen, and the valence band position meets VB (visual basic) values required by oxygen production and VB values required by 5-HMF oxidation. Thus, in the absence of added base, the excited holes oxidize 5-HMF to DFF while oxidizing water to O 2 Oxygen from the oxidation of water further rapidly oxidizes DFF to FDCA.
FIG. 1 is a HRTEM photograph and a particle size distribution chart of a Cu/CoAlO catalyst prepared in example 1 and having a Cu/Co molar ratio of 1/5, from which it can be seen that metal particles are uniformly distributed on the support, the size of the nanoparticles is in the range of 2.0 to 10.0nm, and the average size of the particles is 5.8nm.
FIG. 2 is the results of line scanning of metal particles of Cu and Co by X-ray energy spectrum (EDS) in Cu/CoAlO catalyst with Cu/Co molar ratio of 1/5 prepared in example 1, and comparing the distribution of elements Co and Cu, it can be seen that Co is distributed in the whole metal particles and Cu is concentrated on the surface of the metal particles, therefore, it can be determined that the metal nanoparticles as the active component of the catalyst present a core-shell structure of Co @ CuCo.
FIG. 3 is an XPS valence band diagram and a Tauc diagram of a Cu/CoAlO catalyst prepared in example 1 and having a Cu/Co molar ratio of 1/5, and it can be seen from the valence band diagram of (a) that the Valence Band (VB) value of the catalyst is 1.73eV, and from the Tauc diagram of (b) that the energy band gap (Eg) of the catalyst is 2.67eV.
FIG. 4 is a diagram showing the structure of the energy band of the Cu/CoAlO catalyst prepared in example 1 and having a Cu/Co molar ratio of 1/5, and it can be seen that the CB value of the catalyst is lower than the reduction potential (0 eV) of the H protons, and under the irradiation of a light source with a proper wavelength, the thermodynamic requirement for reducing the H protons into hydrogen gas can be satisfied. Furthermore, due to CuCo/Al 2 O 3 Has proper valence band position, meets the VB value (1.23 eV) required by oxygen generation and also reaches the value5-VB value (0.82 eV) required for HMF oxidation. Thus, the cavities can either oxidize 5-HMF to DFF or oxidize water to produce O 2 Oxygen from subsequent oxidation of water can also further rapidly oxidize DFF to FDCA.
FIG. 5 is a line graph showing the change of hydrogen production with time of the Cu/CoAlO catalyst with the Cu/Co molar ratio of 1/5 prepared in example 1 in the photocatalytic hydrohydrogenesis-5-HMF oxidative coupling reaction, wherein the hydrogen production of the catalyst is gradually increased along with the extension of the reaction time within 6h, and the highest hydrogen production rate can reach 888.3 mu molh -1 g -1 The hydrogen production after 6 hours was 9.78. Mu. Mol.
FIG. 6 is an HPLC chromatogram of the reaction solution of the Cu/CoAlO catalyst with a Cu/Co molar ratio of 1/5 prepared in example 1 in the photocatalytic hydrohydrogenesis-5-HMF oxidative coupling reaction, and it can be seen from the chart that the peak position of 5-HMF is 2.8min, the peak position of 2, 5-furandicarboxylic acid (FDCA) is 2min, only FDCA, 5-HMF and trace DFF are detected in the liquid-phase product after 6h of reaction, and no other product is detected, which indicates that the coupling reaction has high selectivity to FDCA.
FIG. 7 is a graph of FDCA concentration over time, 5-HMF conversion and FDCA selectivity for the photocatalytic hydrohydrogenesis-5-HMF oxidative coupling reaction for the Cu/CoAlO catalyst with a Cu/Co molar ratio of 1/5 prepared in example 1. When reacted for 6h, the conversion of 5-HMF was 11.2% and the selectivity of FDCA was 95.5%.
The beneficial effects of the invention are: the application of the supported Cu-based catalyst obtained based on LDHs precursor topological reduction in the photocatalytic water hydrogen production-5-HMF oxidation coupling reaction is found for the first time, so that the improvement of the hydrogen production efficiency can be promoted, and the efficient directional conversion from 5-HMF to FDCA under a neutral condition can be realized. The Cu-based catalyst has outstanding catalytic performance, simple preparation and environmental protection.
Description of the drawings:
fig. 1 is an HRTEM photograph and a particle size distribution diagram of the catalyst prepared in example 1, in which fig. a is an HRTEM photograph of the catalyst, and fig. b is a size distribution diagram of metal nanoparticles.
FIG. 2 is a line scan of the metal particles of Co and Cu of the catalyst prepared in example 1.
Fig. 3 is an XPS valence band spectrum and a Tauc chart of the catalyst prepared in example 1, in which a is the valence band spectrum and b is the Tauc chart.
FIG. 4 is a diagram showing the structure of the energy band of the catalyst prepared in example 1.
FIG. 5 is a graph showing the variation of hydrogen production with time in the photocatalytic hydrohydrogenesis-5-HMF oxidative coupling reaction of the catalyst prepared in example 1.
Fig. 6 is an HPLC chromatogram of the reaction solution of the catalyst prepared in example 1 in the photocatalytic hydrogen production-5-HMF oxidative coupling reaction, wherein a is an HPLC chromatogram before the reaction, and b is an HPLC chromatogram after 6h of the reaction.
FIG. 7 is a graph of the concentration of FDCA, the conversion of 5-HMF and the selectivity of FDCA in the photocatalytic hydrohydrogen-5-HMF oxidative coupling reaction of the catalyst prepared in example 1 as a function of time. Wherein graph a is the concentration of product FDCA versus time and graph b is the conversion of 5-HMF and FDCA selectivity curve.
The specific implementation mode is as follows:
example 1
With soluble nitrates (Cu (NO) 3 ) 2 ·3H 2 O、Al(NO 3 ) 3 ·9H 2 O and Co (NO) 3 ) 2 ·6H 2 O) as a metal salt, cu 2+ 、Co 2+ With Al 3+ Adding an alkali solution into a mixed salt solution with a metal molar ratio of 1 3 2- -LDHs hydrotalcite-like precursor. The obtained precursor was placed in a tube furnace with a hydrogen volume fraction of 10% H 2 /N 2 Keeping the air flow rate at 30mL/min under the atmosphere, raising the temperature of the tube furnace to 600 ℃ at the temperature raising rate of 2 ℃/min and keeping the constant temperature for 4h. After the reaction is finished, in order to avoid the oxidation of the catalyst, the furnace temperature is naturally cooled to room temperature to obtain the Cu/CoAlO catalyst, wherein the Cu/Co molar ratio is 1/5, and the mass percentages of Cu, co and Al elements are respectively 8.3%, 42.7% and 7.8%. The obtained sample was characterized, and the results are shown in FIGS. 1 to 4, from which it can be seen that the catalyst metal nanoparticles exhibit the characteristics of Co @ CuCo alloyCore-shell structure, and metal nanoparticles are uniformly dispersed in amorphous Al 2 O 3 On the support, the average size of the nanoparticles was 5.8nm. The Valence Band (VB) value of the catalyst is 1.73eV, the Conduction Band (CB) value is-0.94 eV, the conduction band value meets the thermodynamic requirement of reducing H protons into hydrogen, and the valence band value meets the VB value (1.23 eV) required by oxygen generation and the VB value (0.82 eV) required by 5-HMF oxidation.
The obtained catalyst is used for the photocatalytic water hydrogen production-5-HMF oxidation coupling reaction, and the specific method comprises the following steps: in a sealable reactor with a volume of 20mL, 5mg of catalyst and 13mg of 5-hydroxymethylfurfural were added, 10mL of purified water was added, and the reactor was sealed with a capping device. The air in the reaction flask was replaced with high purity Ar for 30min under magnetic stirring, and then a 300W Xe lamp (x: (n))>380 nm), keeping the distance between the lamp and the reaction flask to be about 5cm, controlling the lamp current intensity to be 16A, irradiating the reaction solution, setting the magnetic stirring speed to be 600rpm, and controlling the reaction time to be 6h. Sampling at the reaction time of 1,2,3,4,5,6h, detecting the concentration and content of the gas phase product by gas chromatography, and analyzing the distribution and content of the liquid phase product by high performance liquid chromatography. The results are shown in Table 1, and it can be seen from Table 1 that after 6h of reaction, the FDCA selectivity of the catalyst is 95.5% under the condition of no additional alkali, the hydrogen production after 6h is 9.78 mu mol, and the maximum hydrogen production rate can reach 888.3 mu mol h -1 g -1 。
Example 2
A Cu/coao catalyst was prepared according to the method of example 1, except that the metal molar ratio of Cu, co and Al in the mixed salt solution was 1.
The catalyst obtained by the method of example 1 is used for the photocatalytic water hydrogen production-5-HMF oxidation coupling reaction, the result is shown in Table 1, and the results shown in Table 1 show that after the reaction for 6 hours, the FDCA selectivity of the catalyst under the condition of no external alkali is 94.3 percent, the hydrogen production after 6 hours is 8.03 mu mol, and the maximum hydrogen production rate can reach 798.0 mu mol h -1 g -1 。
Example 3
A Cu/coao catalyst was prepared according to the method of example 1, except that the metal molar ratio of Cu, co and Al in the mixed salt solution was 1; the mass percentage contents of Cu, co and Al elements in the obtained catalyst are respectively 10.8%, 33.7% and 10.4%.
The catalyst obtained by the method of example 1 is used in the photocatalytic water hydrogen production-5-HMF oxidation coupling reaction, the result is shown in Table 1, and the results in Table 1 show that after the reaction for 6 hours, the FDCA selectivity of the catalyst under the condition of no extra alkali is 94.5%, the hydrogen production after 6 hours is 7.4 mu mol, and the maximum hydrogen production rate can reach 796.8 mu mol h -1 g -1 。
TABLE 1
Wherein, the comparative example 1 and the comparative example 2 are both literature values of photocatalytic hydrogen-in-water-production-5-HMF oxidation coupling reaction. Comparative example 1 is the hydrogen production amount of the Ni/CdS NSs catalyst in document 1 after 6 hours of reaction and the DFF selectivity after 22 hours of reaction, but the DFF is rapidly converted into FDCA after the catalyst is added with a strong base in the reaction system. Comparative example 2 is Zn in document 2 x Cd 1-x Performance of the S-P catalyst after 8h of reaction.
As shown in Table 1, the selectivity of the catalyst of the invention to 2, 5-furandicarboxylic acid (FDCA) under the condition without external alkali is higher than that of the comparative example, and the high-efficiency directional conversion of 5-hydroxymethylfurfural (5-HMF) to 2, 5-furandicarboxylic acid (FDCA) under the neutral condition is realized.
Claims (2)
1. The application of the Cu-based catalyst is characterized in that the catalyst is used for photocatalytic hydrogen production with water-5-HMF oxidation coupling reaction; wherein 5-HMF represents 5-hydroxymethylfurfural; the chemical expression of the Cu-based catalyst is Cu/CoAlO, wherein the molar ratio of Cu to Co is 1-3 to 1; the catalyst has structural characteristics of Cu andthe Co species form metal nano particles with a Co @ CuCo core-shell structure on the surface of the carrier, the particles are uniformly distributed, and the average particle size of the metal nano particles is 2-10 nm; the valence band value VB = 1.7-2.0 eV, and the conduction band value CB is-0.8-1.0 eV; the Cu/CoAlO catalyst is prepared from Cu 2+ 、Co 2+ And Al 3+ Hydrotalcite of metal ions as precursor in H 2 /N 2 Or H 2 The catalyst is obtained by roasting at 550-650 ℃ in the mixed atmosphere of/Ar.
2. The use of the Cu-based catalyst according to claim 1, comprising the steps of: adding reactants of 5-HMF, cu/CoAlO and deionized water into a sealable reactor, wherein the mass ratio of the 5-HMF to the Cu/CoAlO is 2-6, and the mass concentration of the 5-HMF is 1.0-3.3 g/L; under the magnetic stirring, fully replacing the air in the reactor with high-purity Ar, irradiating the reaction solution with a 300W Xe lamp, and reacting for 1-8 h under the full stirring to obtain a 2, 5-furandicarboxylic acid product; the reaction is characterized by being carried out under the condition of no additional alkali.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110684551.4A CN113351210B (en) | 2021-06-21 | 2021-06-21 | Cu-based catalyst and application thereof in photocatalytic water hydrogen production-5-HMF oxidation coupling reaction |
| PCT/CN2022/099795 WO2022268021A1 (en) | 2021-06-21 | 2022-06-20 | Cu-based catalyst and use thereof for photocatalytic water-based hydrogen production-5-hydroxymethylfurfural (hmf) oxidation coupling reaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110684551.4A CN113351210B (en) | 2021-06-21 | 2021-06-21 | Cu-based catalyst and application thereof in photocatalytic water hydrogen production-5-HMF oxidation coupling reaction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113351210A CN113351210A (en) | 2021-09-07 |
| CN113351210B true CN113351210B (en) | 2023-02-28 |
Family
ID=77535187
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110684551.4A Active CN113351210B (en) | 2021-06-21 | 2021-06-21 | Cu-based catalyst and application thereof in photocatalytic water hydrogen production-5-HMF oxidation coupling reaction |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN113351210B (en) |
| WO (1) | WO2022268021A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113351210B (en) * | 2021-06-21 | 2023-02-28 | 北京化工大学 | Cu-based catalyst and application thereof in photocatalytic water hydrogen production-5-HMF oxidation coupling reaction |
| CN113698373B (en) * | 2021-09-09 | 2024-03-08 | 昆明理工大学 | Method for preparing 2, 5-furandicarboxylic acid by high-efficiency photocatalytic oxidation |
| CN116173956A (en) * | 2023-01-05 | 2023-05-30 | 北京化工大学 | CO 2 Capturing coupling hydrogen production process, laminate adsorption catalyst used in capturing coupling hydrogen production process and preparation method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105854883A (en) * | 2016-05-17 | 2016-08-17 | 北京化工大学 | Co-based composite metal oxide catalyst and application |
| CN106279080A (en) * | 2016-08-03 | 2017-01-04 | 天津工业大学 | A kind of method that 2,5 furandicarboxylic acids are prepared in 5 Hydroxymethylfurfural photocatalysis |
| CN109796428A (en) * | 2019-03-28 | 2019-05-24 | 北京化工大学 | A kind of copper-based catalysts add the application in hydrogen in 5 hydroxymethyl furfural |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7700788B2 (en) * | 2006-10-31 | 2010-04-20 | Battelle Memorial Institute | Hydroxymethyl furfural oxidation methods |
| US20180023199A1 (en) * | 2016-07-19 | 2018-01-25 | Utah State University | Electrocatalytic hydrogen evolution and biomass upgrading |
| CN111377890B (en) * | 2018-12-28 | 2022-10-11 | 中国石油化工股份有限公司 | Method for producing 2,5-furandicarboxylic acid from 5-hydroxymethylfurfural |
| CN113351210B (en) * | 2021-06-21 | 2023-02-28 | 北京化工大学 | Cu-based catalyst and application thereof in photocatalytic water hydrogen production-5-HMF oxidation coupling reaction |
-
2021
- 2021-06-21 CN CN202110684551.4A patent/CN113351210B/en active Active
-
2022
- 2022-06-20 WO PCT/CN2022/099795 patent/WO2022268021A1/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105854883A (en) * | 2016-05-17 | 2016-08-17 | 北京化工大学 | Co-based composite metal oxide catalyst and application |
| CN106279080A (en) * | 2016-08-03 | 2017-01-04 | 天津工业大学 | A kind of method that 2,5 furandicarboxylic acids are prepared in 5 Hydroxymethylfurfural photocatalysis |
| CN109796428A (en) * | 2019-03-28 | 2019-05-24 | 北京化工大学 | A kind of copper-based catalysts add the application in hydrogen in 5 hydroxymethyl furfural |
Non-Patent Citations (1)
| Title |
|---|
| Interfacial structure-determined reaction pathway and selectivity for 5-(hydroxymethyl) furfural hydrogenation over Cu-based catalysts;Qian Wang,et al;《ACS Catalysis》;20191112;第10卷(第2期);文章摘要，第1355页第2节，第1356页第3节 * |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2022268021A1 (en) | 2022-12-29 |
| CN113351210A (en) | 2021-09-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113351210B (en) | Cu-based catalyst and application thereof in photocatalytic water hydrogen production-5-HMF oxidation coupling reaction | |
| Bi et al. | Research progress on photocatalytic reduction of CO 2 based on LDH materials | |
| CN113634258B (en) | Catalyst for generating ethylene by photocatalytic reduction of carbon dioxide and preparation method thereof | |
| CN113058617B (en) | Photocatalyst and preparation method and application thereof | |
| CN113145138B (en) | Thermal response type composite photocatalyst and preparation method and application thereof | |
| CN102080262A (en) | Visible light catalytic material, and preparation method and application thereof | |
| CN111203231A (en) | Indium zinc sulfide/bismuth vanadate composite material and preparation method and application thereof | |
| CN110013862B (en) | Direct Z-scheme photocatalyst of iron oxyhydroxide/cadmium sulfide nanobelt and preparation method thereof | |
| CN111701601A (en) | Bi4O5Br2Preparation method of self-assembled hollow flower ball and photocatalytic reduction of CO2Application of aspects | |
| CN116139867A (en) | MOFs derived ZnO@CDs@Co 3 O 4 Composite photocatalyst, preparation method and application thereof | |
| CN114768843A (en) | CO (carbon monoxide)2Photocatalyst for reduction-biomass oxidation coupling reaction and preparation method thereof | |
| CN112717958B (en) | Oxygen-rich vacancy BiOBr/HNb3O8Preparation method and application of nanosheet photocatalyst | |
| CN115920929B (en) | MoO3-x/Cu0.5Cd0.5S composite photocatalyst, preparation method and application | |
| CN116726973A (en) | Flower-ball-shaped sulfur indium zinc/carbon nitride heterojunction photocatalyst, and preparation method and application thereof | |
| CN116603541A (en) | Preparation method of photocatalyst for producing ethylene by reducing carbon dioxide | |
| CN113150291A (en) | Glucose modified bimetallic zeolite imidazole ester framework derivative catalyst and preparation method thereof | |
| CN114534746B (en) | Photocatalytic hydrogen production system based on heterojunction photocatalyst and formaldehyde aqueous solution | |
| CN114931949B (en) | Photocatalyst for carbon dioxide reduction and preparation method and application thereof | |
| CN113828331A (en) | Potassium titanate-heptacopper tetrasulfide composite material and preparation method and application thereof | |
| CN114762829A (en) | Simple preparation method of Z-type heterojunction photocatalytic material | |
| CN110756207A (en) | Fe/CN-H nano composite material and preparation method and application thereof | |
| CN116371425B (en) | CdS-Vs/Co rich in sulfur vacancies 2 RuS 6 Preparation and application of composite catalyst | |
| CN113368864B (en) | W-containing photocatalytic hydrogen production catalyst and preparation method thereof | |
| CN114100682B (en) | Lupin She Yizhi junction photocatalyst and preparation method thereof | |
| CN115254146B (en) | P-n junction type trimanganese tetroxide-cadmium sulfide nano composite photocatalyst and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |