CN114768843A - CO (carbon monoxide)2Photocatalyst for reduction-biomass oxidation coupling reaction and preparation method thereof - Google Patents
CO (carbon monoxide)2Photocatalyst for reduction-biomass oxidation coupling reaction and preparation method thereof Download PDFInfo
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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
- B01J27/232—Carbonates
- B01J27/236—Hydroxy carbonates
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- 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
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- 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
- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
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- 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
- C07D307/38—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 substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
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Abstract
The invention provides a CO2The invention discloses a photocatalyst for reduction-biomass oxidation coupling reaction and a preparation method thereof3 2‑. The photocatalyst can be used for photocatalysis of CO2More electrons (e) can be generated in the reduction-biomass oxidation coupling reaction‑) And cavity (h)+) Respectively participate in CO2Reduction half reaction with biomass oxygenIn the chemical half reaction, simultaneously pre-enriched CO between LDH laminates3 2‑The progress of the reduction half reaction is promoted, and therefore the catalyst exhibits excellent catalytic performance.
Description
Technical Field
The invention belongs to CO2The fields of comprehensive utilization and photocatalyst preparation, in particularRelates to a preparation method and application of a composite LDH/N photocatalyst, and the photocatalyst can be used for photocatalysis of CO2Reduction and biomass oxidation are coupled with the reaction process.
Background
Over the last half century, the rapid growth of the population, the dramatic advances in industrial technology, and the over-exploitation and burning of fossil fuels have led to the generation of CO2The emission of the main greenhouse gases is greatly increased, so that the problem of energy crisis caused by the main greenhouse gases is more and more serious, and the survival and sustainable development of human beings are seriously threatened. In this context, CO is photocatalyzed2The reduction technology is widely concerned and researched, and can realize CO under the drive of light2The conversion to a series of products with high added value, such as CO, hydrocarbon, liquid fuel, and the like. Compared with thermal catalysis and electrocatalysis, the photocatalysis uses solar energy with rich and renewable reserves to drive reaction, has the advantages of energy conservation, environmental protection and low operation cost, and is CO with very promising prospect2An emission reduction and utilization method.
Layered double metal Hydroxides (LDH) are used as an important Layered material, and the interlayer pair of the Layered double metal Hydroxides (LDH) is towards CO3 2-Has extremely strong chemical affinity, which makes it possible to use CO in solution or air3 2-Form of capturing and storing CO2Effecting the reaction on CO in a photocatalytic reaction2Utilization and transformation of (1). In addition, in order to further improve the utilization value of the photoproduction electron-hole, researchers replace pure water oxidation with alcohol substances which are more favorable in thermodynamics, and obtain an oxidation product with a higher added value by synergistically utilizing the oxidation capacity of the photoproduction hole while improving the efficiency of the photocatalytic reaction. In patent 1CN202111582145.3, LDH of various carbonate intercalation is synthesized, and reduction of a half-reaction substrate CO is realized2And make the catalyst realize photocatalytic CO2The coupling reaction process of in-situ reduction and biomass oxidation.
Due to the advantages of wide distribution, high added value of products and the like, the alcohol biomass platform compound has attracted wide attention in recent years, so that CO is used for preparing the alcohol biomass platform compound2Coupling reduction with alcohol biomass oxidation processNot only can accelerate photocatalysis CO2The efficiency of the reduction reaction can also be improved, and oxidation products with higher added values can be obtained. However, as for the single LDH as a photocatalyst, the photoresponse and the photo-generated electron-hole separation capability are relatively poor, and further improvement of the coupling reaction efficiency is limited.
In order to further improve the efficiency of the LDH material in the photocatalytic coupling reaction, the metal oxide semiconductor photocatalytic material with excellent photoresponse capability and photo-generated electron capture capability is selected to be compounded with the LDH, so that the compounded LDH photocatalytic material has stronger photo-generated electron-hole separation efficiency and photo-response capability and has excellent catalytic performance in the photocatalytic reaction. Document 1 In Situ Growth of ZnIn2S4on MOF-Derived Ni-Fe LDH to structural Terminary-Shelled Nanotubes for Efficient Photocatalytic Hydrogen evolution, Inorg, chem, 2021,60,13, 9762-9772. NiFe-LDH is grown in situ on ZnIn by self-assembly2S4On the nano-sheet, the ZIS @ NiFe-LDH composite photocatalyst is obtained, compared with NiFe-LDH, the photoresponse capability and the photo-generated electron-hole separation capability of the composite photocatalyst are remarkably improved, and the catalyst shows good catalytic activity in the photocatalytic hydrogen evolution reaction under the drive of light.
Use of LDH composites for photocatalytic reduction of CO2The reaction has also been studied extensively, and document 2 is In the publication of the beta-In2S3/NiAl-LDH heterojunction photocatalyst with enhanced separation of charge carriers for efficient CO2In Photocatalytic reduction. appl. surf. Sci.2020.527.146792, In was synthesized2S3Application of NiAl-LDH photocatalyst in photocatalysis of CO2In the reduction reaction, the compounded photocatalyst has stronger photoresponse and photoproduction electron hole separation capability, and can catalyze CO in photocatalysis2The catalyst shows good catalytic performance in the reaction.
Document 3 discloses a Coupling effect biological updating with H2 production via bifunctional CuxS @ NiCo-LDH core-shell nanoarray electrolytes.J.Mater.chem.A, 2020,8,1138-1146uxThe S @ NiCo-LDH is used for the electrocatalytic oxidation reaction of an alcohol biomass compound 5-hydroxymethylfurfural (5-HMF). Therefore, the LDH/N composite material can be applied to biomass oxidation reaction.
LDH is taken as an anionic layered compound, and research shows that LDH is opposite to CO in a plurality of anions3 2-The highest affinity makes it possible to use CO in solution or in air3 2-Form of capturing and storing CO2Using this property of LDH to interlayer CO3 2-As a carbon source for photocatalytic reaction, the method can realize the reaction on CO in the environment2In situ capture and transformation. In addition, the metal oxide semiconductor photocatalytic material with excellent photoresponse and photo-generated electron capture capacity is compounded with LDH, so that the obtained composite LDH/N photocatalyst has stronger photoresponse and photo-generated electron-hole separation capacity, and metal ions and hydroxyl groups rich in the LDH/N photocatalyst can be respectively used as CO2The site of occurrence of the in situ reduction and biomass oxidation reactions. Therefore, on the basis, by further selecting proper laminated metal ions and photocatalytic semiconductor materials, the photocatalytic CO can be effectively improved2The efficiency of the in-situ reduction and alcohol biomass oxidation coupling reaction.
The invention aims to compound LDH with metal oxide with excellent photoresponse capability and photo-generated electron capture capability to prepare the compound LDH/N photocatalyst, so that the compound LDH/N photocatalyst has excellent catalytic activity in a photocatalytic coupling reaction.
Disclosure of Invention
It is an object of the present invention to provide CO2A photocatalyst for reduction-biomass oxidation coupling reaction and a preparation method thereof.
The photocatalyst provided by the invention has a chemical expression formula as follows: LDH/N, wherein N is metal oxide, N is attached to the surface of LDH, and N is TiO2、Cu2O、CeO2、NiO、ZnO、ZrO2Of these, preferably: TiO 22And ZrO2(ii) a LDH is a layered double hydroxide represented by the formula: [ M ] A1-x 2+Mx 3+(OH)2]x+(CO3 2-)x/n·mH2O, wherein M2+Is Mg2+、Co2+、Zn2+、Mn2 +、Ni2+、Cu2+Is preferably: mg (Mg)2+、Co2+、Ni2+；M3+Is Al3+、Fe3+、Cr3+、Ce3+、In3+、Ga3+Is preferably: al (Al)3+、Fe3+、Cr3+；M2+And M3+The molar ratio of (a) to (b) is 2-4: 1; LDH interlaminar CO enrichment3 2-(ii) a Wherein the mass ratio of N to LDH is 0.25-3, preferably 0.5-1.5; n is an oxide having excellent photoresponsive ability and photogenerated electron capturing ability.
The preparation method of the photocatalyst comprises the following specific preparation steps:
A. dissolving the soluble M2+Salts and M3+Dissolving salt in deionized water to prepare solution A, wherein M2+The molar concentration of (b) is 0.05-0.35mol/L, M2+：M3+The molar ratio of (A) to (B) is 2-4: 1; the anion in the solution is CO3 2-；
Said M2+Is Mg2+、Co2+、Zn2+、Mn2+、Ni2+、Cu2+One of (a) and (b); among them, preferred is Mg2+、Co2+、Ni2+One of them; m is a group of3+Is Al3+、Fe3+、Cr3+、Ce3+、In3+、Ga3+One of (a) and (b); among them, preferred is Al3+、Fe3+、Cr3+One of them.
B. Adding metal oxide N powder and urea into deionized water with the volume equal to that of the solution A, and fully stirring to prepare suspension B with the volume equal to that of the solution A, wherein the concentration of the urea is 0.2-2mol/L, and the mass concentration of N is 6.0-40 g/; specifically, the mass ratio of N to LDH in the target catalyst is determined;
the N is TiO2、Cu2O、CeO2、NiO、ZnO、ZrO2Of (2), preferably TiO2Or ZrO2。
C. Adding the solution A and the suspension B with equal volumes into a reactor at the same time, and dispersing under the conditions of violent stirring and ultrasound until solid powder is uniformly dispersed in the solution to obtain suspension; centrifugally separating out solids, aging in an oven at 80-150 ℃ for 8-48h, and washing to neutrality; drying at 50-80 deg.C or low temperature under vacuum for 12-24 hr, grinding into powder to obtain target photocatalyst represented as LDH/N, wherein the formula of LDH is [ M [ ]1-x 2+Mx 3+(OH)2]x+(CO3 2-)x/n·mH2O。
The photocatalyst is characterized in that: in the LDH/N photocatalyst, metal oxide N is attached to the surface of LDH, and the photocatalyst can generate more electrons (e) in the coupling reaction process under the excitation of light-) And a cavity (h)+) Respectively participate in CO2Reduction half reaction and biomass oxidation half reaction. Simultaneous LDH interlayer pairing with CO3 2-Has strong affinity, and makes the interlayer rich in CO3 2-Pre-enriched CO3 2-And the reaction substrate as the reduction end participates in the coupling reaction to promote the reduction half reaction. Therefore, the photocatalyst can be used for catalyzing CO2Excellent catalytic activity can be shown in reduction-biomass oxidation coupling reaction.
The photocatalyst LDH/N is applied to CO2The reduction-biomass oxidation coupling reaction has the following reaction equation:
oxidation half reaction: R-CH2OH (Biomass molecule) +2h+R-CH ═ O (biomass molecule) +2H+
Reduction half reaction: CO 23 2-+2e-+4H+＝CO+2H2O
Photocatalyst generates photoproduction electrons and holes under the condition of illumination in the reaction, and CO between layers3 2-And the hydroxyl in the biomass molecule and the photoproduction hole are subjected to oxidation reaction to generate aldehyde group.
FIGS. 1-5 are representations of photocatalysts:
as can be seen from FIG. 1, the photocatalyst prepared in example 1 has both LDH and TiO2The 2 theta angle value of the (003) diffraction peak is substituted into the Brad formula, and the interlayer spacing of LDH in the synthesized photocatalyst is 0.758nm through calculation, which indicates that CO is successfully synthesized3 2-Form MgAl-LDH/TiO2A catalyst.
As can be seen from the SEM photograph of FIG. 2, the LDH phase in the photocatalyst prepared in example 1 still maintains the sheet structure, and TiO phase in the photocatalyst prepared in example 1 maintains the sheet structure2Attached to the surface of MgAl-LDH, indicating the successful combination of the two materials.
As seen from FIG. 3, the photocatalyst prepared in example 1 absorbs in the ultraviolet region (wavelength band of 200nm-400 nm), and has a larger light response range and a stronger light response capability than MgAl-LDH.
FIG. 4 shows that the conduction band position of MgAl-LDH is-2.48 eV, and TiO2The positions of the conduction bands are-1.05 eV which are higher than CO2Reducing the required electrode potential. The valence band position of MgAl-LDH is 2.06eV, TiO2The valence band positions of the catalyst are 2.21eV, and the oxidation electromotive force of the catalyst is lower than that of 5-HMF, thereby showing that the catalyst can support CO thermodynamically2The reduction and 5-HMF oxidation coupling reaction occurs.
As shown in FIG. 5, the separation efficiency of the photo-generated electron hole of the photocatalyst is remarkably improved, and the photocatalytic reaction is facilitated.
The invention has the beneficial effects that: the invention adopts a one-step hydrothermal method to synthesize the photocatalyst, and obtains the composite photocatalyst by controlling the aging temperature, the reaction time, the proportion and the variety of LDH and metal oxide. The metal oxide N in the prepared composite photocatalyst is attached to the surface of LDH, wherein interlayer anions in the LDH are CO3 2-Realize the reactant CO2The pre-enrichment of the LDH and the metal oxide can realize the enhancement of the photoproduction electron-hole separation capability after the LDH is compounded with the metal oxide, so that the reactant CO can3 2-And the rapid conversion of biomass. Therefore, the material shows excellent performance in the photocatalysis coupling reaction.
Drawings
FIG. 1 is a schematic view of aIs the XRD diffraction pattern of the photocatalyst prepared in example 1 and the first two materials are compounded, a is TiO2B is MgAl-LDH, c is MgAl-LDH/TiO2。
FIG. 2 is a Scanning Electron Microscope (SEM) photograph of the photocatalyst prepared in example 1, and the two materials before being combined, a being TiO2B is MgAl-LDH, c is MgAl-LDH/TiO2。
FIG. 3 is the solid UV diffuse reflectance spectra of the photocatalyst prepared in example 1, and the first two materials combined, a is TiO2B is MgAl-LDH, c is MgAl-LDH/TiO2。
FIG. 4 shows the band structure of two materials alone in the photocatalyst prepared in example 1, a is TiO2And b is MgAl-LDH.
FIG. 5 is a photo current response spectrum of the photocatalyst prepared in example 1 and the two materials before being compounded, wherein a is TiO2B is MgAl-LDH, c is MgAl-LDH/TiO2。
Detailed Description
Example 1
A, weighing 0.004mol of Mg (NO)3)2·6H2O and 0.002mol of Al (NO)3)3·9H2Powder O, dissolved in a beaker containing 30mL of deionized water.
B, weighing 0.03mol of urea and 0.6000g of TiO2The powder was added to a beaker containing 30mL of deionized water.
C, simultaneously adding the two solutions into another beaker, and carrying out violent stirring and ultrasonic dispersion until the solution is TiO2The powder is evenly dispersed in the solution to obtain MgAl-LDH/TiO2Suspension of (2); transferring to a reactor, aging for 24h at 120 ℃, centrifugally separating, and washing the filtrate to neutrality; drying at 50 deg.C for 12h, taking out, grinding into powder to obtain MgAl-LDH/TiO2Photocatalyst of, wherein TiO2The mass ratio of the MgAl-LDH to the MgAl-LDH is 1.
The photocatalyst prepared by the method is used for photo-driving CO2reduction-5-HMF oxidative coupling reaction experiment:
dissolving 30mg of catalyst powder in 60mL of 0.02 g/L5-HMF solution, placing the solution into a top-illuminated reaction kettle, screwing the reaction kettle, introducing inert gas to replace air in a device, closing an air outlet valve, introducing inert gas to ensure that the pressure in the reaction kettle reaches 0.2MPa, closing a reaction system, opening a 300W Xe lamp for irradiation reaction, taking 1mL of gas sample by using a stainless steel gas-tight needle after the reaction is finished for 4 hours, detecting CO in the sample by using gas chromatography, and evaluating the reaction activity of the catalyst by detecting the content of 2, 5-furan-Dicarbaldehyde (DFF) in liquid by using liquid chromatography, so that the accumulated CO yield of the photocatalyst reaches 103.25 mu mol/g within 4 hours of reaction time; the yield of DFF reached 90.31. mu. mol/g.
Example 2
A, weighing 0.006mol of Ni (NO)3)2·6H2O and 0.002mol of Fe (NO)3)3·9H2O powder, dissolved in a beaker containing 30mL of deionized water.
B, weighing 0.02mol of urea and 0.3000g of Cu2O solids, charged to a beaker containing 30mL of deionized water.
C, adding the solution A and the suspension B into a beaker at the same time, and carrying out vigorous stirring and ultrasonic dispersion until Cu is obtained2O powder is evenly dispersed in the solution to obtain NiFe-LDH/Cu2Suspension of O; transferring to a reactor, aging at 100 deg.C for 12h, washing, and centrifuging to neutral; drying at 60 deg.C for 12h, taking out, grinding into powder to obtain NiFe-LDH/Cu2O photocatalyst, wherein Cu2The mass ratio of O to NiFe-LDH is 0.6.
Example 3
A, weighing 0.004mol of Zn (NO)3)2·6H2O and 0.002mol of Cr (NO)3)3·9H2O powder, dissolved in a beaker containing 30mL of deionized water.
B0.04 mol of urea and 1.2000g of CeO are weighed2Solid, dosed into a beaker containing 30mL of deionized water.
C, adding the solution A and the suspension B into a beaker at the same time, and carrying out violent stirring and ultrasonic dispersion until CeO is obtained2The powder is evenly dispersed in the solution to obtain ZnCr-LDH/CeO2Suspension of (2);transferring to a reactor, aging at 150 ℃ for 36h, washing, and centrifuging until the solution is neutral; drying at 60 ℃ for 12h, taking out, grinding into powder to obtain ZnCr-LDH/CeO2Photocatalyst of CeO2The mass ratio of the ZnCr-LDH to the ZnCr-LDH is 3.
Example 4
A, weighing 0.004mol of Co (NO)3)2·6H2O and 0.002mol of Al (NO)3)3·9H2O powder, dissolved in a beaker containing 30mL of deionized water.
B, weighing 0.06mol of urea and 0.4000g of ZrO2Solid, dosed into a beaker containing 30mL of deionized water.
C, adding the solution A and the suspension B into a beaker at the same time, and after vigorous stirring and ultrasonic dispersion, obtaining ZrO2The powder is uniformly dispersed in the solution to obtain the CoAl-LDH/ZrO2Suspending liquid; transferring the mixture into a reactor, aging the mixture for 36 hours at 120 ℃, washing and centrifugally separating the mixture until the mixture is neutral; drying at 60 deg.C for 12h, taking out, grinding into powder to obtain CoAl-LDH/ZrO2Photocatalyst of, wherein ZrO2The mass ratio to CoAl-LDH was 0.8.
Claims (4)
1. CO (carbon monoxide)2The preparation method of the photocatalyst for reduction-biomass oxidation coupling reaction is characterized by comprising the following steps:
A. dissolving the soluble M2+Salts and M3+Dissolving salt in deionized water to prepare solution A, wherein M2+The molar concentration of (A) is 0.05-0.35mol/L, M2+：M3+The molar ratio of (A) to (B) is 2-4: 1; the anion in solution is CO3 2-；
Said M2+Is Mg2+、Co2+、Zn2+、Mn2+、Ni2+、Cu2+One of (a) and (b); m is a group of3+Is Al3+、Fe3+、Cr3+、Ce3+、In3+、Ga3+One of (1);
B. adding metal oxide N powder and urea into deionized water with the volume equal to that of the solution A, and fully stirring to prepare suspension B with the volume equal to that of the solution A, wherein the concentration of the urea is 0.2-2mol/L, and the mass concentration of the N is 6.0-40 g/L; specifically, the mass ratio of N to LDH in the target catalyst is determined;
the N is TiO2、Cu2O、CeO2、NiO、ZnO、ZrO2One of (1);
C. adding the solution A and the suspension B with equal volumes into a reactor simultaneously, and dispersing under the conditions of vigorous stirring and ultrasound until solid powder is uniformly dispersed in the solution to obtain suspension; centrifugally separating out solids, aging in an oven at 80-150 deg.C for 8-48h, and washing to neutrality; drying at 50-80 deg.C or low temperature under vacuum for 12-24 hr, grinding into powder to obtain target photocatalyst represented as LDH/N, wherein the formula of LDH is [ M ]1-x 2+Mx 3+(OH)2]x+(CO3 2-)x/n·mH2O。
2. CO according to claim 12A method for preparing a photocatalyst for reduction-biomass oxidation coupling reaction is characterized in that M in the step A2+Is Mg2+、Co2+、Ni2+One of them; m is a group of3+Is Al3+、Fe3+、Cr3+One of them; in step B, N is TiO2Or ZrO2(ii) a And D, the mass ratio of N to LDH in the photocatalyst obtained in the step C is 0.5-1.5.
3. CO prepared according to the method of claim 12The photocatalyst for reduction-biomass oxidation coupling reaction is characterized in that the chemical expression formula of the photocatalyst is as follows: LDH/N, wherein N is metal oxide, N is attached to the surface of LDH, and N is TiO2、Cu2O、CeO2、NiO、ZnO、ZrO2One of (1); LDH is a layered composite metal hydroxide represented by the formula: [ M ]1-x 2+Mx 3 +(OH)2]x+(CO3 2-)x/n·mH2O, wherein M2+Is Mg2+、Co2+、Zn2+、Mn2+、Ni2+、Cu2+One of (a) and (b); m is a group of3+Is Al3+、Fe3 +、Cr3+、Ce3+、In3+、Ga3+One of (1); m2+And M3+The molar ratio of (a) to (b) is 2-4: 1; wherein the mass ratio of N to LDH is 0.25-3.
4. CO according to claim 32The photocatalyst for reduction-biomass oxidation coupling reaction is characterized in that N is TiO2Or ZrO2；M2+Is Mg2+、Co2+、Ni2+One of them; m3+Is Al3+、Fe3+、Cr3+One of them; the mass ratio of N to LDH is 0.5-1.5.
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