CN114768818A - Water-heat oxygen decoupling catalyst, preparation method and application - Google Patents

Water-heat oxygen decoupling catalyst, preparation method and application Download PDF

Info

Publication number
CN114768818A
CN114768818A CN202210229811.3A CN202210229811A CN114768818A CN 114768818 A CN114768818 A CN 114768818A CN 202210229811 A CN202210229811 A CN 202210229811A CN 114768818 A CN114768818 A CN 114768818A
Authority
CN
China
Prior art keywords
catalyst
moo
alpha
hydrothermal
salt
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.)
Granted
Application number
CN202210229811.3A
Other languages
Chinese (zh)
Other versions
CN114768818B (en
Inventor
颜蓓蓓
王建
陶俊宇
刘子彪
侯东昊
程占军
苏红
陈冠益
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tianjin University
Tianjin University of Commerce
Original Assignee
Tianjin University
Tianjin University of Commerce
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Tianjin University, Tianjin University of Commerce filed Critical Tianjin University
Priority to CN202210229811.3A priority Critical patent/CN114768818B/en
Publication of CN114768818A publication Critical patent/CN114768818A/en
Application granted granted Critical
Publication of CN114768818B publication Critical patent/CN114768818B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • 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
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/885—Molybdenum and copper
    • 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Catalysts (AREA)

Abstract

The disclosure provides a hydrothermal oxygen decoupling catalyst, a preparation method and application, wherein the preparation method of the catalyst comprises the following steps: step S1: the first catalyst Cu-alpha-Fe is obtained by adopting a sol-gel method2O3·α‑MoO3(ii) a Step S2: for first catalyst Cu-alpha-Fe2O3·α‑MoO3Carrying out thermal hydrogenation treatment to obtain thermally hydrogenated Cu-alpha-Fe2O3·α‑MoO3A catalyst. The molecular formula of the hydrothermal oxygen decoupling catalyst prepared by the method is as follows: Cu-alpha-Fe2O3·α‑MoO3，α‑MoO3Is the main component of the water phase reforming catalyst and is doped with alpha-ion which is beneficial to the water oxidationFe2O3And Cu having oxygen decoupling properties, wherein the Cu is present in the catalyst in a manner comprising CuO and Cu2O; and alpha-MoO370-75% of alpha-Fe2O3The mass fraction of the Cu-Cu alloy accounts for 20-22%, and the mass fraction of the Cu accounts for 3-10%. The hydrothermal oxygen decoupling catalyst can be used for treating organic wastewater, wherein the organic wastewater comprises biogas slurry. Based on the principle of le chatelier, the reaction is promoted to be continuously carried out in the forward direction, the organic matter consumption is facilitated, and the organic matter in the biogas slurry is removed. The catalyst provided by the disclosure has the advantages of simple preparation method and low cost.

Description

Water-heat oxygen decoupling catalyst, preparation method and application
Technical Field
The disclosure belongs to the field of catalyst preparation, and particularly relates to a hydrothermal oxygen decoupling catalyst, a preparation method and application.
Background
The organic solid waste comprises agricultural wastes (livestock and poultry manure, straws, waste vegetables and fruits), kitchen waste, municipal sludge and the like, and the biogas and the organic fertilizer can be produced by an anaerobic fermentation resource utilization method. Under the promotion of the state, the application of organic solid waste biogas gasification is greatly developed, but with the continuous increase of the scale and the quantity of biogas projects, a large amount of biogas slurry treatment problems are generated. At present, the organic fertilizer (biogas fertilizer) is a simple and convenient method for disposing and utilizing biogas slurry, but has some problems in practical biogas engineering application, such as: the biogas manure has large yield, high storage and transportation cost, difficult supply and demand matching, unclear agricultural action mechanism of the biogas manure, incapability of ensuring nutrient content, unprofessional returning equipment, and incapability of effectively ensuring subsequent treatment and final utilization. The above factors severely limit the traditional way of fertilizing biogas slurry. Therefore, the development and optimization of the prior art for harmless treatment and resource utilization of biogas slurry are problems to be solved urgently so as to improve or replace the original traditional biogas fertilizer application technology.
The aqueous phase reforming method is a novel hydrogen production method, and the hydrogen can be obtained by the aqueous phase reforming reaction of carbohydrate in biomass or biomass waste at the temperature of about 227 ℃ in the presence of a catalyst. Meanwhile, as the reaction system is a water phase, some side reactions can be avoided, and the water-gas shift reaction is more favorable to occur thermodynamically, so that a new idea is provided for biogas slurry treatment and utilization. Although the water phase reforming technology has been applied to the research of beer wastewater, cheese whey and fruit juice wastewater treatment and hydrogen production utilization, the research on biogas slurry is very little, and the composition of the biogas slurry is complex, so that it is difficult to construct an efficient and cheap catalyst, and the development of the biogas slurry water phase reforming treatment technology is limited.
Disclosure of Invention
In view of the above technical problems, the present disclosure provides a hydrothermal oxygen decoupling catalyst, a preparation method and an application thereof, which are intended to at least partially solve the above technical problems.
In order to solve the above technical problems, as one aspect of the present disclosure, there is provided a method for preparing a hydrothermal oxygen decoupling catalyst, comprising: step S1: obtaining a first catalyst Cu-alpha-Fe by adopting a sol-gel method2O3·α-MoO3(ii) a Step S2: for the first catalyst Cu-alpha-Fe2O3·α-MoO3Carrying out thermal hydrogenation treatment to obtain thermally hydrogenated Cu-alpha-Fe2O3·α-MoO3A catalyst.
In one embodiment, the step S1 includes:
s1.1, dissolving water-soluble Cu salt, Fe salt, Mo salt precursor and sodium alkylsulfonate surfactant with water to obtain a Cu-Fe-Mo-Na mixed solution;
s1.2, sequentially adding citric acid and ethylene glycol into the Cu-Fe-Mo-Na mixed solution, and heating and stirring to obtain a first solution;
s1.3, adding ammonia water into the first solution to adjust the pH value, and continuously heating and stirring to form gel;
s1.4, drying the gel, and then calcining to obtain a first catalyst Cu-alpha-Fe2O3·α-MoO3。
In one embodiment, the precursors of the Cu salt, the Fe salt and the Mo salt are Cu (NO)3)2·3H2O、Fe(NO3)3·9H2O、(NH4)6Mo7O24·4H2O；
The above-mentioned alkyl sodium sulfonate surfactant is CH3(CH2)11SO3Na。
In one embodiment, the step S2 includes:
s2.1 adding Cu-alpha-Fe to the first catalyst2O3·α-MoO3In which H is added2O2Heating and evaporating to dryness after the reaction is finished;
s2.2, adding a sucrose solution into the evaporated material of the S2.1, and stirring under heating until the evaporated material is evaporated to dryness;
s2.3, drying the evaporated S2.2, and then calcining to obtain the thermally hydrogenated Cu-alpha-Fe2O3·α-MoO3A catalyst.
In one embodiment, adding ammonia to the first solution to adjust the pH range comprises: 8 to 10.
In one embodiment, the heating temperature range includes: 65-85 ℃.
In one embodiment, the calcination temperature range includes 550 to 650 ℃;
the calcining time range comprises 1-2 h.
As another aspect of the present disclosure, there is also provided a hydrothermal oxygen decoupling catalyst prepared by the above method, the above catalyst having a molecular formula as follows:
Cu–α-Fe2O3·α-MoO3wherein the Cu exists in the catalyst in a mode including CuO and Cu2O。
In another embodiment thereof, the above α -MoO370-75% of alpha-Fe2O3The mass fraction of the Cu is 20-22%, and the mass fraction of the Cu is 3-10%.
As still another aspect of the present disclosure, there is also provided a use of the above hydrothermal oxygen decoupling catalyst for treating organic wastewater, wherein the organic wastewater includes: biogas slurry.
Based on the technical scheme, the disclosure provides a hydrothermal oxygen decoupling catalyst, a preparation method and an application, and at least one of the following beneficial effects is included:
(1) in the disclosed embodiment, the hydrothermal oxygen decoupling catalyst is prepared by a two-step catalysis method of firstly adopting a sol-gel method and then carrying out thermal hydrogenation treatment, and the method enables active components in the catalyst to be highly dispersed with Cu, wherein the Cu exists in the catalyst in a mode of CuO and Cu2O, the oxygen decoupling performance of the catalyst is improved, and the preparation method provided by the embodiment of the disclosure is simple and low in use cost of raw materials.
(2) The oxygen decoupling catalyst prepared by the method disclosed by the invention can be used for treating organic wastewater and removing organic matters in the wastewater, wherein the organic wastewater comprises biogas slurry.
Drawings
FIG. 1A shows a first catalyst Cu- α -Fe in example 1 of the present disclosure2O3·α-MoO3Scanning electron microscope images of (a);
FIG. 1B is thermally hydrogenated Cu- α -Fe in example 1 of the present disclosure2O3·α-MoO3Scanning electron microscope images of;
FIG. 2A and FIG. 2B are Cu- α -Fe, respectively, as a first catalyst in example 1 of the present disclosure2O3·α-MoO3And Cu-alpha-Fe after thermal hydrogenation2O3·α-MoO3X-ray diffraction patterns of (a);
FIG. 3A is a first catalyst Cu- α -Fe of example 1 of the present disclosure2O3·α-MoO3Transmission electron microscopy image-elemental surface scan;
FIGS. 3B to 3D are the first catalyst Cu- α -Fe, respectively, in example 1 of the present disclosure2O3·α-MoO3Distribution diagram of middle Fe, Mo, Cu elements;
FIG. 4A is Cu- α -Fe thermally hydrogenated in example 1 of the present disclosure2O3·α-MoO3Transmission electron microscopy image-elemental surface scan;
FIGS. 4B to 4D are thermally hydrogenated Cu-. alpha. -Fe, respectively, in example 1 of the present disclosure2O3·α-MoO3Distribution diagram of middle Fe, Mo, Cu elements;
FIG. 5A is a second catalyst, alpha-Fe, of comparative example 1 of the present disclosure2O3·α-MoO3Scanning electron microscope images of;
FIG. 5B is thermally hydrogenated α -Fe of comparative example 1 of the present disclosure2O3·α-MoO3Scanning electron microscope images of (a);
FIG. 6A and FIG. 6B are respectively the second catalyst α -Fe in comparative example 1 of the present disclosure2O3·α-MoO3And thermally hydrogenated alpha-Fe2O3·α-MoO3X-ray diffraction patterns of (a);
FIG. 7A is a second catalyst, alpha-Fe, of comparative example 1 of the present disclosure2O3·α-MoO3Transmission electron micrograph-elemental surface scan;
FIGS. 7B to 7C are views of the second catalyst α -Fe in comparative example 1 of the present disclosure2O3·α-MoO3Distribution diagram of middle Fe and Mo elements;
FIG. 8A is thermally hydrogenated α -Fe of comparative example 1 of the present disclosure2O3·α-MoO3Transmission electron micrograph-elemental surface scan;
FIGS. 8B to 8C are respectively the thermally hydrogenated α -Fe of comparative example 1 of the present disclosure2O3·α-MoO3Distribution diagram of middle Fe and Mo elements;
FIG. 9 is thermally hydrogenated Cu- α -Fe in example 1 of the present disclosure2O3·α-MoO3And thermally hydrogenated alpha-Fe in comparative example 12O3·α-MoO3Performance diagram for treating organic matters in biogas slurry.
Detailed Description
For the purpose of promoting a better understanding of the objects, aspects and advantages of the present disclosure, reference is made to the following detailed description taken in conjunction with the accompanying drawings.
At present, metals of group VIII, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Hs and Mt have relatively high C-C bond breaking capacity and are recognized as effective catalysts for aqueous phase reforming reaction. Among them, Pt catalyst is the most active and is currently the most commonly used catalyst active component. However, Pt catalysts are expensive, and therefore, it is one of the research hotspots at present to develop a high-efficiency catalyst and a low-cost catalyst without sacrificing the performance of the catalyst. alpha-MoO3Van der Waals heterojunctions and oxygen vacancies in the nanosheets have shown obvious importance in the water phase reforming treatment of the vinasse wastewater (biogas slurry), but have the problems of low organic matter removal rate and the like. It is noted that the presence of a small amount of oxidant can break some refractory molecular bonds, lowering the activation energy required to initiate the reaction, thereby facilitating further gasification of the reactants and increasing the efficiency of hydrogen generation. Therefore, the oxidant is properly introduced to promote the forward progress of the hydrogen production reaction by water phase reforming and promote the degradation of organic matters.
The wet catalytic oxidation is an efficient green technology for efficiently removing high-concentration organic wastewater, and the reaction usually needs to oxidize organic matters and pollutants containing N and the like in the wastewater into CO by using oxygen-rich gas or oxygen as an oxidant under the conditions of high temperature (120-320 ℃) and high pressure (0.5-20MPa) and utilizing the catalytic action of a catalyst2、N2、H2And O, thereby achieving the purpose of purification. Wet catalytic oxidation introduces an oxidant, increasing costs compared to aqueous phase reforming.
Based on the current research results of aqueous phase reforming and wet catalytic oxidation, the defects that the aqueous phase reforming can generate hydrogen but the organic matter removal capacity is limited, an external oxidizing agent needs to be additionally introduced in the wet catalytic oxidation technology, the cost is increased and the like are overcome. Therefore, in order to realize the resource utilization and industrial promotion of the organic solid waste anaerobic fermentation, the development of a novel, efficient and practical biogas slurry treatment method is urgently needed to be researched and solved.
The method fully considers the problems of limited potential for removing organic matters by a water-phase reforming reaction and the need of introducing an external oxidant in a wet catalytic reforming reaction, proposes or optimizes a new process (idea) based on the Lexisler principle, namely a hydrothermal oxygen decoupling catalyst, a preparation method and application, and adopts alpha-MoO3As host and doped with alpha-Fe2O3And Cu, wherein the Cu is present in the catalyst in a form comprising CuO and Cu2And O, a two-step catalyst preparation method of firstly carrying out a sol-gel method and then carrying out thermal hydrogenation is designed, so that the hydrothermal oxygen decoupling catalyst is prepared, and by adopting the preparation method, active components in the catalyst can be highly dispersed, so that the oxygen decoupling performance is improved, and the removal capacity of organic matters in the biogas slurry is improved.
According to an embodiment of the present disclosure, a method of preparing a hydrothermal oxygen decoupling catalyst comprises: step S1: obtaining a first catalyst Cu-alpha-Fe by adopting a sol-gel method2O3·α-MoO3(ii) a Step S2: for the first catalyst Cu-alpha-Fe2O3·α-MoO3Carrying out thermal hydrogenation treatment to obtain thermally hydrogenated Cu-alpha-Fe2O3·α-MoO3A catalyst.
According to the embodiment of the disclosure, the hydrothermal oxygen decoupling catalyst is prepared by a two-step catalysis method of firstly adopting a sol-gel method and then carrying out thermal hydrogenation treatment, active components in the catalyst are highly dispersed, and the oxygen decoupling performance is improved. Due to alpha-MoO in the catalyst component3The catalyst has a Van der Waals heterojunction, and is beneficial to the generation of a hydrogen production reaction through water phase reforming; alpha-Fe2O3Has the characteristic of promoting water oxidation, while Cu (the form of Cu existing in the catalyst comprises CuO and Cu)2O) has oxygen decoupling performance, can release oxygen in situ, and can realize the removal of organic matters and avoid the use of an oxidant.
According to an embodiment of the present disclosure, step S1 includes: s1.1, dissolving water-soluble Cu salt, Fe salt, Mo salt precursor and sodium alkyl sulfonate surfactant with water to obtain a Cu-Fe-Mo-Na mixed solution; s1.2, sequentially adding citric acid and ethylene glycol into the Cu-Fe-Mo-Na mixed solution, heating and stirring to obtain the second solutionA solution; s1.3, adding ammonia water into the first solution to adjust the pH value, and continuously heating and stirring to obtain gel; s1.4, drying the gel, and then calcining to obtain a first catalyst Cu-alpha-Fe2O3·α-MoO3。
According to the embodiment of the disclosure, the precursors of the Cu salt, the Fe salt and the Mo salt are Cu (NO)3)2·3H2O、Fe(NO3)3·9H2O、(NH4)6Mo7O24·4H2O; the sodium alkylsulfonate surfactant is CH3(CH2)11SO3Na。
Through the embodiment of the disclosure, the glycol and the iron ions can ensure alpha-Fe through hydrolysis and condensation reaction2O3And (4) generating.
According to an embodiment of the present disclosure, adding ammonia water to the first solution to adjust the pH range includes: 8-10, wherein the pH is preferably adjusted to 9.
According to an embodiment of the present disclosure, the heating temperature range includes: 65-85 ℃, wherein the temperature can be selected from 65, 70, 75, 80, 85 ℃ and the like.
According to the embodiment of the disclosure, the calcining temperature range comprises 550-650 ℃, wherein the temperature can be selected from 550, 600, 650 ℃ and the like; the calcining time range comprises 1-2 h, wherein 1, 1.5, 2h and the like can be selected; the heating rate of the calcination is 15 ℃/min.
By way of example of the present disclosure, the purpose of the calcination is to change the molybdenum oxide from bulk to flake, with a calcination temperature of preferably 600 ℃.
By way of example of the present disclosure, Cu (NO)3)2·3H2O、Fe(NO3)3·9H2O、(NH4)6Mo7O24·4H2O and surfactant sodium dodecyl sulfate CH3(CH2)11SO3And pouring the Na crystals into a beaker, adding a certain amount of deionized water, and uniformly stirring by using a glass rod to obtain a Cu-Fe-Mo-Na mixed solution. Then, a certain amount of citric acid is slowly added into the Cu-Fe-Mo-Na mixed solution, and the mixture is stirred while being heated until the mixture is straightUntil the solution was clear. Subsequently, adding a certain amount of glycol into the solution; and then, adding ammonia water with the concentration of 25-28% to adjust the pH value of the solution to 8-10, and continuously stirring in a water bath kettle at the constant temperature of 80 ℃ until gel is formed. Then, the gel is put into an oven and dried for 72h at 105 ℃ (error of 30 min); then, the dried sample is placed in a tubular furnace, the temperature is raised to 600 ℃ by a program in the tubular furnace with the temperature rise rate of 15 ℃/min, the sample is calcined for 1.5h at the temperature of 600 ℃, then the prepared sample is cleaned to be neutral by deionized water, the washed sample is dried for 12h at the temperature of 105 ℃ in an oven, and the catalyst prepared by the sol-gel method, namely the first catalyst Cu-alpha-Fe, is obtained2O3·α-MoO3。
According to an embodiment of the present disclosure, step S2 includes: s2.1, adding Cu-alpha-Fe into a first catalyst2O3·α-MoO3In which H is added2O2Heating and evaporating to dryness after the reaction is finished; s2.2, adding a sucrose solution into the evaporated substances of the S2.1, and stirring under heating until the substances are evaporated to dryness; s2.3, drying the evaporated S2.2, and then calcining to obtain the thermally hydrogenated Cu-alpha-Fe2O3·α-MoO3A catalyst.
By way of example of the present disclosure, the first catalyst Cu- α -Fe is first subjected to a thermal hydrogenation treatment2O3·α-MoO3The first catalyst is placed in a drying box and dried for 2 hours at 105 ℃, so that the moisture in the first catalyst can be effectively removed; then, the dried first catalyst was placed in a beaker, and a certain amount of H was added to the beaker2O2(30 wt%), stirring with glass rod, sealing with preservative film after heat release, standing at cool place for 48H, and adding H2O2The primary purpose of (a) is to over-oxidize the first catalyst to provide hydrogen to the first catalyst; then, deionized water was added to the beaker to dilute H2O2The concentration of (c). Then, adding sucrose solution while heating and stirring in water bath, stirring and evaporating to dryness, and consuming excessive H in the beaker by using sucrose2O2. The solution in the beaker is evaporated to dryness, and the evaporated material is placed in a drying oven and dried at 105 deg.C for 8 hr (error tolerance)30 min); then, the dried material is put into a tube furnace to be calcined for 1.5h at 600 ℃ at the heating rate of 15 ℃/min, and then the calcined sample is washed to be neutral by deionized water to obtain the thermally hydrogenated Cu-alpha-Fe2O3·α-MoO3A catalyst.
According to an embodiment of the present disclosure, a hydrothermal oxygen decoupling catalyst is prepared by the above method, and the molecular formula of the catalyst is as follows: Cu-alpha-Fe2O3·α-MoO3Wherein the Cu exists in the catalyst in a mode including CuO and Cu2O。
According to an embodiment of the present disclosure, α -MoO370-75% of alpha-Fe2O3The mass fraction of the Cu is 20-22%, and the mass fraction of the Cu is 3-10%.
According to an embodiment of the present disclosure, Mo salts are α -MoO3The aqueous phase reforming catalyst can be selected and replaced according to specific situations; fe salt alpha-Fe2O3As an auxiliary agent, magnetic gamma-Fe can be replaced2O3The Fe salt is beneficial to water oxidation and is also convenient for catalyst recovery; the Cu salt is a catalyst with oxygen decoupling performance, and the existence form of Cu in the catalyst comprises CuO and Cu2O, Mn or Co oxide can be used for replacing O; the surfactant is preferably a cationic surfactant, which primarily functions to disperse the elements. Generally speaking, under the condition of ensuring the catalytic performance of the aqueous phase reforming catalyst as a main part, the components and the proportion of different types of catalysts can be properly adjusted according to specific requirements.
By the embodiment of the disclosure, a sol-gel and thermal hydrogenation two-step method is adopted to construct a composite material of alpha-MoO3As main component and doped with alpha-Fe2O3CuO and Cu2The catalyst of O 'Van der Waals heterojunction-redox' type has catalytic performance mainly promoting the generation of aqueous phase reforming reaction and secondarily promoting wet oxidation reaction. Wherein the factor is alpha-MoO3The catalyst has van der Waals heterojunction, and can be beneficial to the generation of hydrogen production reaction through aqueous phase reforming; alpha-Fe2O3Has the characteristic of promoting the water oxidation; CuO and Cu2O has good oxygen decoupling propertyOxygen can be released in situ. The three are coupled, so that the organic matter can be ensured to have higher removal rate, the use of an oxidant is avoided, and the cost is reduced.
According to an embodiment of the present disclosure, the application of the oxygen decoupling catalyst for treating organic wastewater is utilized, wherein the organic wastewater comprises biogas slurry.
According to an embodiment of the present disclosure, the operation of the application for treating organic wastewater using the above oxygen decoupling catalyst includes: centrifuging the biogas slurry, collecting supernatant, and subjecting the supernatant and thermally hydrogenated Cu-alpha-Fe2O3·α-MoO3Adding a catalyst into an intermittent high-temperature high-pressure reaction kettle with a magnetic stirrer for reaction, uniformly stirring by using a glass rod, sealing the reaction kettle, purging and replacing air in the kettle by using high-purity nitrogen, and setting the reaction temperature to be 150-250 ℃, preferably 225 ℃. After the reaction is finished, removing the heating sleeve, cooling the reaction kettle by using a fan, opening an exhaust valve to collect gas when the temperature in the kettle is reduced to about 25 ℃, opening the reaction kettle when the pressure in the kettle is close to the ambient pressure, pouring out liquid phase residues, used catalyst and residues, and finally drying the obtained solid to constant weight at 105 ℃.
The specific reaction parameters including mass, reaction temperature and volume are within the range of +/-0.1-0.2 g, +/-55 ℃ and +/-0.5-1 mL of the indicated value; for example, a temperature of 225 ℃ generally refers to, in a broad sense, 225 ℃. + -. 5 ℃ (i.e., 220 ℃ to 230 ℃).
For the purpose of making the objects, aspects and advantages of the present disclosure more apparent, the present disclosure will now be described in further detail with reference to specific embodiments thereof and with reference to the accompanying drawings.
The biogas slurry is obtained from anaerobic fermentation engineering of distiller's grains of Guizhou Maotai Limited company under the conditions of fermentation temperature of 30 ℃ and fermentation time of 40 days (NPOC 19815 + -77.78 mg/L, AN 6200 + -282.84 mg/L, TN 9000 + -848.53 mg/L and COD 63600 + -2262.74 mg/L). Cu (NO)3)2·3H2O、Fe(NO3)3·9H2O、(NH4)6Mo7O24·4H2O, surfactant CH3(CH2)11SO3Na, citric acid, ethylene glycol, ammonia water (25-28 wt%), hydrogen peroxide (30 wt%), cane sugar and deionized water, all of which are analytically pure.
It should be noted that NPOC represents total organic carbon, AN represents ammonia nitrogen, TN represents total nitrogen, and COD represents chemical oxygen demand.
Example 1
1. Preparation of first catalyst Cu-alpha-Fe by sol-gel method2O3·α-MoO3
0.05mol of Cu (NO) is weighed out quickly3)2·3H2O、0.1mol Fe(NO3)3·9H2O、0.0286mol(NH4)6Mo7O24·4H2O and 50g of surfactant CH3(CH2)11SO3And pouring the Na crystals into a beaker, adding 500mL of deionized water, and uniformly stirring by using a glass rod to prepare a Cu-Fe-Mo-Na mixed solution. 100g of citric acid was weighed and slowly added to the prepared Cu-Fe-Mo-Na mixed solution with stirring. Subsequently, 250mL of ethylene glycol was added to the above solution. Then, putting the beaker into a water bath kettle, and continuously stirring for 5 hours at the constant temperature of 70 ℃; adding a proper amount of 25-28 wt% ammonia water to adjust the pH of the solution to 9. Stirring was then continued in a water bath at 80 ℃ until a gel was formed. The gel is put into an oven and dried for 72h at 150 ℃ (error 30 min). And placing the dried sample in a tubular furnace with air flow of 500N mL/min and heating rate of 15 ℃/min, raising the temperature to 600 ℃ by program, and calcining for 1.5h at 600 ℃. Washing the prepared sample by using deionized water until the sample is neutral; drying the washed sample in an oven at 105 ℃ for 12h to obtain a first catalyst Cu-alpha-Fe prepared by a sol-gel method2O3·α-MoO3And filling the first catalyst into a self-sealing bag for later use.
2. Thermal hydrogenation treatment to obtain thermally hydrogenated Cu-alpha-Fe2O3·α-MoO3
Before the thermal hydrogenation treatment, a first catalyst Cu-alpha-Fe2O3·α-MoO3Drying in a drying oven at 105 deg.C for 2 hr; however, the device is not limited to the specific type of the deviceThereafter, the sample was placed in a beaker and 150mL of H was slowly added2O2(30 wt%) is poured into a beaker, stirred uniformly by a glass rod, and after heat release is finished, the beaker is sealed by a preservative film and is kept stand for 48 hours at a cool place at room temperature. Then, 150mL of deionized water was added to the beaker and the solution was diluted. Then, putting the mixture into a water bath kettle, continuously stirring the mixture at a constant temperature of 80 ℃ until the mixture is dried to dryness, quickly weighing the sucrose crystals, pouring the sucrose crystals into a beaker, adding deionized water, and uniformly stirring the mixture by using a glass rod to prepare 342.79g/L sucrose solution; 50mL of the sucrose solution was poured slowly into a beaker. The dried sample was placed in a forced air drying oven and dried in an oven at 150 ℃ for 8h (error 30 min). And placing the dried sample in a tubular furnace with air flow of 500N mL/min and heating rate of 15 ℃/min, raising the temperature to 600 ℃ by program, and calcining for 1.5h at 600 ℃. Washing the prepared sample with deionized water to be neutral, drying the washed sample in an oven at 105 ℃ for 12h to obtain the catalyst Cu-alpha-Fe subjected to heat hydrogenation treatment2O3·α-MoO3And filling the self-sealing bag for standby.
FIG. 1A shows a first catalyst Cu- α -Fe in example 1 of the present disclosure2O3·α-MoO3Scanning electron microscope images of (a); FIG. 1B is thermally hydrogenated Cu- α -Fe in example 1 of the present disclosure2O3·α-MoO3Scanning electron microscope image (c).
As shown in FIGS. 1A and 1B, a first catalyst Cu- α -Fe prepared from sol-gel2O3·α-MoO3Forming a nano-sheet structure, and adding Cu-alpha-Fe as a first catalyst2O3·α-MoO3The nano flaky structure is still maintained after the thermal hydrogenation treatment, which shows that the morphological structure of the first catalyst is not damaged by the thermal hydrogenation treatment, and the nano catalyst has the characteristics of high activity and high selectivity of the homogeneous catalyst.
FIG. 2A and FIG. 2B are the first catalyst Cu- α -Fe, respectively, in example 1 of the present disclosure2O3·α-MoO3And Cu-alpha-Fe after thermal hydrogenation2O3·α-MoO3X-ray diffraction pattern of (a).
As shown in fig. 2A and 2B, the first catalystCu–α-Fe2O3·α-MoO3And Cu-alpha-Fe after thermal hydrogenation2O3·α-MoO3All contain alpha-Fe2O3、α-MoO3And Cu, wherein Cu is present in the catalyst in the form of CuO and Cu2O。
FIG. 3A is a first catalyst Cu- α -Fe of example 1 of the present disclosure2O3·α-MoO3Transmission electron microscopy image-elemental surface scan; FIGS. 3B to 3D are the first catalyst Cu- α -Fe, respectively, in example 1 of the present disclosure2O3·α-MoO3Distribution diagram of medium Fe, Mo and Cu elements.
As shown in FIG. 3A, the first catalyst Cu-alpha-Fe2O3·α-MoO3The alloy is a sheet structure, and Fe, Mo and Cu elements are uniformly distributed in FIGS. 3B to 3D.
FIG. 4A is thermally hydrogenated Cu- α -Fe in example 1 of the present disclosure2O3·α-MoO3Transmission electron microscopy image-elemental surface scan; FIGS. 4B to 4D are thermally hydrogenated Cu-. alpha. -Fe, respectively, in example 1 of the present disclosure2O3·α-MoO3Distribution diagram of middle Fe, Mo, Cu elements.
As shown in FIG. 4A, the first catalyst was subjected to a thermal hydrogenation treatment to obtain thermally hydrogenated Cu- α -Fe2O3·α-MoO3The catalyst is also in a sheet structure, and as shown in fig. 4B to 4D, the elements of Fe, Mo and Cu are uniformly distributed, and the elements in the catalyst after the thermal hydrogenation treatment are more uniformly distributed.
Comparative example 1
The same operation as in example 1 was carried out to prepare a second catalyst, α -Fe2O3·α-MoO3And thermally hydrogenated alpha-Fe2O3·α-MoO3A comparison was made, the only difference being that comparative example 1 contained no Cu salt.
FIG. 5A is a second catalyst, alpha-Fe, of comparative example 1 of the present disclosure2O3·α-MoO3Scanning electron microscope images of;
FIG. 5B is thermally hydrogenated α -Fe of comparative example 1 of the present disclosure2O3·α-MoO3Sweeping ofScanning electron microscope images.
As shown in FIGS. 5A and 5B, the second catalyst alpha-Fe prepared without adding Cu salt2O3·α-MoO3Also has a nano sheet structure, and the appearance is not changed after the thermal hydrogenation treatment.
FIG. 6A and FIG. 6B are respectively the second catalyst α -Fe in comparative example 1 of the present disclosure2O3·α-MoO3And thermally hydrogenated alpha-Fe2O3·α-MoO3X-ray diffraction pattern of (a).
As shown in FIGS. 6A and 6B, the second catalyst α -Fe before and after the thermal hydrogenation treatment2O3·α-MoO3And thermally hydrogenated alpha-Fe2O3·α-MoO3The compositions are the same and all contain alpha-Fe2O3And alpha-MoO3。
FIG. 7A is a second catalyst, α -Fe, comparative example 1 of the present disclosure2O3·α-MoO3Transmission electron microscopy image-elemental surface scan; FIGS. 7B to 7C are respectively the second catalyst alpha-Fe in comparative example 1 of the present disclosure2O3·α-MoO3Distribution diagram of middle Fe and Mo elements.
As shown in fig. 7A, the second catalyst in comparative example 1 also has a plate-like structure, and the Fe and Mo element distributions in fig. 7B to 7C are relatively concentrated, and are not uniformly dispersed in the first catalyst in example 1.
FIG. 8A is thermally hydrogenated α -Fe of comparative example 1 of the present disclosure2O3·α-MoO3Transmission electron micrograph-elemental surface scan; FIGS. 8B to 8C are respectively the thermally hydrogenated α -Fe of comparative example 1 of the present disclosure2O3·α-MoO3Distribution diagram of middle Fe and Mo elements.
As shown in FIG. 8A, the second catalyst of comparative example 1 was subjected to a thermal hydrogenation treatment to obtain thermally hydrogenated α -Fe2O3·α-MoO3The structure is also a flaky structure, and the appearance is not obviously changed; the distribution of Fe and Mo elements shown in FIGS. 8B to 8C is relatively compact, and is inferior to that of Cu-. alpha. -Fe after the heat-hydrogenation treatment in example 12O3·α-MoO3The Fe and Mo elements are dispersed uniformly.
Passing the biogas slurry throughCentrifuging at 1000rpm to obtain supernatant, collecting 50mL supernatant of the biogas slurry, and adding alpha-Fe without catalyst and second catalyst2O3·α-MoO3Thermally hydrogenated alpha-Fe2O3·α-MoO3First catalyst Cu-alpha-Fe2O3·α-MoO3And thermally hydrogenated Cu-alpha-Fe2O3·α-MoO3The reaction was carried out in a 100mL batch autoclave (design pressure 32MPa) equipped with a magnetic stirrer. Before the reaction, a glass rod is used for stirring uniformly, then high-purity nitrogen is used for purging air in the replacement kettle and sealing the reaction kettle, and then the reaction conditions are set to be 225 ℃ and the retention time is 30 min. After the reaction is finished, removing the heating sleeve, cooling the reaction kettle by using a fan, opening the reaction kettle when the temperature in the kettle is reduced to about 25 ℃ and the pressure in the kettle is close to the ambient pressure, opening an exhaust valve to collect gas, and pouring out liquid-phase residues, used catalyst and residues; wherein the solid is dried at 105 ℃ to constant weight.
FIG. 9 is thermally hydrogenated Cu- α -Fe in example 1 of the present disclosure2O3·α-MoO3And thermally hydrogenated alpha-Fe in comparative example 12O3·α-MoO3Performance diagram for treating organic matters in biogas slurry.
As shown in FIG. 9, final thermally hydrogenated Cu- α -Fe2O3·α-MoO3After the catalyst is used for treating biogas slurry, the removal rates of water quality indexes, namely total organic carbon (NPOC), Total Nitrogen (TN), Ammonia Nitrogen (AN) and Chemical Oxygen Demand (COD), respectively reach 76.29%, 45.56%, 29.03% and 79.56%, compared with that of thermally hydrogenated alpha-Fe in comparative example 12O3·α-MoO3The effect of treating total organic carbon (NPOC) in organic matters is better. After one-time reuse, the results also show thermally hydrogenated Cu-alpha-Fe2O3·α-MoO3The NPOC and TN removal effect is better.
The above-mentioned embodiments are intended to illustrate the objects, aspects and advantages of the present disclosure in further detail, and it should be understood that the above-mentioned embodiments are only illustrative of the present disclosure and are not intended to limit the present disclosure, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present disclosure should be included in the scope of the present disclosure.

Claims (10)

1. A method of preparing a hydrothermal oxygen decoupling catalyst, comprising:
step S1: obtaining a first catalyst Cu-alpha-Fe by adopting a sol-gel method2O3·α-MoO3；
Step S2: for the first catalyst Cu-alpha-Fe2O3·α-MoO3Carrying out thermal hydrogenation treatment to obtain thermally hydrogenated Cu-alpha-Fe2O3·α-MoO3A catalyst.
2. The method of claim 1, wherein the step S1 includes:
s1.1, dissolving water-soluble Cu salt, Fe salt, Mo salt precursor and sodium alkylsulfonate surfactant with water to obtain a Cu-Fe-Mo-Na mixed solution;
s1.2, sequentially adding citric acid and ethylene glycol into the Cu-Fe-Mo-Na mixed solution, heating and stirring to obtain a first solution;
s1.3, adding ammonia water into the first solution to adjust the pH value, and continuously heating and stirring to form gel;
s1.4, drying the gel, and then calcining to obtain a first catalyst Cu-alpha-Fe2O3·α-MoO3。
3. The method of claim 2, wherein,
the precursors of the Cu salt, the Fe salt and the Mo salt are Cu (NO)3)2·3H2O、Fe(NO3)3·9H2O、(NH4)6Mo7O24·4H2O；
The sodium alkylsulfonate surfactant is CH3(CH2)11SO3Na。
4. The method of claim 1, wherein the step S2 includes:
s2.1, adding Cu-alpha-Fe into the first catalyst2O3·α-MoO3In which H is added2O2Heating and evaporating to dryness after the reaction is finished;
s2.2, adding a sucrose solution into the evaporated material of the S2.1, and stirring under heating until the evaporated material is evaporated to dryness;
s2.3, drying the evaporated S2.2, and then calcining to obtain the thermally hydrogenated Cu-alpha-Fe2O3·α-MoO3A catalyst.
5. The method of claim 2, wherein adding ammonia to the first solution to adjust the pH range comprises: 8 to 10.
6. The method of claim 2 or 4,
the heating temperature range includes: 65-85 ℃.
7. The method of claim 2 or 4,
the calcining temperature range comprises 550-650 ℃;
the calcining time range comprises 1-2 h.
8. A hydrothermal oxygen decoupling catalyst prepared by the process of any one of claims 1 to 7, the catalyst having the formula:
Cu–α-Fe2O3·α-MoO3wherein the Cu exists in the catalyst in a mode including CuO and Cu2O。
9. The hydrothermal oxygen decoupling catalyst of claim 8, wherein the alpha-MoO370-75% of alpha-Fe2O3The mass fraction of the Cu-Cu alloy accounts for 20-22%, and the mass fraction of the Cu accounts for 3-10%.
10. Use of the hydrothermal oxygen decoupling catalyst of claim 9 for treating organic wastewater, wherein the organic wastewater comprises: biogas slurry.
CN202210229811.3A 2022-03-10 2022-03-10 Hydrothermal oxygen decoupling catalyst, preparation method and application Active CN114768818B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210229811.3A CN114768818B (en) 2022-03-10 2022-03-10 Hydrothermal oxygen decoupling catalyst, preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210229811.3A CN114768818B (en) 2022-03-10 2022-03-10 Hydrothermal oxygen decoupling catalyst, preparation method and application

Publications (2)

Publication Number Publication Date
CN114768818A true CN114768818A (en) 2022-07-22
CN114768818B CN114768818B (en) 2023-08-15

Family

ID=82423950

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210229811.3A Active CN114768818B (en) 2022-03-10 2022-03-10 Hydrothermal oxygen decoupling catalyst, preparation method and application

Country Status (1)

Country Link
CN (1) CN114768818B (en)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2007144577A (en) * 2005-05-03 2009-06-10 Зюд-Хеми Аг (De) PRODUCTION OF Cu / Zn / Al-CATALYSTS BY FORMATIC METHOD
KR20130092711A (en) * 2012-02-13 2013-08-21 에스케이이노베이션 주식회사 A noble catalyst of aqueous phase reforming reaction and manufacturing method of the same
CN103289777A (en) * 2013-06-25 2013-09-11 南京理工大学 Composite oxide oxygen carrier as well as preparation method and application thereof in chemical chain oxygen decoupling
CN103586029A (en) * 2013-10-29 2014-02-19 天津大学 Catalyst for hydrogen production by water-phase reforming of biomass depolymerization product and preparation method thereof
CN104707636A (en) * 2015-02-02 2015-06-17 北京大学 Pt/alpha-MoC1-x supported catalyst, and synthesis method and application thereof
CN107008479A (en) * 2016-06-23 2017-08-04 北京大学 Metal/α MoC1‑xSupport type single atomic dispersion catalyst, its synthetic method and application
CN110642225A (en) * 2019-10-16 2020-01-03 天津大学 Method for preparing hydrogen by reforming biogas slurry water phase
CN110950513A (en) * 2019-11-26 2020-04-03 西安交通大学 Method for treating bottom mud by utilizing surfactant pretreatment-hydrothermal oxidation-thermal cracking coupling method

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2007144577A (en) * 2005-05-03 2009-06-10 Зюд-Хеми Аг (De) PRODUCTION OF Cu / Zn / Al-CATALYSTS BY FORMATIC METHOD
KR20130092711A (en) * 2012-02-13 2013-08-21 에스케이이노베이션 주식회사 A noble catalyst of aqueous phase reforming reaction and manufacturing method of the same
CN103289777A (en) * 2013-06-25 2013-09-11 南京理工大学 Composite oxide oxygen carrier as well as preparation method and application thereof in chemical chain oxygen decoupling
CN103586029A (en) * 2013-10-29 2014-02-19 天津大学 Catalyst for hydrogen production by water-phase reforming of biomass depolymerization product and preparation method thereof
CN104707636A (en) * 2015-02-02 2015-06-17 北京大学 Pt/alpha-MoC1-x supported catalyst, and synthesis method and application thereof
CN107008479A (en) * 2016-06-23 2017-08-04 北京大学 Metal/α MoC1‑xSupport type single atomic dispersion catalyst, its synthetic method and application
CN110642225A (en) * 2019-10-16 2020-01-03 天津大学 Method for preparing hydrogen by reforming biogas slurry water phase
CN110950513A (en) * 2019-11-26 2020-04-03 西安交通大学 Method for treating bottom mud by utilizing surfactant pretreatment-hydrothermal oxidation-thermal cracking coupling method

Also Published As

Publication number Publication date
CN114768818B (en) 2023-08-15

Similar Documents

Publication Publication Date Title
CN111036243B (en) Oxygen vacancy-containing transition metal-doped BiOBr nanosheet photocatalyst and preparation method and application thereof
CN107649168A (en) The method of bisphenol-A and its catalyst used in a kind of photocatalytic degradation water
CN113398936B (en) Zinc oxide/ZnFe-LDH @ charcoal visible-light-driven photocatalyst and preparation method and application thereof
CN106944028A (en) A kind of preparation method of the graphene-based complex solid base catalyst of 3D structures
WO2022268021A1 (en) Cu-based catalyst and use thereof for photocatalytic water-based hydrogen production-5-hydroxymethylfurfural (hmf) oxidation coupling reaction
CN112553651B (en) Preparation method of selenide coated carbon nanotube material
CN113952986A (en) WO (WO)3TpPa-1-COF composite material and preparation method and application thereof
CN112774718A (en) Cuprous oxide/tubular graphite-like phase carbon nitride composite catalyst and preparation method and application thereof
CN110404585B (en) Method for preparing MOF (Metal organic framework) sheet on substrate by utilizing water bath heating
CN113321255B (en) Preparation method and application of manganese oxide-biochar composite solar interface evaporation material
CN106807382A (en) A kind of preparation method of high dispersive Ni/C catalyst
Wang et al. Ni/MOFs-derived α-MoO3 catalyst for renewable hydrogen production and treatment of biogas slurry by aqueous-phase reforming
CN114768818B (en) Hydrothermal oxygen decoupling catalyst, preparation method and application
CN112316962A (en) BiPO4BiOBr p-n heterojunction composite photocatalytic material and preparation method thereof
CN115029724B (en) Preparation method and application of metal-doped 2H-phase molybdenum disulfide electrocatalyst
CN116726973A (en) Flower-ball-shaped sulfur indium zinc/carbon nitride heterojunction photocatalyst, and preparation method and application thereof
CN114904534B (en) Bismuth molybdate/ferric vanadate composite nano material, preparation method thereof and application thereof in acousto-optic catalytic degradation of pollutants in water
CN114214640B (en) Biomass carbon-based nano molybdenum carbide-molybdenum nitride heterojunction composite catalyst and method
CN116351438A (en) Cerium oxide indium sulfide photocatalytic material and preparation method and application thereof
CN115490258B (en) Copper oxide nano-sheet catalyst, preparation method and application thereof in electrocatalytic reduction of carbon dioxide and carbon monoxide
CN112774689B (en) Manganese-doped bismuth ferrite nanowire and preparation method and application thereof
Wang et al. Hydrothermal oxygen uncoupling of high-concentration biogas slurry over Cu-α-Fe2O3· α-MoO3 catalyst
CN113546615A (en) Bi2WO6/Black-TiO2Composite catalyst and preparation method and application thereof
CN109759092B (en) Preparation method and application of flower-shaped cobalt molybdenum sulfur microsphere embedded graphene nanosheet
CN112604717A (en) Preparation method of quantum dot iron-based metal organic framework composite material

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