CN113842904B - Tungsten single-atom catalyst with graphene substrate, and preparation method and application thereof - Google Patents

Tungsten single-atom catalyst with graphene substrate, and preparation method and application thereof Download PDF

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CN113842904B
CN113842904B CN202111215969.7A CN202111215969A CN113842904B CN 113842904 B CN113842904 B CN 113842904B CN 202111215969 A CN202111215969 A CN 202111215969A CN 113842904 B CN113842904 B CN 113842904B
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graphene
catalyst
tungsten
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atom
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CN113842904A (en
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李阳
蔡安
范晓彬
张凤宝
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Tianjin University
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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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • 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
    • B01J35/391—Physical properties 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/617—500-1000 m2/g
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
    • C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
    • C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
    • C07C209/365—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst by reduction with preservation of halogen-atoms in compounds containing nitro groups and halogen atoms bound to the same carbon skeleton
    • 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
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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Abstract

The invention discloses a tungsten monoatomic catalyst with a graphene substrate, wherein the catalyst takes oligolayer graphene as the substrate, and metal tungsten is uniformly dispersed in a monoatomic form and anchored on the surface of the substrate graphene. The invention also discloses a preparation method and application of the tungsten single-atom catalyst with the graphene substrate. The catalyst of the invention has higher efficiency and higher stability.

Description

Tungsten single-atom catalyst with graphene substrate, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a tungsten single-atom porous catalyst taking graphene as a substrate, and a preparation method and application thereof.
Background
The halogenated aniline can be applied to the synthesis of pigments, dyes and the like. According to the current international market demand analysis of parachloroaniline, the demand of parachloroaniline increases at an average 6.5% increase rate per year, wherein the enterprise for producing parachloroaniline increases 43.9% from 2015 to 2019, and the industry profit increases 37.6%. The domestic demand for p-chloroaniline also increases at an average rate of 7.9% per year, and the export amount is also increasing as compared to the import amount. It is therefore a current direction of development how to effectively increase the capacity of halogenated anilines and reduce the production costs. Although the existing industrial mature technology exists in the halogenated aniline synthesis technology, the problems of low yield and unstable product quality exist all the time. Thus, research and development of the synthesis process of halogenated aniline and the catalyst are still hot spots of research.
The halogenated nitrobenzene is widely applied to the chemical industry such as dye, pesticide and the like and the field of medicine synthesis, and the productivity thereof is rapidly increased in recent years. The halonitrobenzene is easy to leak into the environment and causes pollution due to improper operation in production, transportation, use and wastewater treatment. Halonitrobenzene is difficult to degrade naturally and has certain genetic toxicity, which negatively affects the environment and human life. The existing treatment modes of halogenated nitrobenzene generally comprise a physical adsorption method, a biological degradation method, a chemical oxidation method, a reduction method and the like; wherein the reduction process using selective hydrogenation is capable of converting halonitrobenzene into haloaniline. The reduction method has mild reaction conditions, and the product is an aniline compound with high added value, so that on one hand, the pollution problem of halogenated nitrobenzene is solved, and on the other hand, the productivity of halogenated aniline is improved, and the method has good industrial application value. The core of the hydrogenation reduction process of halogenated nitrobenzene is a catalyst; conventional catalysts include Raney nickel, noble metal catalysts, iron-based catalysts, and the like; however, raney nickel and noble metal catalysts have high production and use costs, while iron catalysts have low atomic utilization and poor selectivity. Therefore, the development of a reduction catalyst with low cost and high activity for selectively hydrogenating the halogenated nitrobenzene, which can efficiently convert the halogenated nitrobenzene into halogenated aniline, has profound significance.
The single-atom catalyst has high atom utilization rate and is widely focused. Compared with a metal substrate, the metal single-atom catalyst constructed by the carbon substrate is easier to obtain and lower in cost, and the carbon substrate generally has good thermal conductivity and high temperature resistance, so that the catalyst can be ensured to keep activity at high temperature; meanwhile, the carbon substrate has good chemical stability, and the catalyst is not easy to poison and inactivate. The research on the preparation of the tungsten single-atom catalyst of the carbon substrate is relatively lacking, and the application of the tungsten single-atom catalyst to the hydrogenation reduction reaction of halogenated nitrobenzene is still in a blank stage.
The present invention has been made to solve the above problems.
Disclosure of Invention
The invention provides a preparation method of a tungsten single-atom porous catalyst taking graphene as a substrate. The catalyst is prepared by taking oligolayer graphene as a substrate, uniformly dispersing metal tungsten in a single atom form, anchoring the metal tungsten on the surface of the substrate graphene, and forming a porous network structure by cross-linking the layers of the substrate graphene, wherein the substrate graphene has a large specific surface area. The catalyst is used for the reaction of reducing halogenated nitrobenzene into halogenated aniline by selective hydrogenation, and has high catalytic efficiency and difficult deactivation.
The technical scheme of the invention is as follows:
the first aspect of the invention discloses a tungsten monoatomic catalyst with a graphene substrate, wherein the catalyst takes oligolayer graphene as the substrate, and metal tungsten is uniformly dispersed in a monoatomic form and anchored on the surface of the substrate graphene.
Preferably, the layers of the substrate graphene are mutually crosslinked to form a porous network structure, and the specific surface area of the porous network structure is 500-700m 2 g -1 。
Preferably, the tungsten monoatoms are anchored on the surface of the base graphene.
The invention discloses a preparation method of the tungsten single-atom catalyst with the graphene substrate, which comprises the following steps:
(1) adding a tungsten metal precursor into the aqueous dispersion liquid of the graphene oxide, and uniformly dispersing;
(2) adding ethylenediamine into the dispersion liquid in the step (1), uniformly mixing, heating and reacting for a period of time to obtain graphene hydrogel, and freeze-drying the graphene hydrogel to obtain graphene aerogel;
(3) and (3) pyrolyzing the graphene aerogel obtained in the step (2) to obtain the tungsten single-atom catalyst with the graphene substrate.
Preferably, in step (1), a nitrogen source is added, wherein the added nitrogen source is a soluble nitrate such as lithium nitrate, sodium nitrate, potassium nitrate or ammonium nitrate, and if sodium nitrate is added, the added amount is as follows: the mass ratio of the graphene oxide to the sodium nitrate is (2-10) to 1.
Preferably, the tungsten metal precursor in the step (1) is ammonium tungstate, and the mass ratio of the graphene oxide to the ammonium tungstate is 1:2-15.
Preferably, the adding amount of the ethylenediamine in the step (2) is that the volume ratio of graphene oxide to ethylenediamine is (2-10) to 1; the reaction temperature is 160-180 ℃ and the reaction time is 8-15h.
Preferably, the pyrolysis temperature of step (3) is 800-1000 ℃ for 1-5 hours.
The third aspect of the invention discloses the application of the tungsten single-atom catalyst with the graphene substrate in the selective hydrogenation reduction of halogenated nitrobenzene into halogenated aniline.
The invention has the beneficial effects that:
1. according to the tungsten single-atom catalyst with the graphene substrate, the substrate graphene is a single layer or a few layers (oligolayers), the graphene layers are mutually crosslinked to form a porous network-like structure, the specific surface area is large, and the specific surface area is 500m 2 g -1 The above; the tungsten metal monoatoms are uniformly dispersed on the surface of the graphene, and the tungsten metal monoatoms are anchored on the surface of the graphene, so that more active sites can be exposed, and the contact between the active sites and a reaction substrate is increased; the graphene has good physical and chemical properties such as thermal conductivity and stability, and the catalyst is not easy to deactivate in the use process. The catalyst is used for catalyzing the reaction of halogenated nitrobenzene selective hydrogenation reduction to halogenated aniline, the conversion rate can reach 100%, and the selectivity is not lower than 97%; and the catalyst may be reused at least 8 times. The conversion rate of the catalyst in the prior art for catalyzing nitrobenzene only can reach 55% at most, and the catalyst can be reused for no more than 2 times. Therefore, the catalyst of the invention has higher efficiency and higher stability, and is superior to the catalyst in the prior art.
2. The preparation method of the tungsten single-atom catalyst with the graphene substrate is relatively simple, and the single-atom catalyst can be prepared without post-treatment such as acid washing and the like and can be prepared in a large quantity. The metal precursor and the nitrogen source are added and reacted simultaneously, so that the anchoring of nitrogen atoms to metal atoms can be promoted, and the metal atoms are more stable and more uniformly dispersed; meanwhile, the preparation method can form a porous structure, and a porous network structure with larger specific surface area can be obtained without an additional pore-forming step. In the prior art, metal salts are limited between graphene sheets and defects in a mode of adding hydrogen peroxide to form a pore defect limiting domain, and then the catalyst is further calcined in an ammonia atmosphere to prepare the monoatomic catalyst with metal coordinated with nitrogen. According to the invention, the nitrogen source and the metal salt are directly added in one step, and the metal salt and the nitrogen atom form active site elements first and then are compounded with the carrier, so that the effect of anchoring metal is improved, the stability of the metal atom is improved, and the risk of calcining under an ammonia atmosphere is reduced.
3. The ethylenediamine added in the invention has double functions of reduction and serving as a nitrogen source; but adding a nitrogen source, such as a soluble nitrate, to the aqueous dispersion of graphene oxide of the metal precursor is better.
Drawings
Fig. 1 is an XRD pattern of a tungsten monoatomic catalyst with graphene substrate obtained in example 3.
Fig. 2 a and b are XPS graphs of graphene aerogel (a) before pyrolysis and tungsten monoatomic catalyst (b) with graphene substrate after pyrolysis, respectively, obtained in example 3.
Fig. 3 is an SEM image of the graphene-based tungsten monoatomic catalyst obtained in example 3.
Fig. 4 is a TEM image and a Mapping image of the tungsten single-atom catalyst with graphene substrate obtained in example 3.
Fig. 5 is a STEM diagram of a tungsten single-atom catalyst with a graphene substrate obtained in example 3.
Detailed Description
In order to make the objects, technical solutions and advantageous effects of the present invention more apparent, the following detailed description will be made with reference to examples so as to facilitate understanding by the skilled person.
Example 1: preparing a tungsten monoatomic catalyst with a graphene substrate, comprising the following steps:
step 1: adding 0.5000g of tungsten metal precursor ammonium tungstate into aqueous dispersion liquid containing 0.0800g of graphene oxide, and uniformly dispersing;
step 2: adding 4.0mL of ethylenediamine into the dispersion liquid in the step 1, uniformly mixing, heating to 180 ℃, and reacting for 12 hours to obtain graphene hydrogel; drying the graphene hydrogel by a freeze dryer to remove a solution in the hydrogel, so as to obtain graphene aerogel;
step 3: and (3) pyrolyzing the graphene hydrogel obtained in the step (2) for 3 hours at 900 ℃ in a nitrogen atmosphere to obtain the tungsten monoatomic catalyst with the graphene substrate.
Example 2
The procedure and conditions were the same as in example 1 except that 0.0100g of sodium nitrate was added in step 1 to obtain the tungsten monoatomic catalyst with graphene substrate.
Example 3
The procedure and conditions were the same as in example 2 except that the amount of ethylenediamine added in step 2 was changed and the amount of ethylenediamine added was adjusted to 8.0mL, to obtain the graphene-based tungsten monoatomic catalyst.
Example 4
The procedure and conditions were the same as in example 3 except that the amount of the precursor ammonium tungstate was changed in step 1, and the amount of ammonium tungstate added was adjusted to 1.0000g, to obtain the tungsten monoatomic catalyst with a graphene substrate.
FIG. 1 is an XRD pattern of a tungsten single-atom catalyst with graphene substrate obtained in example 3; figures 2 a and b are XPS graphs of graphene aerogel (a) before pyrolysis and tungsten monoatomic catalyst (b) with graphene substrate after pyrolysis, respectively; FIG. 3 is an SEM image of a tungsten single-atom catalyst with graphene substrate obtained in example 3; FIG. 4 is a TEM image and a Mapping image of a tungsten single-atom catalyst with a graphene substrate obtained in example 3; fig. 5 is a STEM diagram of a tungsten single-atom catalyst with a graphene substrate obtained in example 3. From FIG. 1 it is possible toIt was seen that the resulting catalyst exhibited only graphitic carbon peaks, without peaks of tungsten metal element nanoparticles. It can be seen from fig. 2 that the tungsten metal element presents a non-0 valence metal state in the material, and that after pyrolysis (fig. b) of the graphene aerogel, there is a significant shift in the peaks of the tungsten metal element compared to before pyrolysis (fig. a), indicating a bonding effect between the tungsten metal atom and the nitrogen atom, indicating an anchoring effect of the nitrogen atom to the tungsten metal atom. As can be seen from fig. 3, the graphene is an oligolayer (i.e. a single layer or a few layers), and graphene sheets are mutually crosslinked to form a network-like structure; specific surface area of 630m by BET calculation 2 g -1 . From fig. 4a it can be seen that graphene sheets in the material have folds and no nanoparticles, and from a further Mapping graph (fig. 4 b) it can be seen that carbon, nitrogen, oxygen, tungsten elements are distributed on the material surface, wherein the tungsten metal elements are uniformly distributed on the graphene surface. It can be further confirmed from fig. 5 that the tungsten metal element exists as a tungsten monoatomic form on the surface of graphene. It can be seen from fig. 1 to 5 that the tungsten metal element exists as a tungsten monoatom on the surface of graphene.
Example 5: the tungsten single-atom catalyst with graphene substrate obtained in example 3 was used for the reaction of selective hydrogenation reduction of halogenated nitrobenzene to halogenated aniline.
Methanol or ethanol and the like are selected as solvents, and 100mg of p-chloronitrobenzene as a reaction substrate and 20mg of the catalyst obtained in example 3 are added to the solvents and placed in a reaction kettle. And (3) replacing air in the kettle by adopting hydrogen, stamping to about 2Mpa, setting the reaction temperature to 180 ℃, setting the stirring speed to 300r/min, and stopping the reaction after 4 hours of reaction. Samples were taken before and after the reaction, and the reactants and products were quantitatively and qualitatively analyzed using a gas chromatograph and a gas chromatograph-mass spectrometer. The results were: the conversion rate can reach 100%, and the selectivity is 98%; after 8 times of repeated use of the catalyst, the conversion and the selectivity were not substantially lowered.
Example 6: the procedure and conditions were the same as in example 5, except that the tungsten single-atom catalyst with graphene substrate obtained in example 1 was used for the reaction of selective hydrogenation reduction of halogenated nitrobenzene to halogenated aniline.
The results were: the conversion rate can reach 44% and the selectivity is 88%.
Example 7: the procedure and conditions were the same as in example 5, except that the tungsten single-atom catalyst with graphene substrate obtained in example 2 was used for the reaction of selective hydrogenation reduction of halogenated nitrobenzene to halogenated aniline.
The results were: the conversion rate can reach 60% and the selectivity is 93%.
Example 8: the procedure and conditions were the same as in example 5, except that the tungsten single-atom catalyst with graphene substrate obtained in example 4 was used for the reaction of selective hydrogenation reduction of halogenated nitrobenzene to halogenated aniline.
The results were: the conversion rate can reach 97% and the selectivity is 96%.
From the above results, it is clear that when the ratio of sodium nitrate to ethylenediamine is high in a certain range, the conversion rate and selectivity of the catalyst for selective hydrogenation reduction of halogenated nitrobenzene to halogenated aniline are high.
Comparative example
Co monoatomic catalyst in literature (Sun, X.; olivos-Suarez, A.I.; osadcii, D.; romero, M.J.V.; kapteijn, F.; gascon, J.; single cobalt sites in mesoporous N-doped carbon matrix for selective catalytic hydrogenation of nitroarenes. Journalysis 2018,357, 20-28.) (note: experiments with halonitrobenzene were also performed in this literature but no data for conversion were given.) this literature is to demonstrate performance on nitrobenzene as a representative, if nitrobenzene performance should not be good, the performance should also be general;) a mass ratio of 1:14.3, the reaction temperature is 110 ℃ (note: the literature pressure is higher, so the temperature and time can be correspondingly reduced, and this literature is intended to highlight materials with higher selectivities, so avoiding high conversions resulting in reduced catalyst selectivities), and reaction pressure 3MPa; when the reaction time is 2h (note: this document is to highlight that the catalyst selectivity is high, so that no highlight is made in terms of the conversion rate, and the time is short), the conversion rate is up to 55%, the selectivity is larger than or equal to 99%, the cobalt metal element is gradually precipitated after the catalyst is repeatedly used for 2 times, and the conversion rate and the selectivity of the catalyst are obviously reduced (note: the conditions in the comparative document are not completely consistent with the examples of the present invention but can also illustrate the problems).
From the results of example 5 and comparative example, the catalyst in this patent has higher conversion rate and higher stability, and can be reused many times.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the foregoing embodiments, which have been described in the foregoing description merely illustrates the principles of the invention, and that various changes and modifications may be made therein without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (3)

1. The tungsten monoatomic catalyst with the graphene substrate is characterized in that the catalyst takes oligolayer graphene as the substrate, and metal tungsten is uniformly dispersed on the surface of the substrate graphene in a monoatomic mode; the preparation method of the tungsten single-atom catalyst with the graphene substrate comprises the following steps:
(1) adding a tungsten metal precursor into the aqueous dispersion liquid of the graphene oxide, and uniformly dispersing; the tungsten metal precursor is ammonium tungstate, and the mass ratio of graphene oxide to ammonium tungstate is 1:2-15;
(2) adding ethylenediamine into the dispersion liquid in the step (1), uniformly mixing, heating and reacting for a period of time to obtain graphene hydrogel, and freeze-drying the graphene hydrogel to obtain graphene aerogel; the reaction temperature is 160-180 ℃ and the reaction time is 8-15h;
(3) pyrolyzing the graphene aerogel obtained in the step (2) to obtain the tungsten single-atom catalyst with the graphene substrate; the pyrolysis temperature is 800-1000 ℃ and the time is 1-5h.
2. The catalyst according to claim 1Characterized in that the substrate graphene is a porous network structure formed by cross-linking graphene layers, and the specific surface area is 500-700m 2 g -1 。
3. Use of a tungsten single-atom catalyst with graphene substrate according to any one of claims 1-2 for the selective hydrogenation reduction of halonitrobenzene to haloaniline.
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