CN108144631B - Transition metal sulfide catalyst, method for producing same, and method for producing aromatic amine compound - Google Patents

Transition metal sulfide catalyst, method for producing same, and method for producing aromatic amine compound Download PDF

Info

Publication number
CN108144631B
CN108144631B CN201711419312.6A CN201711419312A CN108144631B CN 108144631 B CN108144631 B CN 108144631B CN 201711419312 A CN201711419312 A CN 201711419312A CN 108144631 B CN108144631 B CN 108144631B
Authority
CN
China
Prior art keywords
transition metal
catalyst
graphene oxide
metal sulfide
sulfide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201711419312.6A
Other languages
Chinese (zh)
Other versions
CN108144631A (en
Inventor
江鸿
徐万飞
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.)
University of Science and Technology of China USTC
Original Assignee
University of Science and Technology of China USTC
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 University of Science and Technology of China USTC filed Critical University of Science and Technology of China USTC
Priority to CN201711419312.6A priority Critical patent/CN108144631B/en
Publication of CN108144631A publication Critical patent/CN108144631A/en
Application granted granted Critical
Publication of CN108144631B publication Critical patent/CN108144631B/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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0219—Coating the coating containing organic 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/043—Sulfides with iron group metals or platinum group metals
    • 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
    • B01J35/33—Electric or magnetic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J35/393—Metal or metal oxide crystallite size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/394—Metal dispersion value, e.g. percentage or fraction
    • 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
    • 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
    • B01J37/16—Reducing
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Catalysts (AREA)

Abstract

The invention provides a transition metal sulfide catalyst which is composed of reduced graphene oxide and transition metal sulfide loaded on the surface of the reduced graphene oxide. The application also provides a preparation method of the transition metal sulfide catalyst. The present application also provides a method for preparing an aromatic amine compound using the transition metal sulfide catalyst. The transition metal sulfide catalyst provided by the application takes transition metal sulfide as a main active ingredient, and reduced graphene oxide as a carrier has certain catalytic activity, so that the catalyst has the characteristics of high conversion rate, high selectivity and the like.

Description

Transition metal sulfide catalyst, method for producing same, and method for producing aromatic amine compound
Technical Field
The invention relates to the technical field of catalyst synthesis, in particular to a transition metal sulfide catalyst, a preparation method thereof and a preparation method of an aromatic amine compound.
Background
Aromatic amine compounds are extremely important organic synthesis intermediates, and are widely applied to synthesis of dyes, pesticides and medicines. The aromatic amine is generally obtained by reducing aromatic nitro compounds, common reduction methods comprise a metal/acid reduction method and a catalytic hydrogenation method, but the metal/acid catalyst is adopted to cause the generation of a large amount of metal mud, and the catalytic hydrogenation method is usually carried out under high pressure, so that higher requirements on the safety performance of equipment are provided. In the reduction method, hydrazine hydrate serving as a liquid-phase reducing agent has certain toxicity, and in comparison, sodium borohydride has the characteristics of low price, no toxicity, mild reaction conditions and the like, so the sodium borohydride is a good reducing agent. The traditional catalysts for catalytic reduction of aromatic nitro compounds by sodium borohydride are Pd/C, Pt, Au and Ag, but all of them are noble metals and expensive, so the development of a novel cheap catalyst is particularly urgent.
In recent years, iron catalysts such as Fe (III) compounds, FeO (OH) and the like are used more often, and the catalysts are low in price, but the FeO (OH) catalysts are converted into alpha-Fe at the temperature higher than 70 DEG C2O3Resulting in rapid deactivation of the catalyst. Therefore, it is very urgent to develop a highly efficient and inexpensive catalyst for catalytic reduction of aromatic nitro compounds.
Graphene serving as a novel carbon material has an ultra-large specific surface area given by a unique two-dimensional structure of the thickness of a monoatomic layer, and the theoretical specific surface area is as high as 2600m2The specific surface area of the material is much higher than that of other existing materials, and the material has excellent mechanical property, thermal property and electrical property and has wide prospect in the aspect of catalytic application. The graphene material can be prepared from graphite, graphite oxide and derivatives thereof, and can realize batch production. The conjugated structure of the graphene enables the graphene to have strong adsorption capacity on reaction raw materials, and the excellent electron transport performance of the graphene can promote electron transfer in catalytic reaction, so that the catalytic activity is improved, and the graphene can be used as an active component of a catalyst and a carrier. Traditional hydrogenation catalysts are generally in a supported type, a carrier material is used as a supporting medium, some carriers do not provide an active center and only provide a larger surface for supporting an active component, so that the high dispersion and high activity of the active component are kept; some carriers can also cooperate with active components to play a synergistic role in regulating and controlling the activity or selectivity of the catalyst. The special structural characteristics of the graphene enable the graphene to be capable of loading active components with high dispersion and high stability, regulating and controlling the microscopic properties of the active components, and the graphene has high adsorbability on hydrogen molecules, and is an ideal hydrogenation catalyst carrier. Therefore, the catalyst can be used as a carrier of transition metal to prepare a high-efficiency and low-cost catalyst for catalytic reduction of aromatic nitro compounds.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a transition metal sulfide catalyst, and the transition metal sulfide catalyst provided by the application has the characteristics of high conversion rate, high selectivity and high cycle stability when being used as a catalyst for preparing an aromatic amine compound.
In view of the above, the present application provides a transition metal sulfide catalyst, which is composed of reduced graphene oxide and a transition metal sulfide supported on the surface of the reduced graphene oxide.
Preferably, the transition metal in the transition metal sulfide is selected from one or more metal elements of group VIII, IB, and IIB transition metals, and Ru, Rh, Pt, and Ir are not included.
Preferably, the transition metal sulfide is selected from FeS, CoS or NiS.
The application also provides a preparation method of the transition metal sulfide catalyst, which comprises the following steps:
mixing transition metal salt, sulfide, a reducing agent, a dispersing agent, water and graphene oxide, and carrying out hydrothermal reaction in a high-pressure reaction kettle to obtain the transition metal sulfide catalyst.
Preferably, the reducing agent is selected from one or more of ethylene glycol, glycerol, acetaldehyde and propionaldehyde; the dispersant is PVP (K-30); the transition metal salt is transition metal nitrate; the transition metal in the transition metal salt is selected from one or more metal elements in VIII group, IB group and IIB group transition metals, and Ru, Rh, Pt and Ir are not included; the sulfide is inorganic sulfide selected from Na2S、K2S、(NH4)2SO4One or more of (a).
Preferably, the molar ratio of the transition metal salt to the sulfide is (0.5-2): 1.
preferably, the mixing further comprises:
and dispersing the graphene oxide powder into an aqueous solution, and ultrasonically stripping to obtain a graphene oxide dispersion liquid.
Preferably, the temperature of the hydrothermal reaction is 150-200 ℃ and the time is 24-36 h.
The present application also provides a method for preparing an aromatic amine compound, comprising:
carrying out water bath reaction on an aromatic nitro compound, a reducing agent, a catalyst and water to obtain an aromatic amine compound; the catalyst is the transition metal sulfide catalyst prepared by the preparation method described in the scheme or the preparation method described in the scheme.
Preferably, the reducing agent is sodium borohydride or potassium borohydride.
The application provides a transition metal sulfide catalyst, which consists of reduced graphene oxide and transition metal sulfide loaded on the surface of the reduced graphene oxide. According to the method, the transition metal sulfide catalyst is used as a catalyst for preparing the aromatic amine compound, and the reduced graphene oxide is used as a carrier and has certain catalytic activity; meanwhile, the transition metal in the transition metal sulfide has a special 3 d-valence electron shell structure, and the special electron structure endows the transition metal sulfide with good electrochemical performance, so that the obtained catalyst can quickly obtain the aromatic amine compound at normal temperature, and has the characteristics of high conversion rate, high selectivity and high cycle stability. Furthermore, the catalyst provided by the application is a heterogeneous catalyst, and can be quickly separated after the reaction is finished, so that the catalyst can be recycled.
Drawings
FIG. 1 is a schematic diagram of the present invention for preparing aromatic amine compounds;
FIG. 2 is a scanning electron micrograph of FeS @ rGO prepared in example 1 of the present invention;
FIG. 3 is a FeS @ rGO XRD spectrum prepared in example 1 of the present invention;
FIG. 4 is a graph showing the effect of FeS @ rGO on the reduction of 4-NP catalyzed by the catalyst prepared in example 1 of the present invention;
FIG. 5 is a scanning electron micrograph of CoS @ rGO prepared in example 2 of the present invention;
FIG. 6 is an XRD spectrum of CoS @ rGO prepared in example 2 of the present invention;
FIG. 7 is a graph of the effect of CoS @ rGO on the reduction of 4-NP catalyzed by example 2 of the present invention;
FIG. 8 is a scanning electron micrograph of NiS @ rGO prepared in example 3 of the present invention;
FIG. 9 is an XRD spectrum of NiS @ rGO prepared in example 3 of the present invention;
FIG. 10 is a graph showing the effect of NiS @ rGO on the reduction of 4-NP catalyzed by the catalyst prepared in example 3 of the present invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
Aiming at the problem that the price of a catalyst for preparing aromatic amine compounds in the prior art is higher, the embodiment of the invention discloses a transition metal sulfide catalyst which is cheap and efficient; specifically, the application provides a transition metal sulfide catalyst, which consists of reduced graphene oxide and a transition metal sulfide loaded on the surface of the reduced graphene oxide.
In the present application, the transition metal sulfide catalyst consists of reduced graphene oxide and a transition metal sulfide, wherein the transition metal sulfide is supported on the surface of the reduced graphene oxide. Graphene is used as a novel two-dimensional carbon material, the huge specific surface area of the graphene enables the graphene to be capable of loading active components with high dispersion and high stability, the conjugated structure of the graphene enables the graphene to have strong adsorption capacity on reaction raw materials, and the excellent electron transport performance of the graphene can promote electron migration in catalytic reaction, so that the catalytic activity is improved, and therefore the graphene can be used as an active component of a catalyst and a carrier, and further plays a synergistic effect on the catalytic reaction, and the activity or selectivity of the catalyst is regulated and controlled; the reduced graphene oxide has better conductivity; the transition metal sulfide has a special 3 d-valence electron shell structure, and the special electron structure endows the transition metal sulfide with good electrochemical performance, and the transition metal sulfide is loaded on the surface of reduced graphene oxide, so that the activity of the transition metal sulfide can be further improved.
In the application, most transition metals in the transition metal sulfide are selected from one or more metal elements in VIII group, IB group and IIB group transition metals, and Ru, Rh, Pt and Ir are not included; specifically, the transition metal can be selected from Fe, Co, Cu, Zn or Ni; in particular embodiments, the transition metal is selected from Fe, Co, or Ni. The transition metal sulfide described herein is selected from FeS, CoS or NiS.
The invention also provides a preparation method of the transition metal sulfide catalyst, which comprises the following steps:
mixing transition metal salt, sulfide, a reducing agent, a dispersing agent, water and graphene oxide, and carrying out hydrothermal reaction in a high-pressure reaction kettle to obtain the transition metal sulfide catalyst.
In the process of preparing the transition metal sulfide catalyst, water is used as a solvent, graphene oxide is used as a carrier, a proper amount of transition metal salt and sulfide are subjected to hydrothermal reaction, a reducing agent is used for reducing the graphene oxide, the valence state of metal is controlled at the same time, the reduced graphene oxide with better conductivity can be obtained, and the dispersing agent is beneficial to more uniform dispersion of the metal sulfide on the carrier.
In the present application, the reducing agent is selected from one or more of ethylene glycol, glycerol, acetaldehyde and propionaldehyde, in particular embodiments the reducing agent is selected from ethylene glycol or glycerol; the dispersant is PVP (K-30); the transition metal salt is transition metal nitrate; the transition metal in the transition metal salt is selected from one or more metal elements selected from VIII group, IB group and IIB group transition metals, and Ru, Rh, Pt and Ir are not included; the sulfide is inorganic sulfur compound selected from Na2S、K2S、(NH4)2SO4One or more of (a).
The molar ratio of the transition metal salt to the sulfide is (0.5-2): 1.
in the process of preparing the transition metal sulfide catalyst, a one-step reaction occurs, and the specific reaction process is M2++S2+→ MS, the generated transition metal sulfide is deposited on the graphene sheet and then grows in situ, PVP is taken as a dispersing agent to ensure the uniform dispersion of nano particles, the weak reducibility of a reducing agent can ensure that transition metal ions are in positive bivalence state, and then the transition metal main body is ensuredThe minor form is bivalent and exists in the form of MS.
The above reaction process is carried out in one step, but the order of addition of the raw materials may be carried out in the following manner to ensure sufficient mixing of the raw materials:
dispersing graphene oxide powder into an aqueous solution, and ultrasonically stripping to obtain a uniform graphene oxide dispersion liquid;
adding a transition metal salt and a dispersing agent into the graphene oxide dispersion liquid, and performing ultrasonic dispersion to obtain a first solution;
adding sulfide into a reducing agent for dissolving to obtain a second solution;
adding the second solution into the first solution, and stirring at room temperature; and transferring the solution to a Teflon hydrothermal reaction kettle for hydrothermal reaction, naturally cooling to room temperature, and filtering and drying to obtain the reduced graphene oxide supported transition metal sulfide catalyst.
According to the invention, in the hydrothermal reaction process, the temperature of the hydrothermal reaction is 150-200 ℃ and the time is 24-36 h.
In the preparation process of the transition metal sulfide catalyst, the molar ratio of the transition metal salt to the sulfide is (0.5-2): 1, the ratio of sulfide to graphene is 1mmol:100mg, H2The volume ratio of O to the reducing agent is 3:1, and the concentration of the dispersing agent is 0.5 mg/ml.
The present application provides a method for preparing an aromatic amine compound using the above transition metal sulfide catalyst, comprising:
carrying out water bath reaction on an aromatic nitro compound, a reducing agent, a catalyst and water to obtain an aromatic amine compound; the catalyst is the transition metal sulfide catalyst prepared by the preparation method described in the scheme or the preparation method described in the scheme.
In the above process for preparing the aromatic amine compound, the aromatic nitro compound is an aromatic nitro compound well known to those skilled in the art, and the application is not particularly limited, and in specific examples, the aromatic nitro compound is selected from para-nitro compounds, and more specifically, the aromatic nitro compound is selected from para-nitrophenol, and the reduction thereof produces para-aminophenol. The reducing agent is selected from sodium borohydride or potassium borohydride. As shown in fig. 1, fig. 1 is a schematic view of a reaction for preparing an aromatic amine compound according to the present application. In the present application, an aromatic nitro compound is reacted with a reducing agent and a catalyst to obtain an aromatic amine compound.
In the preparation process of the aromatic amine compound, the concentration of the catalyst is 0.33mg/mL, the concentration of the aromatic nitro compound is 1mmol/L, the concentration of the reducing agent is 10mmol/L, the reaction temperature is 20-70 ℃, and in the specific embodiment, the reaction temperature is 30 ℃.
The transition metal sulfide catalyst provided by the invention can quickly obtain corresponding amine compounds at normal temperature and normal pressure, and has the characteristics of high conversion rate, high selectivity, high cycle stability and the like. In addition, the catalyst provided by the application is a heterogeneous catalyst, and can be quickly separated after the reaction is finished, so that the catalyst can be recycled. Experimental results show that the catalyst provided by the application can ensure that the conversion rate and the selectivity of raw materials are both more than 99%. The invention also provides a synthesis method of aromatic amine, under the action of the catalyst, sodium borohydride is used as a reducing agent, and after reaction raw materials, a solvent, the sodium borohydride and the catalyst are mixed, the mixture is stirred at normal temperature and normal pressure, and then the corresponding amine compound can be quickly obtained. The synthesis method provided by the invention is simple to operate, does not need high temperature or pressurization, reduces the requirements on reaction equipment, and saves equipment cost; the method is rapid and efficient, has high conversion rate and selectivity, and can be well applied to large-scale production of amine compounds.
For further understanding of the present invention, the transition metal sulfide catalyst and its application provided by the present invention will be described in detail with reference to the following examples, and the scope of the present invention is not limited by the following examples.
Example 1
Dispersing 0.1g of graphene oxide powder into 60ml of water solution, carrying out ultrasonic stripping to obtain uniform graphene oxide dispersion liquid, and adding 404mg of Fe (NO) into the solution3)3·9H2O and 40mg PVP (K-30), ultrasonically dispersing for 30min, and mixing with 20ml of Na with ethylene glycol as a solvent2And (3) mixing the S (1mmol, 78mg) solution, continuously stirring at room temperature, transferring to a Teflon hydrothermal reaction kettle after 60min, carrying out hydrothermal reaction at 180 ℃ for 24h, naturally cooling to room temperature, and filtering and drying to obtain the FeS @ rGO catalyst. Fig. 2 is a scanning electron microscope photograph of the FeS @ rGO catalyst prepared in this example, and it can be seen from the figure that the reduced graphene oxide sheet after hydrothermal treatment becomes wrinkled, which greatly increases the specific surface area of the carrier, is more favorable for adsorbing reactants and mass transfer, and the shiny part is FeS, and FeS can be seen to be uniformly dispersed on the reduced graphene oxide. FIG. 3 is an XRD pattern of the FeS @ rGO catalyst prepared in this example, in which the main peak positions are consistent with the FeS Standard template library (JCPDS65-9124), and the obtained product is confirmed to be a FeS/rGO composite material.
Example 2
Dispersing 0.1g of graphene oxide powder into 60ml of water solution, carrying out ultrasonic stripping to obtain uniform graphene oxide dispersion liquid, and adding 291mg of Co (NO) into the solution3)2·6H2O and 40mg PVP (K-30), ultrasonically dispersing for 30min, and mixing with 20ml of Na with ethylene glycol as a solvent2And mixing the S (1mmol, 78mg) solution, continuously stirring for 60min at room temperature, transferring to a Teflon hydrothermal reaction kettle, carrying out hydrothermal reaction for 24h at 180 ℃, naturally cooling to room temperature, and filtering and drying to obtain the CoS @ rGO catalyst. Fig. 5 is a scanning electron microscope photograph of the CoS @ rGO catalyst prepared in this example, and it can be seen from the figure that the reduced graphene oxide sheet after hydrothermal treatment becomes wrinkled, which greatly increases the specific surface area of the carrier, is more favorable for adsorbing reactants and mass transfer, and the shiny part is CoS, and the CoS can be seen to be uniformly dispersed on the reduced graphene oxide. FIG. 6 is an XRD pattern of the CoS @ rGO catalyst prepared in this example, in which the main peak positions are matched with the CoS Standard template library (PDF65-3418), and the obtained product is confirmed to be a CoS/rGO composite material.
Example 3
Dispersing 0.1g of graphene oxide powder into 60ml of water solution, carrying out ultrasonic stripping to obtain uniform graphene oxide dispersion liquid, and adding 291mg of Ni (NO) into the solution3)2·6H2O and 40mg PVP (K-30), ultrasonic dispersing for 30min, and mixing with 20ml ethylene glycolNa with alcohol as solvent2And mixing the S (1mmol, 78mg) solution, continuously stirring for 60min at room temperature, transferring to a Teflon hydrothermal reaction kettle, carrying out hydrothermal reaction for 24h at 180 ℃, naturally cooling to room temperature, and filtering and drying to obtain the NiS @ rGO catalyst. Fig. 8 is a scanning electron microscope photograph of the NiS @ rGO catalyst prepared in this embodiment, and it can be seen from the figure that the reduced graphene oxide sheet after hydrothermal treatment becomes wrinkled, which greatly increases the specific surface area of the carrier, is more favorable for adsorbing reactants and mass transfer, and the bright part is NiS, and it can be seen that NiS is uniformly dispersed on the reduced graphene oxide. FIG. 9 is an XRD pattern of the NiS @ rGO catalyst prepared in this example, in which the main peak positions were matched with the NiS Standard template library (PDF 65-3419), confirming that the resulting product is a NiS/rGO composite.
The performance evaluation of the catalyst prepared in the embodiment 1-3 for catalyzing and synthesizing amine is carried out according to the following method:
1mmol of p-nitrophenol (4-NP) and 20mg of catalyst are added into a 100mL beaker, 60mL of purified water and 22.6mg of NaBH are added4Reacting in water bath at 30 ℃, sampling 2ml each time under the stirring condition, separating the catalyst from the reaction liquid after passing through a 0.22 mu m membrane, measuring the reaction liquid by using an ultraviolet visible spectrophotometer, wherein the wavelength range is 200-500nm, the characteristic absorption peak of p-nitrophenol (4-NP) at 400nm is shown, and the characteristic absorption peak of p-aminophenol (4-AP) is shown near 290 nm.
FIG. 4 is a graph showing the reduction effect of the FeS @ rGO catalyst prepared in example 1 on 4-NP, and it can be seen from FIG. 4 that the FeS @ rGO catalyst has a good reduction effect on 4-NP, 4-NP can be completely converted into 4-AP within 2min, and the selectivity is 100%;
FIG. 7 is a graph showing the reduction effect of the CoS @ rGO catalyst prepared in example 2 on 4-NP, and it can be seen from FIG. 7 that the CoS @ rGO catalyst has a good reduction effect on 4-NP, 4-NP can be completely converted into 4-AP within 2min, and the selectivity is 100%;
FIG. 10 is a graph showing the reduction effect of the NiS @ rGO catalyst prepared in example 3 on 4-NP, and it can be seen from FIG. 10 that the reduction effect of the NiS @ rGO catalyst on 4-NP is very good, 4-NP can be completely converted into 4-AP within 1.5min, and the selectivity is 100%.
Example 4
Dispersing 0.1g of graphene oxide powder into 60ml of water solution, carrying out ultrasonic stripping to obtain uniform graphene oxide dispersion liquid, and adding 404mg of Fe (NO) into the solution3)3·9H2O and 40mg PVP (K-30), ultrasonically dispersing for 30min, and mixing with 20ml ethylene glycol as solvent K2And (3) mixing the S (1mmol, 110mg) solution, continuously stirring for 60min at room temperature, transferring to a Teflon hydrothermal reaction kettle, carrying out hydrothermal reaction at 180 ℃ for 24h, naturally cooling to room temperature, and filtering and drying to obtain the FeS @ rGO catalyst.
Example 5
Dispersing 0.1g of graphene oxide powder into 60ml of water solution, carrying out ultrasonic stripping to obtain uniform graphene oxide dispersion liquid, and adding 291mg of Co (NO) into the solution3)2·6H2O and 40mg PVP (K-30), ultrasonically dispersing for 30min, and mixing with 20ml ethylene glycol as solvent K2And mixing the S (1mmol, 110mg) solution, continuously stirring for 60min at room temperature, transferring to a Teflon hydrothermal reaction kettle, carrying out hydrothermal reaction at 180 ℃ for 24h, naturally cooling to room temperature, and filtering and drying to obtain the CoS @ rGO catalyst.
Example 6
Dispersing 0.1g of graphene oxide powder into 60ml of water solution, carrying out ultrasonic stripping to obtain uniform graphene oxide dispersion liquid, and adding 291mg of Ni (NO) into the solution3)2·6H2O and 40mg PVP (K-30), ultrasonically dispersing for 30min, and mixing with 20ml ethylene glycol as solvent K2And (3) mixing the S (1mmol, 110mg) solution, continuously stirring for 60min at room temperature, transferring to a Teflon hydrothermal reaction kettle, carrying out hydrothermal reaction at 180 ℃ for 24h, naturally cooling to room temperature, and filtering and drying to obtain the NiS @ rGO catalyst.
Example 7
Dispersing 0.1g of graphene oxide powder into 60ml of water solution, carrying out ultrasonic stripping to obtain uniform graphene oxide dispersion liquid, and adding 404mg of Fe (NO) into the solution3)3·9H2O and 40mg PVP (K-30), ultrasonically dispersing for 30min, and mixing with Na with 20ml of glycerol as solvent2Mixing S (1mmol, 78mg) solution, stirring at room temperature, transferring to Teflon hydrothermal reaction kettle after 60min, and adding 180 deg.C waterAnd heating for 24h, naturally cooling to room temperature, and filtering and drying to obtain the FeS @ rGO catalyst.
Example 8
Dispersing 0.1g of graphene oxide powder into 60ml of water solution, carrying out ultrasonic stripping to obtain uniform graphene oxide dispersion liquid, and adding 291mg of Co (NO) into the solution3)2·6H2O and 40mg PVP (K-30), ultrasonically dispersing for 30min, and mixing with Na with 20ml of glycerol as solvent2And mixing the S (1mmol, 78mg) solution, continuously stirring for 60min at room temperature, transferring to a Teflon hydrothermal reaction kettle, carrying out hydrothermal reaction for 24H at 180 ℃, naturally cooling to room temperature, and filtering and drying to obtain the CoS @ rGO catalyst.
Example 9
Dispersing 0.1g of graphene oxide powder into 60ml of water solution, carrying out ultrasonic stripping to obtain uniform graphene oxide dispersion liquid, and adding 291mg of Ni (NO) into the solution3)2·6H2O and 40mg PVP (K-30), ultrasonically dispersing for 30min, and mixing with Na with 20ml of glycerol as solvent2And mixing the S (1mmol, 78mg) solution, continuously stirring for 60min at room temperature, transferring to a Teflon hydrothermal reaction kettle, carrying out hydrothermal reaction for 24h at 180 ℃, naturally cooling to room temperature, and filtering and drying to obtain the NiS @ rGO catalyst.
Example 10
Dispersing 0.1g of graphene oxide powder into 60ml of water solution, carrying out ultrasonic stripping to obtain uniform graphene oxide dispersion liquid, and adding 404mg of Fe (NO) into the solution3)3·9H2O and 40mg PVP (K-30), ultrasonically dispersing for 30min, and mixing with K with 20ml of glycerol as a solvent2And (3) mixing the S (1mmol, 110mg) solution, continuously stirring for 60min at room temperature, transferring to a Teflon hydrothermal reaction kettle, carrying out hydrothermal reaction at 180 ℃ for 24h, naturally cooling to room temperature, and filtering and drying to obtain the FeS @ rGO catalyst.
Example 11
Dispersing 0.1g of graphene oxide powder into 60ml of water solution, carrying out ultrasonic stripping to obtain uniform graphene oxide dispersion liquid, and adding 291mg of Co (NO) into the solution3)2·6H2O and 40mg PVP (K-30), ultrasonically dispersing for 30min, and mixing with K with 20ml of glycerol as a solvent2And mixing the S (1mmol, 110mg) solution, continuously stirring for 60min at room temperature, transferring to a Teflon hydrothermal reaction kettle, carrying out hydrothermal reaction at 180 ℃ for 24h, naturally cooling to room temperature, and filtering and drying to obtain the CoS @ rGO catalyst.
Example 12
Dispersing 0.1g of graphene oxide powder into 60ml of water solution, carrying out ultrasonic stripping to obtain uniform graphene oxide dispersion liquid, and adding 291mg of Ni (NO) into the solution3)2·6H2O and 40mg PVP (K-30), ultrasonically dispersing for 30min, and mixing with K with 20ml of glycerol as a solvent2And (3) mixing the S (1mmol, 110mg) solution, continuously stirring for 60min at room temperature, transferring to a Teflon hydrothermal reaction kettle, carrying out hydrothermal reaction at 180 ℃ for 24h, naturally cooling to room temperature, and filtering and drying to obtain the NiS @ rGO catalyst.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (4)

1. A method for preparing an aromatic amine compound, comprising:
carrying out water bath reaction on an aromatic nitro compound, a reducing agent, a catalyst and water to obtain an aromatic amine compound;
the preparation method of the catalyst comprises the following steps:
mixing transition metal salt, sulfide, a reducing agent, a dispersing agent, water and graphene oxide, and carrying out hydrothermal reaction in a high-pressure reaction kettle to obtain a transition metal sulfide catalyst;
in the preparation method of the catalyst, the reducing agent is selected from one or more of ethylene glycol, glycerol, acetaldehyde and propionaldehyde; the dispersant is PVP K-30; the transition metal salt is transition metal nitrate; the transition metal in the transition metal salt is selected from Fe, Co or Ni; the sulfide is selected from Na2S or K2S；
The transition metal sulfide catalyst consists of reduced graphene oxide and transition metal sulfide loaded on the surface of the reduced graphene oxide;
the molar ratio of the transition metal salt to the sulfide is (0.5-2): 1;
the ratio of the sulfide to the graphene is 1mmol to 100 mg; the transition metal sulfide is selected from FeS, CoS or NiS.
2. The method of claim 1, further comprising, prior to mixing:
and dispersing the graphene oxide powder into an aqueous solution, and ultrasonically stripping to obtain a graphene oxide dispersion liquid.
3. The preparation method according to claim 1, wherein the hydrothermal reaction is carried out at a temperature of 150-200 ℃ for 24-36 h.
4. The method according to claim 1, wherein the reducing agent is sodium borohydride or potassium borohydride.
CN201711419312.6A 2017-12-25 2017-12-25 Transition metal sulfide catalyst, method for producing same, and method for producing aromatic amine compound Active CN108144631B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201711419312.6A CN108144631B (en) 2017-12-25 2017-12-25 Transition metal sulfide catalyst, method for producing same, and method for producing aromatic amine compound

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201711419312.6A CN108144631B (en) 2017-12-25 2017-12-25 Transition metal sulfide catalyst, method for producing same, and method for producing aromatic amine compound

Publications (2)

Publication Number Publication Date
CN108144631A CN108144631A (en) 2018-06-12
CN108144631B true CN108144631B (en) 2020-12-25

Family

ID=62464529

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711419312.6A Active CN108144631B (en) 2017-12-25 2017-12-25 Transition metal sulfide catalyst, method for producing same, and method for producing aromatic amine compound

Country Status (1)

Country Link
CN (1) CN108144631B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114976052A (en) * 2022-06-06 2022-08-30 济南大学 Preparation method of grain boundary-rich ultrathin rhodium nanosheet electrocatalyst

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102760877A (en) * 2012-07-23 2012-10-31 浙江大学 Transition metal sulfide/graphene composite material, and preparation method and application thereof
CN102910615A (en) * 2012-08-24 2013-02-06 江苏大学 Preparation method of graphene oxide/iron disulfide composite nano particles
CN103602362A (en) * 2013-11-21 2014-02-26 镇江市高等专科学校 Preparation method of ferrous disulfide-graphene composite nano lubricant
CN103950989A (en) * 2014-05-07 2014-07-30 安徽师范大学 FeS nano-material and preparation method thereof
CN104134783A (en) * 2014-07-31 2014-11-05 北京科技大学 Nano-NiS/graphene composite anode material and preparation method thereof
CN104347874A (en) * 2014-09-09 2015-02-11 上海纳旭实业有限公司 High uniformly dispersed cobalt disulfide/graphene composite material and preparation method thereof
CN105233842A (en) * 2015-10-14 2016-01-13 上海理工大学 Preparation method of multi-metal sulfide/graphene composite visible-light-driven photocatalyst
CN106140307A (en) * 2016-06-20 2016-11-23 吉林大学 A kind of redox graphene/conducting polymer/metal sulfide trielement composite material, preparation method and applications
CN106207127A (en) * 2016-08-30 2016-12-07 安徽师范大学 The preparation method of a kind of nickel sulfide/graphene nanocomposite material, lithium ion battery negative, lithium ion battery

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102760877A (en) * 2012-07-23 2012-10-31 浙江大学 Transition metal sulfide/graphene composite material, and preparation method and application thereof
CN102910615A (en) * 2012-08-24 2013-02-06 江苏大学 Preparation method of graphene oxide/iron disulfide composite nano particles
CN103602362A (en) * 2013-11-21 2014-02-26 镇江市高等专科学校 Preparation method of ferrous disulfide-graphene composite nano lubricant
CN103950989A (en) * 2014-05-07 2014-07-30 安徽师范大学 FeS nano-material and preparation method thereof
CN104134783A (en) * 2014-07-31 2014-11-05 北京科技大学 Nano-NiS/graphene composite anode material and preparation method thereof
CN104347874A (en) * 2014-09-09 2015-02-11 上海纳旭实业有限公司 High uniformly dispersed cobalt disulfide/graphene composite material and preparation method thereof
CN105233842A (en) * 2015-10-14 2016-01-13 上海理工大学 Preparation method of multi-metal sulfide/graphene composite visible-light-driven photocatalyst
CN106140307A (en) * 2016-06-20 2016-11-23 吉林大学 A kind of redox graphene/conducting polymer/metal sulfide trielement composite material, preparation method and applications
CN106207127A (en) * 2016-08-30 2016-12-07 安徽师范大学 The preparation method of a kind of nickel sulfide/graphene nanocomposite material, lithium ion battery negative, lithium ion battery

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
In situ Growth of Phase-Controlled Nickel Sulfide Nanostructures on Reduced Graphene Oxide Nanosheets: A Improved Cost-effective Catalyst for 4-Nitrophenol Reduction;Rajan Karthikeyan等;《Chemistry Select》;20170227;第2卷;摘要，第2187页introduction部分,第2192-2194页catalytic activity in the reduction of 4-nitrophenol部分，图14,15b *
One-step synthesis of nickel sulfide/N-doped graphene composite as anode materials for lithium ion batteries;Hua-Chao Tao等;《Journal of Electroanalytical Chemistry》;20141212;第739卷;第37页左栏第2段，左栏第2.1节 *
Rajan Karthikeyan等.In situ Growth of Phase-Controlled Nickel Sulfide Nanostructures on Reduced Graphene Oxide Nanosheets: A Improved Cost-effective Catalyst for 4-Nitrophenol Reduction.《Chemistry Select》.2017,第2卷 *

Also Published As

Publication number Publication date
CN108144631A (en) 2018-06-12

Similar Documents

Publication Publication Date Title
Duan et al. Bimetallic nanoparticles/metal-organic frameworks: Synthesis, applications and challenges
Sharma et al. Silver nanomaterials: synthesis and (electro/photo) catalytic applications
CN109305918B (en) Synthesis method of halogenated aniline
Chen et al. Metal–organic framework-derived porous materials for catalysis
US9421527B2 (en) Inorganic nanoparticle deposited catalyst for hydrogenation and manufacturing method of the same, and hydrogenation for biomass derived hydrocarbon compounds
Guo et al. Cobalt Entrapped in N, S‐Codoped Porous Carbon: Catalysts for Transfer Hydrogenation with Formic Acid
Chen et al. Solvent-driven selectivity control to either anilines or dicyclohexylamines in hydrogenation of nitroarenes over a bifunctional Pd/MIL-101 catalyst
JP6994458B2 (en) Process for catalytic hydrogenation of halonitroaromatics
Li et al. Porous materials confining noble metals for the catalytic reduction of nitroaromatics: controllable synthesis and enhanced mechanism
CN109482235B (en) Preparation method and application of N-doped mesoporous carbon supported metal nano catalyst
Kharisov et al. Iron-based nanomaterials in the catalysis
Ergen et al. One-pot reductive amination of aldehydes with nitroarenes using formic acid as the hydrogen donor and mesoporous graphitic carbon nitride supported AgPd alloy nanoparticles as the heterogeneous catalyst
Cai et al. MOF derived C/Co@ C with a “one-way-valve”-like graphitic carbon layer for selective semi-hydrogenation of aromatic alkynes
Liu et al. A CuZn-BTC derived stable Cu/ZnO@ SiO2 catalyst for ethanol dehydrogenation
She et al. Bimetallic CuZn-MOFs derived Cu-ZnO/C catalyst for reductive amination of nitroarenes with aromatic aldehydes tandem reaction
Ghamari Kargar et al. A novel water‐dispersible and magnetically recyclable nickel nanoparticles for the one‐pot reduction‐Schiff base condensation of nitroarenes in pure water
Du et al. Temperature-dependent synthesis of MOF-derived Co@ N-doped carbon nanotube nanocomposites toward accelerated reduction of 4-nitrophenol
Dutta et al. Metal–organic framework based catalytic nanoreactors: synthetic challenges and applications
Ning et al. Rare earth oxide anchored platinum catalytic site coated zeolitic imidazolate frameworks toward enhancing selective hydrogenation
Li et al. Platinum clusters anchored on sulfur-doped ordered mesoporous carbon for chemoselective hydrogenation of halogenated nitroarenes
CN108144631B (en) Transition metal sulfide catalyst, method for producing same, and method for producing aromatic amine compound
Lakshminarayana et al. Switching of support materials for the hydrogenation of nitroarenes: A review
CN111167515B (en) Monomolecular heteropoly acid inlaid honeycomb-shaped carbon material loaded nano metal catalyst and preparation method and application thereof
KR102046686B1 (en) Carrier-nano particles complex, method for fabricating the same and membrane electrode assembly comprising the same
Xu et al. N, S-Co-doping Significantly Improves the Co–Nx Content of the Co-NSPC Catalyst and Enhances the Catalytic Performance for Selective Hydrogenation of Halogenated Nitrobenzenes

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