CN112501641B - Method for preparing azobenzene and azoxybenzene compounds through electrocatalysis - Google Patents
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Abstract
The invention relates to a method for preparing azobenzene and azoxybenzene compounds by electrocatalysis, wherein aromatic nitro compounds are reduced and coupled with aromatic amino compounds to be oxidized by electrocatalysis under the conditions of room temperature and inert gas to obtain azoxybenzene compounds; the method has the advantages of mild conditions, high efficiency and selectivity and high universality, and can realize the synthesis of asymmetric azobenzene and azoxybenzene compounds.
Description
Technical Field
The invention belongs to the field of electrocatalysis, relates to a synthesis method of azobenzene and azoxybenzene compounds, and particularly relates to a method for preparing azobenzene and azoxybenzene compounds through electrocatalysis.
Background
Azobenzene and azoxybenzene are industrially important raw materials, and as organic synthesis intermediates, azobenzene and azoxybenzene are widely applied to the industries of dye synthesis, biomedicine, electronic liquid crystal materials and the like. The diazotization process of the traditional azobenzene and azoxybenzene synthesis is very dangerous, and the generated diazonium salt compound is very unstable and is very easy to explode. Therefore, the method for efficiently and environmentally synthesizing azobenzene and azoxybenzene compounds and derivatives thereof has important application value.
The Chinese patent with application number 201911100238.0 discloses a method for preparing asymmetric azobenzene and azoxybenzene compounds by photocatalysis, wherein an aromatic nitro compound and an aromatic amino compound are reacted under the conditions of illumination and inert gas through a photocatalyst to obtain the asymmetric azobenzene compounds and the asymmetric azoxybenzene compounds, the asymmetric azobenzene compounds and the asymmetric azoxybenzene compounds can be used for replacing the existing mature organic synthesis process, and the method has the advantages of mild conditions, high selectivity, universality and suitability for industrial production.
Under the condition of no illumination, the electrocatalytic energy conversion becomes an important way for obtaining high-value chemicals. Electrocatalytic organic synthesis is an emerging direction in organic synthesis methodology. By reasonably controlling the electrode potential, the electrocatalyst and the electrolyte, the simultaneous electron transfer and chemical reaction can be realized on an electrode/solution interface, and some chemicals which are difficult to synthesize by the traditional thermal catalysis method can be synthesized with high selectivity.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a method for preparing azobenzene and azoxybenzene compounds through electrocatalysis.
In order to achieve the purpose, the invention adopts the technical scheme that: a method for preparing azobenzene and azoxybenzene compounds by electrocatalysis comprises the steps of carrying out reduction coupling on aromatic nitro compounds and oxidizing aromatic amino compounds by electrocatalysis at room temperature under the condition of inert gas to obtain azobenzene compounds shown in a formula I and azoxybenzene compounds shown in a formula II;
the electrocatalysis is that an electrode loaded with a catalyst is subjected to an electrolytic reaction under a constant-voltage or constant-current working condition.
Optimally, the structural general formula of the aromatic nitro compound is shown as a formula III:
further, the structural general formula of the aromatic amino compound is shown as a formula IV:
optimally, it comprises the following steps:
(a) adding the aromatic nitro compound and the aromatic amino compound into an electrolytic cell, adding a solvent and an electrolyte, dispersing to obtain a mixed solution, and inserting into an electrode loaded with a catalyst; the molar concentration ratio of the aromatic nitro compound to the aromatic amino compound is 1: (0.1-10);
(b) carrying out an electrolytic reaction on the mixed solution under the condition of inert atmosphere and under the working condition of constant pressure or constant current;
(c) drying and concentrating the organic phase obtained in the step (b) to obtain azobenzene and azoxybenzene compounds.
Further, the electrocatalyst is a mixture of one or more selected from the group consisting of metals, alloys, metal oxides, metal nitrogen compounds, metal sulfides, perovskites, delafossite, carbon-based and nitrogen-based polymeric materials.
Optimally, the inert gas is He, Ar and N2 、CO2CO or H2One or more of (a).
Further, in the step (a), the concentrations of the aromatic nitro compound and the aromatic amino compound in the mixed solution are independently 0.1-10000 mmol/L, and the content of the supported electrocatalyst on the electrode is 0.1-1000 mg/cm2。
Further, in the step (a), the electrolyte is an acid electrolyte, and the concentration of the acid electrolyte is 0.1-10 mol/L; the electrolyte is a mixture consisting of one or more of sulfuric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, nitric acid, phosphoric acid, hypochlorous acid, perchloric acid and oxalic acid.
Further, in the step (a), the electrolyte is an alkaline electrolyte, and the concentration of the alkaline electrolyte is 0.1-10 mol/L; the electrolyte is a mixture consisting of one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide and ammonia water.
Further, in the step (a), the electrolyte is a neutral electrolyte, and the concentration of the neutral electrolyte is 0.1-10 mol/L; the electrolyte is a mixture consisting of one or more of sulfate, sulfite, phosphate, phosphite, carbonate, bicarbonate, nitrate, nitrite and halide.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages: according to the method for preparing azobenzene and azoxybenzene compounds through electrocatalysis, the aromatic nitro compound is subjected to reduction coupling, the aromatic amino compound is oxidized to realize electrocatalysis nitrogen-nitrogen coupling reaction, the conditions are mild, the efficiency and the selectivity are high, the universality is high, and the synthesis of asymmetric azobenzene and azoxybenzene compounds can be realized.
Drawings
FIG. 1 is a schematic diagram of the principle of the method for preparing azobenzene and azoxybenzene compounds by electrocatalysis;
FIG. 2 is a mass spectrum of 4-chlorophenylazobenzene in example 1.
Detailed Description
According to the method for preparing azobenzene and azoxybenzene compounds through electrocatalysis, aromatic nitro compounds are subjected to reduction coupling and aromatic amino compounds are oxidized through electrocatalysis at room temperature under the condition of inert gas, and azobenzene compounds shown in a formula I and azoxybenzene compounds shown in a formula II are obtained;
in the formulae I and II, R1And R2Is 1, 2, 3, 4 or 5 substituents attached to the benzene ring, each of said substituents being independently of the others hydrogen, halogen, C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Alkynyl, C6-C20Aryl, -OR', -OCF3Any one of-NHR ', -C (═ O) OR ', -NHC (═ O) R ', and-C (═ O) R ', wherein R ' is H, C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Any one of alkynyl, phenyl and benzyl; the electrocatalysis is that an electrode loaded with a catalyst is subjected to an electrolytic reaction under a constant-voltage or constant-current working condition. The electrocatalytic nitrogen-nitrogen coupling reaction is realized by reducing and coupling the aromatic nitro compound and oxidizing the aromatic amino compound, the conditions are mild, the efficiency and the selectivity are high, the universality is high, and the synthesis of asymmetric azobenzene and azoxybenzene compounds can be realized (as shown in figure 1).
The structural general formula of the aromatic nitro compound is shown as a formula III:
(III). The aromatic ammoniaThe structural general formula of the base compound is shown as formula IV:
(IV). Specifically, the method comprises the following steps: (a) adding the aromatic nitro compound and the aromatic amino compound into an electrolytic cell, adding a solvent and an electrolyte, dispersing to obtain a mixed solution, and inserting into an electrode loaded with a catalyst; the molar concentration ratio of the aromatic nitro compound to the aromatic amino compound is 1: (0.1-10); (b) carrying out an electrolytic reaction on the mixed solution under the condition of inert atmosphere and under the working condition of constant pressure or constant current; (c) drying and concentrating the organic phase obtained in the step (b) to obtain azobenzene and azoxybenzene compounds. The electrocatalyst is a mixture of one or more selected from the group consisting of metals, alloys, metal oxides, metal nitrogen compounds, metal sulfides, perovskites, delafossite, carbon-based and nitrogen-based polymeric materials. The inert gas is He, Ar, N2 、CO2CO or H2One or more of (a). In the step (a), the concentrations of the aromatic nitro compound and the aromatic amino compound in the mixed solution are independently 0.1-10000 mmol/L (preferably 0.1-10 mmol/L), and the content of the supported electrocatalyst on the electrode is 0.1-1000 mg/cm2. In the step (a), the electrolyte is an acid electrolyte, and the concentration of the acid electrolyte is 0.1-10 mol/L; the electrolyte is a mixture consisting of one or more of sulfuric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, nitric acid, phosphoric acid, hypochlorous acid, perchloric acid and oxalic acid. In the step (a), the electrolyte is alkaline electrolyte, and the concentration of the electrolyte is 0.1-10 mol/L; the electrolyte is a mixture consisting of one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide and ammonia water. In the step (a), the electrolyte is neutral electrolyte, and the concentration of the electrolyte is 0.1-10 mol/L; the electrolyte is a mixture consisting of one or more of sulfate, sulfite, phosphate, phosphite, carbonate, bicarbonate, nitrate, nitrite and halide.
In the step (b), the electrode is selected from one or more of carbon material (graphite, carbon paper, carbon fiber), glassy carbon, metal (platinum, palladium, gold, ruthenium, iridium, tungsten, silver, titanium, zinc, copper, nickel, aluminum, stainless steel and other alloys) electrodes; the structure of the material is bulk, porous, film, net and the like. In the step (b), the constant voltage is 1.0-100000 mV (preferably 1-2000 mV); the constant current is 0.1-10000 mA (preferably 1-100 mA); in the step (b), the electrolysis time is 0.01-100 h (preferably 0.01-5 h).
The present invention will be further described with reference to examples.
Example 1
This example provides a method for preparing azobenzene and azoxybenzene compounds by electrocatalysis, which comprises the following steps:
(a) adding 0.12 mmol/L nitrobenzene, 0.12 mmol/L parachloroaniline and 2 mol/L potassium hydroxide electrolyte into a diaphragm-free electrolytic cell; then dripping the graphite electrode with the concentration of 10 mg/cm2 IrO of (1)2An electrocatalyst is used as a working electrode;
(b) in N2Under the atmosphere, controlling the reaction current to be 10 mA, and stirring for reaction for 2 h;
(c) drying and concentrating the organic phase obtained in the step (b) to obtain a product 4-chlorophenylazobenzene, and testing and analyzing the result by a gas chromatograph: the nitrobenzene conversion was 95%, the parachloroaniline conversion was 97% (mass spectrum shown in fig. 2), and the 4-chlorophenylazobenzene selectivity was 98%.
Example 2
This example provides a method for preparing azobenzene and azoxybenzene compounds by electrocatalysis, which comprises the following steps:
(a) respectively adding 1 mmol/L nitrobenzene, 3 mmol/L para-methylaniline and 2.4 mol/L sodium tert-butoxide electrolyte into a diaphragm-free electrolytic cell, and uniformly mixing; then dripping 40 mg/cm concentration on the glassy carbon electrode2 The nickel-loaded graphene oxide (Ni/GO) of (1) is used as a working electrode;
(b) under Ar atmosphere, controlling the reaction current to be 32 mA, and stirring for reaction for 3 h;
(c) drying and concentrating the organic phase obtained in the step (b) to obtain a product 4-methylazobenzene, and analyzing the result through a gas chromatograph: the nitrobenzene conversion was 89%, the p-methylaniline conversion was 92% and the 4-methylazobenzene selectivity was 92%.
Example 3
This example provides a method for preparing azobenzene and azoxybenzene compounds by electrocatalysis, which comprises the following steps:
(a) adding 5 mmol/L p-methoxynitrobenzene, 2 mmol/L aniline and 3.6 mol/L sodium sulfite electrolyte into a diaphragm-free electrolytic cell, and uniformly mixing; then dripping the titanium plate electrode with the concentration of 40 mg/cm2 The iron-cobalt alloy electrocatalyst is used as a working electrode;
(b) in N2Under the atmosphere, controlling the voltage to be 1500 mV, and stirring for reaction for 2.5 h;
(c) drying and concentrating the organic phase obtained in the step (b) to obtain a product 4-methoxy azobenzene, and analyzing the result through a gas chromatograph: the conversion rate of p-methoxynitrobenzene is 95%, the conversion rate of aniline is 96.5%, and the selectivity of 4-methoxyazobenzene is 98%.
Example 4
This example provides a method for preparing azobenzene and azoxybenzene compounds by electrocatalysis, which comprises the following steps:
(a) adding 10 mmol/L p-methyl nitrobenzene, 10 mmol/L p-chloroaniline and 5 mol/L perchloric acid electrolyte into an electrolytic cell; then dripping 50 mg/cm on carbon paper2 Perovskite structure LaFeO3An electrocatalyst as a working electrode;
(b) in N2Under the atmosphere, controlling the reaction voltage to be 1600 mV, and stirring for reaction for 3 h;
(c) drying and concentrating the organic phase obtained in the step (b) to obtain a product 4-chlorobenzeneazo-4-methylbenzene, and testing and analyzing the result by a gas chromatograph: the conversion rate of p-methyl nitrobenzene is 91%, the conversion rate of p-chloroaniline is 95%, and the selectivity of 4-chlorobenzeneazo-4-methylbenzene is 85%.
Example 5
This example provides a method for preparing azobenzene and azoxybenzene compounds by electrocatalysis, which comprises the following steps:
(a) adding 6 mmol/L nitrobenzene and 2 mmol/L4-trifluoromethyl aniline into an electrolytic cell, and then adding 5 mol/L sulfuric acid electrolyte; the dripping concentration of the carbon fiber cloth is 100 mg/cm2 MoS of (1)2An electrocatalyst as a working electrode;
(b) under the Ar atmosphere, controlling the reaction current to be 25 mA, and stirring to react for 5 hours;
(c) drying and concentrating the organic phase obtained in the step (b) to obtain a product 4-trifluoromethyl phenylazo, and analyzing the result through a gas chromatograph: the nitrobenzene conversion was 95%, the 4-trifluoromethylaniline conversion was 97%, the 4-trifluoromethylazobenzene selectivity was 70%, and the 4-trifluoromethylazoxybenzene selectivity was 25%.
Example 6
This example provides a process for the electrocatalytic preparation of azobenzene and azoxybenzene compounds, which is essentially identical to that of example 1, except that: in the step (a), 0.12 mmol/L nitrobenzene and 0.012 mmol/L parachloroaniline are added into a diaphragm-free electrolytic cell; results were analyzed by gas chromatograph test: the nitrobenzene conversion was 90%, the parachloroaniline conversion was 100%, and the 4-chlorophenylazobenzene selectivity was 75%.
Example 7
This example provides a process for the electrocatalytic preparation of azobenzene and azoxybenzene compounds, which is essentially identical to that of example 1, except that: in the step (a), 1.2 mmol/L nitrobenzene and 0.12 mmol/L parachloroaniline are added into a diaphragm-free electrolytic cell; results were analyzed by gas chromatograph test: the nitrobenzene conversion was 86%, the parachloroaniline conversion was 95%, and the 4-chlorophenylazobenzene selectivity was 80%.
Example 8
This example provides a process for the electrocatalytic preparation of azobenzene and azoxybenzene compounds, which is essentially identical to that of example 1, except that: in the step (a), 2 mol/L lithium tert-butoxide is added; results were analyzed by gas chromatograph test: the nitrobenzene conversion was 93%, the parachloroaniline conversion was 90%, and the 4-chlorophenylazobenzene selectivity was 80%.
Example 9
This example provides a process for the electrocatalytic preparation of azobenzene and azoxybenzene compounds, which is essentially identical to that of example 1, except that: in the step (a), 2 mol/L sulfuric acid electrolyte is added; results were analyzed by gas chromatograph test: the nitrobenzene conversion was 95%, the parachloroaniline conversion was 89%, and the 4-chlorophenylazobenzene selectivity was 95%.
Example 10
This example provides a process for the electrocatalytic preparation of azobenzene and azoxybenzene compounds, which is essentially identical to that of example 1, except that: in the step (a), 2 mol/L oxalic acid is added; results were analyzed by gas chromatograph test: the nitrobenzene conversion was 55%, the parachloroaniline conversion was 67%, and the 4-chlorophenylazobenzene selectivity was 90%.
Example 11
This example provides a process for the electrocatalytic preparation of azobenzene and azoxybenzene compounds, which is essentially identical to that of example 1, except that: in the step (a), the graphite electrode is then coated by dripping with a concentration of 10 mg/cm2 The CoMoNx electrocatalyst of (a) as a working electrode; results were analyzed by gas chromatograph test: the nitrobenzene conversion was 79%, the parachloroaniline conversion was 86%, and the 4-chlorophenylazobenzene selectivity was 90%.
Example 12
This example provides a process for the electrocatalytic preparation of azobenzene and azoxybenzene compounds, which is essentially identical to that of example 1, except that: in the step (a), the graphite electrode is then coated by dripping with a concentration of 10 mg/cm2 The NiCo alloy electrocatalyst is used as a working electrode; results were analyzed by gas chromatograph test: the nitrobenzene conversion was 82%, the parachloroaniline conversion was 90%, and the 4-chlorophenylazobenzene selectivity was 90%.
Example 13
This example provides a process for the electrocatalytic preparation of azobenzene and azoxybenzene compounds, substantially as described in example 1Thus, the differences are: in the step (a), the graphite electrode is then coated by dripping with a concentration of 10 mg/cm2 CuFeO (g)2An electrocatalyst is used as a working electrode; results were analyzed by gas chromatograph test: the nitrobenzene conversion was 85%, the parachloroaniline conversion was 90%, and the 4-chlorophenylazobenzene selectivity was 89%.
Example 14
This example provides a process for the electrocatalytic preparation of azobenzene and azoxybenzene compounds, which is essentially identical to that of example 1, except that: in the step (a), the graphite electrode is then coated by dripping with a concentration of 10 mg/cm2 The nickel-loaded graphene oxide (Ni/GO) of (1) is used as a working electrode; results were analyzed by gas chromatograph test: the nitrobenzene conversion was 75%, the parachloroaniline conversion was 90%, and the 4-chlorophenylazobenzene selectivity was 90%.
Example 15
This example provides a process for the electrocatalytic preparation of azobenzene and azoxybenzene compounds, which is essentially identical to that of example 1, except that: in the step (a), the graphite electrode is then coated by dripping with a concentration of 10 mg/cm2 The iron-cobalt alloy electrocatalyst is used as a working electrode; results were analyzed by gas chromatograph test: the nitrobenzene conversion was 65%, the parachloroaniline conversion was 82%, and the 4-chlorophenylazobenzene selectivity was 95%.
Example 16
This example provides a process for the electrocatalytic preparation of azobenzene and azoxybenzene compounds, which is essentially identical to that of example 1, except that: in the step (a), the graphite electrode is then coated by dripping with a concentration of 10 mg/cm2 LaFeO of perovskite structure3An electrocatalyst as a working electrode; results were analyzed by gas chromatograph test: the nitrobenzene conversion was 75%, the parachloroaniline conversion was 83%, and the 4-chlorophenylazobenzene selectivity was 90%.
Example 17
This example provides a process for the electrocatalytic preparation of azobenzene and azoxybenzene compounds, which is essentially identical to that of example 1, except that: in step (a), the graphite electrode is then coated by droppingThe concentration is 10 mg/cm2 MoS of (1)2An electrocatalyst as a working electrode; results were analyzed by gas chromatograph test: the conversion rate of nitrobenzene is 95%, the conversion rate of parachloroaniline is 97%, and the selectivity of 4-chlorophenylazobenzene is 98%.
Example 18
This example provides a process for the electrocatalytic preparation of azobenzene and azoxybenzene compounds, which is essentially identical to that of example 1, except that: in the step (b), the reaction current is controlled to be 1 mA, and the stirring reaction is carried out for 5 hours; results were analyzed by gas chromatograph test: the nitrobenzene conversion was 65%, the parachloroaniline conversion was 81%, and the 4-chlorophenylazobenzene selectivity was 98%.
Example 19
This example provides a process for the electrocatalytic preparation of azobenzene and azoxybenzene compounds, which is essentially identical to that of example 1, except that: in the step (b), the reaction current is controlled to be 100 mA, and stirring reaction is carried out for 1 h; results were analyzed by gas chromatograph test: the conversion rate of nitrobenzene is 95%, the conversion rate of parachloroaniline is 99%, and the selectivity of 4-chlorophenylazobenzene is 98%.
Comparative example 1
This example provides a process for the electrocatalytic preparation of azobenzene and azoxybenzene compounds which is essentially identical to that of example 1, except that: azobenzene and azoxybenzene compounds cannot be obtained finally without adding electrolyte.
Comparative example 2
This example provides a process for the electrocatalytic preparation of azobenzene and azoxybenzene compounds which is essentially identical to that of example 1, except that: the method provides a method for polymerizing carbon nitride (photocatalyst) to react under illumination to obtain azobenzene and azoxybenzene compounds, wherein the nitrobenzene conversion rate is 65%, the p-chloroaniline conversion rate is 81%, the selectivity of asymmetric coupling products is reduced, and the selectivity of 4-chlorobenzene azobenzene is 58%.
Comparative example 3
This example provides a process for the electrocatalytic preparation of azobenzene and azoxybenzene compounds which is essentially identical to that of example 1, except that: the molar ratio of nitrobenzene to parachloroaniline is 1: 100, results were analyzed by gas chromatograph test: the nitrobenzene conversion was 95%, the parachloroaniline conversion was 30%, and the 4-chlorophenylazobenzene selectivity was 75%. The selectivity of the asymmetric product 4-chlorophenylazobenzene is reduced because the concentration of p-chloroaniline is too high and the coupling products of p-chloroaniline are increased.
Comparative example 4
This example provides a process for the electrocatalytic preparation of azobenzene and azoxybenzene compounds which is essentially identical to that of example 1, except that: the molar ratio of nitrobenzene to parachloroaniline is 100: 1, results were analyzed by gas chromatograph test: the nitrobenzene conversion rate is 35%, the parachloroaniline conversion rate is 94%, the selectivity of asymmetric coupling products is reduced, and the selectivity of 4-chlorophenylazobenzene is 58%.
The above examples are only for illustrating the technical idea and features of the present invention, and the purpose of the present invention is to enable those skilled in the art to understand the content of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (8)
1. A method for preparing azobenzene and azoxybenzene compounds by electrocatalysis is characterized in that: under the conditions of room temperature and inert gas, carrying out electrocatalysis to ensure that the aromatic nitro compound is subjected to reduction coupling and the aromatic amino compound is oxidized to obtain the azobenzene compound shown as the formula I and the azobenzene oxide compound shown as the formula II;
the structural general formula of the aromatic nitro compound is shown as a formula III:
r in the structural general formula of the aromatic nitro compound1Is hydrogen, methoxy or methyl;
the structural general formula of the aromatic amino compound is shown as a formula IV:
r in the structural general formula of the aromatic amino compound2Is chlorine, methyl, hydrogen or trifluoromethyl;
the electrocatalysis is that an electrode loaded with a catalyst is subjected to an electrolytic reaction under a constant-voltage or constant-current working condition.
2. The process for electrocatalytic production of azobenzene and azoxybenzene compounds according to claim 1, characterized in that it comprises the following steps:
(a) adding the aromatic nitro compound and the aromatic amino compound into an electrolytic cell, adding a solvent and an electrolyte, dispersing to obtain a mixed solution, and inserting into an electrode loaded with a catalyst; the molar concentration ratio of the aromatic nitro compound to the aromatic amino compound is 1: (0.1-10);
(b) carrying out an electrolytic reaction on the mixed solution under the condition of inert atmosphere and under the working condition of constant pressure or constant current;
(c) drying and concentrating the organic phase obtained in the step (b) to obtain azobenzene and azoxybenzene compounds.
3. The process for electrocatalytic production of azobenzene and azoxybenzene compounds according to claim 2, wherein: the catalyst is a mixture of one or more selected from the group consisting of metals, alloys, metal oxides, metal nitrogen compounds, metal sulfides, perovskites, delafossite, carbon-based and nitrogen-based polymeric materials.
4. The process for electrocatalytic production of azobenzene and azoxybenzene compounds according to claim 1, wherein: the inert gas is He, Ar, N2 、CO2CO or H2One or more of (a).
5. The process for electrocatalytic production of azobenzene and azoxybenzene compounds according to claim 2, wherein: in the step (a), the concentrations of the aromatic nitro compound and the aromatic amino compound in the mixed solution are mutually independent and are 0.1-10000 mmol/L, and the content of the supported electrocatalyst on the electrode is 0.1-1000 mg/cm2。
6. The process for electrocatalytic production of azobenzene and azoxybenzene compounds according to claim 2, wherein: in the step (a), the electrolyte is an acid electrolyte, and the concentration of the acid electrolyte is 0.1-10 mol/L; the electrolyte is a mixture consisting of one or more of sulfuric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, nitric acid, phosphoric acid, hypochlorous acid, perchloric acid and oxalic acid.
7. The process for electrocatalytic production of azobenzene and azoxybenzene compounds according to claim 2, wherein: in the step (a), the electrolyte is alkaline electrolyte, and the concentration of the electrolyte is 0.1-10 mol/L; the electrolyte is a mixture consisting of one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide and ammonia water.
8. The process for electrocatalytic production of azobenzene and azoxybenzene compounds according to claim 2, wherein: in the step (a), the electrolyte is neutral electrolyte, and the concentration of the electrolyte is 0.1-10 mol/L; the electrolyte is a mixture consisting of one or more of sulfate, sulfite, phosphate, phosphite, carbonate, bicarbonate, nitrate, nitrite and halide.
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