CN108715439A - A kind of cadmium base chalcogenide nanometer rods and preparation method, elctro-catalyst and application - Google Patents
A kind of cadmium base chalcogenide nanometer rods and preparation method, elctro-catalyst and application Download PDFInfo
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Abstract
The invention discloses a kind of cadmium base chalcogenide nanometer rods, preparation, elctro-catalyst, application and application processes, cadmium base chalcogenide nanometer rods are one kind in cadmium sulfoselenide alloy nano stick, cadmium sulfide nano-stick, cadmium selenide nanorod, cadmium base chalcogenide nanorod diameter is 5-7nm, length 70-170nm；The preparation method of cadmium base chalcogenide nanometer rods, including：Cadmium salt is dissolved in anhydrous ethylenediamine, mixed liquor A is stirred evenly to obtain；Sulphur powder and/or selenium powder, hydrazine hydrate are added in mixed liquor A, mixed liquid B is stirred to obtain；It is post-processed after mixed liquid B is carried out solvent thermal reaction.The preparation method of cadmium base chalcogenide nanometer rods of the present invention easily largely synthesizes, it is at low cost, catalyst of the gained nanometer rods as the catalysis reaction of carbon dioxide electroreduction, activity and stability are high, it is easy to regulate and control the selectivity of catalysate, while keeping high current density, the gaseous mixture of ratio adjustable carbon monoxide and hydrogen in a wide range of is obtained.
Description
Technical field
The present invention relates to catalyst technical field more particularly to a kind of cadmium base chalcogenide nanometer rods, preparation method and
Elctro-catalyst, application and application process.
Background technology
Synthesis gas refers to the gaseous mixture of carbon monoxide and hydrogen.Different industrial process, such as F- T synthesis, methanol close
At etc., need the synthesis gas of different composition ratio.In recent years, the prior art was to different types of nano material (gold nano
Grain, palladium nano-particles, silver nano-grain, two tungsten selenide nanometer sheets, sulphur selenizing molybdenum alloy nanometer sheet etc.) it is used for electroreduction titanium dioxide
A large amount of research has been carried out in terms of carbon production of synthetic gas.For example,《Science》(Science 2016,353,467-470) reports two
Tungsten selenide nanometer sheet electroreduction carbon dioxide in water and ionic liquid mixed electrolytic solution obtains carbon monoxide and hydrogen mixed gas,
The molar ratio of middle carbon monoxide and hydrogen is 4:1.《Energy & environmental sciences》(Energy Environ.Sci.2017,10,
The palladium nano-particles electroreduction carbon dioxide for 1180-1185) reporting Activated Carbon Supported obtains carbon monoxide and hydrogen mixed gas,
Wherein carbon monoxide and hydrogen mole can be 1:1 to 1:Between 2.《German applied chemistry》
(Angew.Chem.Int.Ed.2017,56,9121-9125) monolayer thiolate selenizing molybdenum alloy nanometer sheet is reported as high activity
Electroreduction carbon dioxide catalyst generates synthesis gas.Although the catalysis material of electroreduction carbon dioxide is varied, at present
Catalyst the synthesis gas of wide range ratio can not be generated under higher current density.How high current density is being kept
Meanwhile the gaseous mixture of ratio adjustable carbon monoxide and hydrogen in a wide range of is obtained as possible, become a very significant work
Make.
Invention content
Technical problems based on background technology, the present invention propose a kind of cadmium base chalcogenide nanometer rods, prepare
Method and elctro-catalyst, application and application process, the preparation method is easy to largely synthesize, of low cost, obtained cadmium base sulphur
Compounds of group nanometer rods are catalyzed the catalyst of production of synthetic gas as carbon dioxide electroreduction, and catalytic activity, stability are high, are easy to adjust
Control the selectivity of catalysate, can while keeping high current density, obtain in a wide range of the adjustable carbon monoxide of ratio with
The gaseous mixture of hydrogen.
A kind of cadmium base chalcogenide nanometer rods proposed by the present invention are received for cadmium sulfoselenide alloy nano stick, cadmium sulfide
One kind in rice stick, cadmium selenide nanorod, and a diameter of 5-7nm, length 70- of the cadmium base chalcogenide nanometer rods
170nm。
A kind of preparation method for cadmium base chalcogenide nanometer rods that the present invention also proposes, includes the following steps：It will
Cadmium salt is dissolved in anhydrous ethylenediamine, is uniformly mixing to obtain mixed liquor A；Mixed liquor A is added in sulphur powder and/or selenium powder, hydrazine hydrate
In, mixed liquid B is obtained after stirring；Mixed liquid B is carried out at 130-150 DEG C to solvent thermal reaction 10-15h, it is cold after reaction
But it, centrifuges, wash, being dried to obtain the cadmium base chalcogenide nanometer rods.
Preferably, the cadmium salt is one or two kinds of mixture in caddy, cadmium nitrate.
Preferably, the cadmium salt is caddy.
Preferably, the preparation method of the cadmium base chalcogenide nanometer rods, includes the following steps：By 0.5-1.5mmol
Caddy is dissolved in 20-50mL anhydrous ethylenediamines, is uniformly mixing to obtain mixed liquor A；By 0.5-1.5mmol sulphur powders and/or selenium
Powder, 2-5mL hydrazine hydrates are added in mixed liquor A, and mixed liquid B is obtained after stirring 20-35min；By mixed liquid B at 130-150 DEG C
Solvent thermal reaction 10-15h is carried out, is cooled down after reaction, then centrifuging 5-15min under the rotating speed of 8000-10000rpm obtains
It must precipitate, be washed with ethyl alcohol after precipitation is washed with water, be then dried in vacuo to obtain the cadmium base sulfur family at 50-70 DEG C
Compound nano rod.
Preferably, the preparation method of the cadmium base chalcogenide nanometer rods, includes the following steps：By 1mmol caddies
It is dissolved in 30mL anhydrous ethylenediamines, is uniformly mixing to obtain mixed liquor A；1mmol sulphur powders and/or selenium powder, 3mL hydrazine hydrates are added
In mixed liquor A, mixed liquid B is obtained after stirring 30min；Mixed liquid B is transferred in 45mL reaction kettles, is carried out at 140 DEG C molten
Agent thermal response 12h, natural cooling, then centrifuges 8min under the rotating speed of 10000rpm and is precipitated, will be precipitated after reaction
It is washed 2 times with ethyl alcohol after being washed with water 3 times, is then dried in vacuo to obtain the cadmium base chalcogenide nanometer at 60 DEG C
Stick.
A kind of elctro-catalyst that the present invention also proposes, active ingredient include the cadmium base chalcogenide nanometer rods.
A kind of application of the elctro-catalyst that the present invention also proposes in the catalysis reaction of carbon dioxide electroreduction.
A kind of application process of the elctro-catalyst that the present invention also proposes in the catalysis reaction of carbon dioxide electroreduction, packet
Include following steps：Cadmium base chalcogenide nanometer rods, activated carbon and Nafion solution are scattered in ethyl alcohol, obtained after ultrasound
Solution is uniformly brushed and obtains carbon paper electrode on carbon paper by solution, and using carbon paper electrode as working electrode, silver/silver chloride electrode is made
For reference electrode, graphite rod is used as to electrode, and carbon dioxide electricity is carried out also in the H-type electrolytic cell containing saleratus electrolyte
Original catalysis reaction is catalyzed the carbon monoxide and hydrogen of generation by the additional overpotential of electrochemical workstation and detection current density
Pass through gas chromatographic detection.
Preferably, application process of the elctro-catalyst in the catalysis reaction of carbon dioxide electroreduction, includes the following steps：
It is 2-7%'s by 0.5-1.0mg cadmium base chalcogenides nanometer rods, 3-3.5mg activated carbons and 25-35 μ L mass fractions
Nafion solution is scattered in 2-3mL ethyl alcohol, and ultrasonic 0.5-1.5h obtains solution, and taking the above-mentioned solution of 220-280 μ L, uniformly brush exists
Carbon paper electrode is obtained on the carbon paper of 1cm × 0.5cm, using carbon paper electrode as working electrode, silver/silver chloride electrode is as reference electricity
Pole, graphite rod is used as to electrode, in the H-type electrolysis containing a concentration of 0.08-0.12mol/L saleratus electrolyte of 50-70mL
The catalysis reaction of carbon dioxide electroreduction is carried out in pond, passes through the additional overpotential of electrochemical workstation and detection current density, catalysis
The carbon monoxide and hydrogen of generation pass through gas chromatographic detection.
Preferably, application process of the elctro-catalyst in the catalysis reaction of carbon dioxide electroreduction, includes the following steps：
The Nafion solution that 0.8mg cadmium base chalcogenides nanometer rods, 3.2mg activated carbons and 30 μ L mass fractions are 5% is disperseed
In 1mL ethyl alcohol, ultrasonic 1h obtains solution, and taking the 250 above-mentioned solution of μ L, uniformly brush obtains carbon paper on the carbon paper of 1cm × 0.5cm
Electrode, using carbon paper electrode as working electrode, as reference electrode, graphite rod is used as to electrode silver/silver chloride electrode, containing
The catalysis reaction of carbon dioxide electroreduction is carried out in the H-type electrolytic cell of a concentration of 0.1mol/L saleratus electrolyte of 60mL, is passed through
The additional overpotential of electrochemical workstation and detection current density, the carbon monoxide and hydrogen for being catalyzed generation are examined by gas-chromatography
It surveys.
Preferably, past to contain a concentration of 0.1mol/L bicarbonates of 60mL before carrying out the catalysis reaction of carbon dioxide electroreduction
The carbon dioxide that few 30min is passed in the H-type electrolytic cell of potassium electrolyte drives other gases away, and the electrolytic cell is by 115 matter of Nafion
Proton exchange separates anode and cathode.
In cadmium sulfoselenide alloy nano stick of the present invention, the molar ratio of sulphur and selenium is adjustable arbitrary proportion.
A kind of cadmium base chalcogenide nanometer rods proposed by the present invention, preparation method and elctro-catalyst, application and application side
Method, the preparation method is easy to largely synthesize, of low cost, and obtained cadmium base chalcogenide nanometer rods are as carbon dioxide electricity
The catalyst of reduction catalysts production of synthetic gas, catalytic activity, stability are high, are easy to regulate and control the selectivity of catalysate, can keep
While high current density, the gaseous mixture of ratio adjustable carbon monoxide and hydrogen in a wide range of is obtained；By adjusting cadmium base sulphur
Sulphur in compounds of group nanometer rods and selenium molar ratio, can in regulation of carbon dioxide electroreduction product syngas carbon monoxide and
The molar ratio of hydrogen, its adjustable range is 4 under relative standard's hydrogen electrode -1.2V overpotentials:1 to 1:4；In relative standard's hydrogen electricity
Under -1.2V the overpotentials of pole, using the cadmium base chalcogenide nanometer rods of arbitrary sulphur and selenium molar ratio, current density is above
25 milliamps per square centimeter.
Description of the drawings
Fig. 1 is the scanning electron microscope diagram piece of different cadmium base chalcogenide nanometer rods in the present invention；
Fig. 2 is the transmission electron micrograph of monodispersed different cadmium base chalcogenide nanometer rods in the present invention；
Fig. 3 is in the catalysis reaction of carbon dioxide electroreduction, and different cadmium base chalcogenide nanometer rods are in difference in the present invention
The molar ratio curve of CO gas in the product under overpotential；
Fig. 4 is that different cadmium base chalcogenide nanometer rods in the overpotential of relative standard's hydrogen electrode are -1.2V in the present invention
Under, the proportioning and current density of the synthesis gas that electroreduction carbon dioxide generates；
Fig. 5 is in the catalysis reaction of carbon dioxide electroreduction, and cadmium base chalcogenide nanometer rods of the present invention are in relative standard's hydrogen
The overpotential of electrode is that the current density under -1.2V changes over time figure；
Fig. 6 is in the catalysis reaction of carbon dioxide electroreduction, and the different cadmium base chalcogenide nanometer rods of the present invention are opposite
The overpotential of standard hydrogen electrode is under -1.2V, and the molar ratio of gas with various in the product changes over time figure.
Specific implementation mode
In the following, technical scheme of the present invention is described in detail by specific embodiment.
Embodiment 1
A kind of cadmium base chalcogenide nanometer rods proposed by the present invention, are cadmium sulfide nano-stick, and the cadmium sulfide is received
The a diameter of 5-6nm, length 120-170nm of rice stick.
A kind of preparation method for cadmium base chalcogenide nanometer rods that the present invention also proposes, includes the following steps：It will
Cadmium salt is dissolved in anhydrous ethylenediamine, is uniformly mixing to obtain mixed liquor A；Sulphur powder, hydrazine hydrate are added in mixed liquor A, after stirring
Obtain mixed liquid B；Mixed liquid B is subjected to solvent thermal reaction 10h at 150 DEG C, cooling after reaction, centrifugation, washing, drying
Obtain the cadmium base chalcogenide nanometer rods.
A kind of elctro-catalyst that the present invention also proposes, active ingredient include the cadmium base chalcogenide nanometer rods.
A kind of application of the elctro-catalyst that the present invention also proposes in the catalysis reaction of carbon dioxide electroreduction.
Embodiment 2
A kind of cadmium base chalcogenide nanometer rods proposed by the present invention are cadmium sulfoselenide alloy nano stick, and the sulphur
A diameter of 6-7nm of cadmium selenide alloy nanometer rods, length 70-110nm；Wherein, in cadmium sulfoselenide alloy nano stick, sulphur and
The molar ratio of selenium is 3：1, i.e., the molar fraction of sulphur be sulphur, selenium total mole number 75%.
A kind of preparation method for cadmium base chalcogenide nanometer rods that the present invention also proposes, includes the following steps：It will
Cadmium nitrate is dissolved in anhydrous ethylenediamine, is uniformly mixing to obtain mixed liquor A；Sulphur powder, selenium powder, hydrazine hydrate are added in mixed liquor A,
Mixed liquid B is obtained after stirring；Mixed liquid B is subjected to solvent thermal reaction 15h at 130 DEG C, cools down, centrifuge, wash after reaction
It washs, be dried to obtain the cadmium base chalcogenide nanometer rods.
A kind of elctro-catalyst that the present invention also proposes, active ingredient include the cadmium base chalcogenide nanometer rods.
A kind of application of the elctro-catalyst that the present invention also proposes in the catalysis reaction of carbon dioxide electroreduction.
A kind of application process of the elctro-catalyst that the present invention also proposes in the catalysis reaction of carbon dioxide electroreduction, packet
Include following steps：Cadmium base chalcogenide nanometer rods, activated carbon and Nafion solution are scattered in ethyl alcohol, obtained after ultrasound
Solution is uniformly brushed and obtains carbon paper electrode on carbon paper by solution, and using carbon paper electrode as working electrode, silver/silver chloride electrode is made
For reference electrode, graphite rod is used as to electrode, and carbon dioxide electricity is carried out also in the H-type electrolytic cell containing saleratus electrolyte
Original catalysis reaction is catalyzed the carbon monoxide and hydrogen of generation by the additional overpotential of electrochemical workstation and detection current density
Pass through gas chromatographic detection.
Embodiment 3
A kind of cadmium base chalcogenide nanometer rods proposed by the present invention are cadmium sulfoselenide alloy nano stick, and the sulphur
A diameter of 5-7nm of cadmium selenide alloy nanometer rods, length 70-170nm；Wherein, in cadmium sulfoselenide alloy nano stick, sulphur and
The molar ratio of selenium is 1:1, i.e., the molar fraction of sulphur be sulphur, selenium total mole number 50%.
A kind of preparation method of cadmium base chalcogenide nanometer rods proposed by the present invention, includes the following steps：It will
1.5mmol caddies are dissolved in 20mL anhydrous ethylenediamines, are uniformly mixing to obtain mixed liquor A；Sulphur powder and selenium powder are mixed to get
Mixed-powder；1.5mmol mixed-powders and 2mL hydrazine hydrates are added in mixed liquor A, mixed liquid B is obtained after stirring 35min；It will
Mixed liquid B carries out solvent thermal reaction 15h at 130 DEG C, cools down after reaction, is then centrifuged under the rotating speed of 8000rpm
15min is precipitated, and is washed with ethyl alcohol after precipitation is washed with water, and is then dried in vacuo to obtain the cadmium base at 50 DEG C
Chalcogenide nanometer rods.
A kind of elctro-catalyst that the present invention also proposes, active ingredient include the cadmium base chalcogenide nanometer rods.
A kind of application of the elctro-catalyst that the present invention also proposes in the catalysis reaction of carbon dioxide electroreduction.
A kind of application process of the elctro-catalyst that the present invention also proposes in the catalysis reaction of carbon dioxide electroreduction, packet
Include following steps：The Nafion for being 2% by 1.0mg cadmium base chalcogenides nanometer rods, 3mg activated carbons and 35 μ L mass fractions
Solution is scattered in 3mL ethyl alcohol, and ultrasonic 0.5h obtains solution, takes the 280 above-mentioned solution of μ L uniformly carbon paper of the brush in 1cm × 0.5cm
Upper acquisition carbon paper electrode, using carbon paper electrode as working electrode, silver/silver chloride electrode is as reference electrode, graphite rod conduct pair
Electrode, progress carbon dioxide electroreduction is urged in the H-type electrolytic cell containing a concentration of 0.12mol/L saleratus electrolyte of 50mL
Change reaction, by the additional overpotential of electrochemical workstation and detection current density, the carbon monoxide and hydrogen for being catalyzed generation pass through
Gas chromatographic detection.
Embodiment 4
A kind of cadmium base chalcogenide nanometer rods proposed by the present invention are cadmium sulfoselenide alloy nano stick, and a diameter of
5.5-6.5nm, length 90-130nm；Wherein, in cadmium sulfoselenide alloy nano stick, the molar ratio of sulphur and selenium is 1:3, i.e. sulphur
Molar fraction be sulphur, selenium total mole number 25%.
A kind of preparation method of cadmium base chalcogenide nanometer rods proposed by the present invention, includes the following steps：It will
0.5mmol caddies are dissolved in 50mL anhydrous ethylenediamines, are uniformly mixing to obtain mixed liquor A；Sulphur powder and selenium powder are mixed to get
Mixed-powder；0.5mmol mixed-powders and 5mL hydrazine hydrates are added in mixed liquor A, mixed liquid B is obtained after stirring 20min；It will
Mixed liquid B is transferred in reaction kettle, and solvent thermal reaction 10h is carried out at 150 DEG C, cools down, then exists after reaction
5min is centrifuged under the rotating speed of 10000rpm to be precipitated, and is washed with ethyl alcohol after precipitation is washed with water, is then carried out at 70 DEG C
Vacuum drying obtains the cadmium base chalcogenide nanometer rods.
A kind of elctro-catalyst that the present invention also proposes, active ingredient include the cadmium base chalcogenide nanometer rods.
A kind of application of the elctro-catalyst that the present invention also proposes in the catalysis reaction of carbon dioxide electroreduction.
A kind of application process of the elctro-catalyst that the present invention also proposes in the catalysis reaction of carbon dioxide electroreduction, packet
Include following steps：It is 7% by 0.5mg cadmium base chalcogenides nanometer rods, 3.5mg activated carbons and 25 μ L mass fractions
Nafion solution is scattered in 2mL ethyl alcohol, and ultrasonic 1.5h obtains solution, and the 220 above-mentioned solution of μ L is taken uniformly to brush in 1cm × 0.5cm
Carbon paper on obtain carbon paper electrode, using carbon paper electrode as working electrode, silver/silver chloride electrode is as reference electrode, graphite rod
As to electrode, carbon dioxide electricity is carried out in the H-type electrolytic cell containing a concentration of 0.08mol/L saleratus electrolyte of 70mL
Reduction catalysts react, and by the additional overpotential of electrochemical workstation and detection current density, are catalyzed the carbon monoxide and hydrogen of generation
Gas passes through gas chromatographic detection.
Embodiment 5
A kind of cadmium base chalcogenide nanometer rods proposed by the present invention, are cadmium selenide nanorod, and a diameter of 6-7nm,
Length is 100-150nm.
A kind of preparation method for cadmium base chalcogenide nanometer rods that the present invention also proposes, includes the following steps：It will
1mmol caddies are dissolved in 30mL anhydrous ethylenediamines, are uniformly mixing to obtain mixed liquor A；By 1mmol selenium powders and 3mL hydrazine hydrates
It is added in mixed liquor A, mixed liquid B is obtained after stirring 30min；Mixed liquid B is transferred in 45mL reaction kettles, at 140 DEG C into
Row solvent thermal reaction 12h, natural cooling, then centrifuges 8min under the rotating speed of 10000rpm and is precipitated after reaction, will
Precipitation is washed 2 times after being washed with water 3 times with ethyl alcohol, is then dried in vacuo to obtain the cadmium base chalcogenide at 60 DEG C
Nanometer rods.
A kind of elctro-catalyst that the present invention also proposes, active ingredient include the cadmium base chalcogenide nanometer rods.
A kind of application of the elctro-catalyst that the present invention also proposes in the catalysis reaction of carbon dioxide electroreduction.
A kind of application process of the elctro-catalyst that the present invention also proposes in the catalysis reaction of carbon dioxide electroreduction, packet
Include following steps：It is 5% by 0.8mg cadmium base chalcogenides nanometer rods, 3.2mg activated carbons and 30 μ L mass fractions
Nafion solution is scattered in 1mL ethyl alcohol, and ultrasonic 1h obtains solution, and the 250 above-mentioned solution of μ L is taken uniformly to brush 1cm × 0.5cm's
Carbon paper electrode is obtained on carbon paper, using carbon paper electrode as working electrode, silver/silver chloride electrode is made as reference electrode, graphite rod
For to electrode, carbon dioxide electricity is carried out also in the H-type electrolytic cell containing a concentration of 0.1mol/L saleratus electrolyte of 60mL
Original catalysis reaction is catalyzed the carbon monoxide and hydrogen of generation by the additional overpotential of electrochemical workstation and detection current density
Pass through gas chromatographic detection；Wherein, past to contain a concentration of 0.1mol/L carbonic acid of 60mL before carrying out carbon dioxide electrocatalytic reaction
The carbon dioxide for leading to 30min in the H-type electrolytic cell of hydrogen potassium electrolyte drives other gases away, and the electrolytic cell is by 115 protons of Nafion
Exchange membrane separates anode and cathode.
Fig. 1 is the scanning electron microscope diagram piece of different cadmium base chalcogenide nanometer rods in the present invention；As shown in Figure 1,
All cadmium base chalcogenide nanometer rods all have uniform nanorod structure.
Fig. 2 is the transmission electron micrograph of monodispersed cadmium base chalcogenide nanometer rods in the present invention；It can by Fig. 2
Know, the nanorod structure a diameter of 5-7nm, length 70-170nm.
Current density and gas in carbon dioxide reaction are catalyzed in electroreduction to different cadmium base chalcogenide nanometer rods
Selectivity of product is tested：In the condition of application process of the elctro-catalyst of the present invention in the catalysis reaction of carbon dioxide electroreduction
Under, take constant potential to test.The overpotential that relative standard's hydrogen electrode is arranged is -0.8V, and constant potential is tested 40 minutes.It was reacting
Cheng Zhong needs to be continually fed into carbon dioxide with the speed of 10mL/min.The oxygen that reaction Anodic generates is discharged into air.Reaction
Every 8 minutes of the gaseous product (carbon monoxide and hydrogen) generated in the process is examined by the thermal conductivity cell detector of online gas-chromatography
It surveys.After the completion of test, overpotential is changed to -0.9V, -1.0V, -1.1V, -1.2V, identical process is utilized respectively and is tested.By
Test is it is found that all nanometer rods current density under fixed overpotential is differed in 3mA/cm2Within, under -1.2V overpotentials all
It can exceed that 25mA/cm2；CO gas molar ratio in the product as shown in figure 3, from the figure 3, it may be seen that with S ratios increasing
Add, the selectivity of CO gas is consequently increased.
Under the conditions of the overpotential of relative standard's hydrogen electrode is -1.2V, exist to different cadmium base chalcogenide nanometer rods
The activity and stability test of electroreduction carbon dioxide production of synthetic gas：In elctro-catalyst of the present invention in carbon dioxide electroreduction
Under conditions of application process in catalysis reaction, constant potential is taken to test.Be arranged relative standard's hydrogen electrode overpotential be-
1.2V, constant potential are tested 10 hours.During the reaction, it needs to be continually fed into carbon dioxide with the speed of 10mL/min.Reaction
The oxygen that Anodic generates is discharged into air.Every 8 minutes of the gaseous product generated in reaction process is by online gas-chromatography
Thermal conductivity cell detector detects.The synthesis that electroreduction carbon dioxide generates under the current potential of different cadmium base chalcogenide nanometer rods
The proportioning and current density of gas are shown in Fig. 4, and as shown in Figure 4, under the overpotential of -1.2V, which can be with
Realize that the molar ratio of carbon monoxide and hydrogen is 1 in synthesis gas:4 to 4:It is adjustable between 1, and the current density of all synthesis gas is big
In 25mA/cm2；Figure is changed over time by electrochemical workstation record current density and sees Fig. 5, and in Figure 5, curve is from bottom to top
Respectively pure selenium cadmium, sulphur molar fraction are sulphur, the cadmium sulfoselenide alloy nano stick of selenium total moles score 50%, pure selenium cadmium
Current density changes over time curve, as shown in Figure 5, in the continuous use of 10 hours, the serial nano stick catalyst
Current density loss is less than 3%；Fig. 6 is seen by the variation of chromatography detection gas selectivity of product, it will be appreciated from fig. 6 that small at 10
When continuous use in, the variation of the selectivity of the serial nano stick catalyst is less than 3%.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Any one skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of cadmium base chalcogenide nanometer rods, which is characterized in that it is cadmium sulfoselenide alloy nano stick, cadmium sulfide nano
One kind in stick, cadmium selenide nanorod, and a diameter of 5-7nm, length 70- of the cadmium base chalcogenide nanometer rods
170nm。
2. a kind of preparation method of cadmium base chalcogenide nanometer rods as described in claim 1, which is characterized in that including following step
Suddenly：Cadmium salt is dissolved in anhydrous ethylenediamine, mixed liquor A is uniformly mixing to obtain；Sulphur powder and/or selenium powder, hydrazine hydrate are added mixed
It closes in liquid A, mixed liquid B is obtained after stirring；Mixed liquid B is subjected to solvent thermal reaction 10-15h at 130-150 DEG C, reaction terminates
Postcooling centrifugation, washs, is dried to obtain the cadmium base chalcogenide nanometer rods.
3. the preparation method of cadmium base chalcogenide nanometer rods according to claim 2, which is characterized in that the cadmium salt is chlorine
One or two kinds of mixture in cadmium, cadmium nitrate；Preferably, the cadmium salt is caddy.
4. according to the preparation method of cadmium base chalcogenide nanometer rods described in Claims 2 or 3, which is characterized in that including following
Step：0.5-1.5mmol caddies are dissolved in 20-50mL anhydrous ethylenediamines, mixed liquor A is uniformly mixing to obtain；By 0.5-
1.5mmol sulphur powders and/or selenium powder, 2-5mL hydrazine hydrates are added in mixed liquor A, and mixed liquid B is obtained after stirring 20-35min；It will mix
It closes liquid B and carries out solvent thermal reaction 10-15h at 130-150 DEG C, cool down after reaction, then turn in 8000-10000rpm
The lower centrifugation 5-15min of speed is precipitated, and is washed with ethyl alcohol after precipitation is washed with water, it is dry that vacuum is then carried out at 50-70 DEG C
It is dry to obtain the cadmium base chalcogenide nanometer rods.
5. according to the preparation method of any one of the claim 2-4 cadmium base chalcogenide nanometer rods, which is characterized in that packet
Include following steps：1mmol caddies are dissolved in 30mL anhydrous ethylenediamines, mixed liquor A is uniformly mixing to obtain；By 1mmol sulphur
Powder and/or selenium powder, 3mL hydrazine hydrates are added in mixed liquor A, and mixed liquid B is obtained after stirring 30min；Mixed liquid B is transferred to 45mL
In reaction kettle, solvent thermal reaction 12h is carried out at 140 DEG C, after reaction natural cooling, then under the rotating speed of 10000rpm
Centrifugation 8min is precipitated, and is washed 2 times with ethyl alcohol after precipitation is washed with water 3 times, then is carried out being dried in vacuo at 60 DEG C
To the cadmium base chalcogenide nanometer rods.
6. a kind of elctro-catalyst, which is characterized in that its active ingredient includes cadmium Ji Liuzuhuahewuna as described in claim 1
Rice stick.
7. a kind of application of elctro-catalyst as claimed in claim 6 in the catalysis reaction of carbon dioxide electroreduction.
8. a kind of application process of elctro-catalyst as claimed in claim 6 in the catalysis reaction of carbon dioxide electroreduction, feature
It is, includes the following steps：Cadmium base chalcogenide nanometer rods, activated carbon and Nafion solution are scattered in ethyl alcohol, surpassed
Solution is obtained after sound, solution is uniformly brushed and obtains carbon paper electrode on carbon paper, using carbon paper electrode as working electrode, silver/chlorination
Silver electrode is used as reference electrode, graphite rod to electrode, and dioxy is carried out in the H-type electrolytic cell containing saleratus electrolyte
Change the catalysis reaction of carbon electroreduction and one oxidation of generation is catalyzed by the additional overpotential of electrochemical workstation and detection current density
Carbon and hydrogen pass through gas chromatographic detection.
9. application process of the elctro-catalyst in the catalysis reaction of carbon dioxide electroreduction, feature exist according to claim 8
In including the following steps：By 0.5-1.0mg cadmium base chalcogenides nanometer rods, 3-3.5mg activated carbons and 25-35 μ L mass
Score is that the Nafion solution of 2-7% is scattered in 2-3mL ethyl alcohol, and ultrasonic 0.5-1.5h obtains solution, takes 220-280 μ L above-mentioned
Uniformly brush obtains carbon paper electrode to solution on the carbon paper of 1cm × 0.5cm, using carbon paper electrode as working electrode, silver/silver chlorate electricity
As reference electrode, graphite rod is used as to electrode, is containing a concentration of 0.08-0.12mol/L saleratus electrolysis of 50-70mL for pole
The catalysis reaction of carbon dioxide electroreduction is carried out in the H-type electrolytic cell of liquid, passes through the additional overpotential of electrochemical workstation and detection electricity
Current density, the carbon monoxide and hydrogen for being catalyzed generation pass through gas chromatographic detection.
10. application process of the elctro-catalyst in the catalysis reaction of carbon dioxide electroreduction according to claim 8 or claim 9, special
Sign is, includes the following steps：It is by 0.8mg cadmium base chalcogenides nanometer rods, 3.2mg activated carbons and 30 μ L mass fractions
5% Nafion solution is scattered in 1mL ethyl alcohol, and ultrasonic 1h obtains solution, take the 250 above-mentioned solution of μ L uniformly brush 1cm ×
Carbon paper electrode is obtained on the carbon paper of 0.5cm, using carbon paper electrode as working electrode, silver/silver chloride electrode is as reference electrode, stone
Inker is used as to electrode, and titanium dioxide is carried out in the H-type electrolytic cell containing a concentration of 0.1mol/L saleratus electrolyte of 60mL
The catalysis reaction of carbon electroreduction is catalyzed the carbon monoxide of generation by the additional overpotential of electrochemical workstation and detection current density
Pass through gas chromatographic detection with hydrogen.
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| CN109453818A (en) * | 2018-11-23 | 2019-03-12 | 淮北师范大学 | A kind of cadmium sulphur selenium/diethylenetriamine/diamine hybrid inorganic-organic highly effective hydrogen yield material and preparation method thereof |
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