CN114318378A - Catalyst for preparing ethanol by electrically reducing CO and preparation method thereof - Google Patents
Catalyst for preparing ethanol by electrically reducing CO and preparation method thereof Download PDFInfo
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Abstract
A catalyst for preparing alcohol by electric reduction of CO is Cu/Cu protected by alkylamine or unsaturated alkylamine2O catalyst, Cu as core, Cu2O is a shell layer. The preparation method comprises the following steps: 1) mixing the raw material Cu (acac)2Uniformly mixing the solution A with a reaction solvent DMF, and stirring to obtain a solution A; 2) dropwise adding an aqueous solution B containing a reducing agent, CTAB, PVP and alkylamine or unsaturated hydrocarbyl amine into the solution A, and stirring to obtain a solution C; 3) transferring the solution C into a high-pressure kettle, sealing, reacting at a certain temperature, filtering and collecting a solid catalyst, washing with an organic solvent, and drying to obtain the catalyst Cu/Cu2And O. at-0.7V vs RHE, C2+The product has Faraday efficiency up to 95% and current density of 151mA cm‑2Wherein the faradaic efficiency of ethanol is 70%.
Description
Technical Field
The invention relates to the technical field of electrochemical catalysis, in particular to a catalyst for preparing ethanol by electrically reducing CO and a preparation method thereof.
Background
Electrochemical reduction of carbon dioxide to fuels and chemicals may be a solution to mitigate dependence on fossil fuels and to mitigate greenhouse gas effects. Production of single carbon products is relatively simple, e.g. CO2RR to CO production is currently in commercial use. Containing two or more carbons (C)2+Products), such as ethylene, acetic acid and ethanol, are useful chemicals or fuels with significant economic value. Thus, efficient reduction of carbon dioxide to C2+The product is very important. Copper-based catalysts have proven effective for converting carbon dioxide to C2+The product has obvious selectivity. However, research efforts still focus on reducing cathode overpotential and further increasing C2+And (4) the product selectivity is high.
CO is considered to form C2+Key reaction intermediates of the compounds. A recent study has demonstrated that CO can be converted at high rates, and therefore CO reduction reactions are receiving increasing attention. Therefore, CO is used as an intermediate raw material and is further converted into C in an electrochemical mode2+Has attractive development prospect.
It is reported that by optimizing the cathode structure, promoting the diffusion of CO on the electrode and copper catalyst surface, the Faradaic Efficiency (FE) of CO reduction to ethylene is as high as 52.7%. In contrast, there has been little research on the reduction of CO to form ethanol. Ethanol has a high energy density, a high market price, and a consistent global demand, and is therefore of particular interest. Unfortunately, the total current density is higher than 100mAcm-2The best faradaic efficiency for CO reduction to ethanol reported to date is only 33%, and the catalyst stability is poor. The search for catalysts with high catalytic activity, selectivity and stability in the reduction of CO to ethanol therefore remains a challenging task.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a catalyst for preparing ethanol by electroreduction of CO and a preparation method thereof, wherein a simple one-pot method is adopted to synthesize Cu/Cu2And the O catalyst improves the Faraday efficiency of the ethanol.
In order to achieve the purpose, the invention adopts the following technical scheme:
a catalyst for preparing ethanol by electrically reducing CO is Cu/Cu protected by alkylamine or unsaturated hydrocarbyl amine2O catalyst, Cu as core, Cu2O is a shell layer, and alkylamine or unsaturated alkyl amine is an outer protective layer.
The preparation method of the catalyst for preparing ethanol by electrically reducing CO comprises the following steps:
1) mixing the raw material Cu (acac)2Evenly mixing the solution and a reaction solvent Dimethylformamide (DMF), and stirring to obtain a solution A;
2) dropwise adding a reducing agent, Cetyl Trimethyl Ammonium Bromide (CTAB), polyvinylpyrrolidone (PVP) and alkylamine or unsaturated alkyl amine aqueous solution B into the solution A, and stirring to obtain a solution C;
3) transferring the solution C into a high-pressure kettle, sealing, reacting at a certain temperature, filtering and collecting a solid catalyst, washing with an organic solvent, and drying to obtain the catalyst Cu/Cu2O。
In the step 1), the stirring is carried out for 3-30 min violently; in the step 2), the stirring time is 10-60 min.
In step 1), Cu (acac)2The mass ratio of the N-dimethylformamide to the N-dimethylformamide is 2-8: 1.
In the step 2), the concentration of the alkylamine or unsaturated alkylamine aqueous solution is 10 wt% to 45 wt%.
In the step 2), the reducing agent is one or more of hexamethylene tetramine, ascorbic acid, tannic acid, citric acid, sodium hypophosphite hydrate, glucose and sodium borohydride; the mass ratio of the reducing agent to the copper element is 1: 1-15.
In the step 2), the mass ratio of Cetyl Trimethyl Ammonium Bromide (CTAB) to copper element is 1: 2-15.
In the step 2), the mass ratio of polyvinylpyrrolidone (PVP) to copper element is 1: 0.5-5.
In the step 3), the certain temperature is 120-200 ℃.
In the step 3), the organic solvent is methanol, ethanol or cyclohexane
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
the invention adopts a simple one-pot method to synthesize Cu/Cu2O catalyst, alkylamine or unsaturated hydrocarbyl amine are loaded on the catalyst, so that the hydrophobicity of the catalyst can be adjusted. The hydrophobic catalyst with a proper amount of alkylamine or unsaturated alkyl amine layer can reduce the affinity of water to an electrode and promote the diffusion of CO to a water electrode interface, thereby inhibiting surface H in CO saturated electrolyte to a certain extent2The transformation of (3). at-0.7V vs RHE, C2+The product has Faraday efficiency up to 95% and current density of 151mA cm-2Wherein the faradaic efficiency of ethanol is 70%. With respect to CO before2Compared with reports of CO electroreduction, the ethanol has the highest Faraday efficiency.
Cu/Cu prepared in the invention2The O catalyst is prepared from metal copper core and Cu2And the shell layer is formed by covering a layer of alkylamine or unsaturated hydrocarbyl amine. The combination of the reducing agent and the stabilizing agent is used for successfully synthesizing Cu/Cu2The key of the O catalyst. The reducing agent may reduce Cu (ii) to Cu (0) or Cu (i). Meanwhile, alkylamine or unsaturated or hydrocarbyl amine is adsorbed on the surface of the catalyst, so that the surface energy is reduced, and agglomeration is avoided. In addition, the alkylamine or unsaturated hydrocarbylamine as a stabilizer may inhibit Cu or Cu2The oxidation of O provides good stability of the oxidation state of the catalyst, which can last for 16 months under ambient conditions without any change.
Drawings
FIG. 1 shows Cu/Cu2SEM image of O catalyst;
FIG. 2 shows Cu/Cu2One of TEM images of O catalyst;
FIG. 3 shows Cu/Cu2A second TEM image of the O catalyst;
FIG. 4 shows Cu/Cu2Wrapping the infrared absorption spectrogram of n-butylamine on the surface of the O catalyst;
FIG. 5 shows Cu/Cu2XRD pattern of O after 8 and 16 months of fresh exposure to air at room temperature.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects of the present invention clearer and clearer, the present invention is further described in detail below with reference to the accompanying drawings and embodiments.
In this example, the electrodes were prepared as follows: 20mg of Cu/Cu2O and 80 mu L of 5 wt% perfluorosulfonic acid solution are dispersed in 1mL of water/ethanol (volume ratio is 4:1) solution, and the catalyst ink is prepared after 3 hours of ultrasonic treatment.
And (3) testing the electrocatalytic activity performance: the CO electroreduction performance was performed by a three-compartment electrochemical flow cell connected to an electrochemical workstation (CHI760 e). The prepared electrode, Ag/AgCl (saturated potassium chloride) and nickel foam materials are respectively used as a working electrode, a reference electrode and an anode. The cathode and anode chambers were separated by an anion exchange membrane (FFA-3(Fumatech)) using 30mL KOH (0.5M, 1.0M, or 2.0M) solution in deionized water as the electrolyte on both sides of the cathode and anode. The CO gas flow rate was controlled to 20mL/min using a mass flow controller (SevenStar D07-7). At the same time, the electrolyte was circulated at a flow rate of 5mL/min by a peristaltic pump. CO can diffuse to the interface between the cathode and the electrolyte. All potentials were measured using Ag/AgCl as a reference electrode (saturated potassium chloride). The gas phase product is analyzed from the outlet of a CO chamber connected with a Gas Chromatograph (GC) during electrolysis, and the liquid phase product passes through after electrolysis1H NMR analysis. The Faraday Efficiency (FE) is calculated from equation (1):
wherein n isprocuctsIs the amount (mol) of the product to be measured, nelectronsIs from CO/H2The number of electrons transferred from O to the product and F is the Faraday constant (C/mo 1). Qt＝0Is the amount of charge passed by the injection site, Qt＝xIs an injectionThe amount of charge passed in the first x seconds (C). x is the time required for CO to fill the GC (gas phase product) sample loop or the amount of time required for catholyte to accumulate in the NMR analysis (liquid phase product).
The potential relative to RHE was calculated using equation (2):
E(RHE) ＝E (Ag/AgCl)+0.197+ pH×0.0591 (2)
after the electrolysis is finished, the applied potential is subjected to ohmic drop correction by using the resistance measured by an electrochemical impedance spectrum under the open-circuit potential. The electrocatalytic reactions involved in the invention are all carried out at normal temperature and normal pressure, and the measurement involved in the invention adopts 85% of ohmic resistance correction. The potentials involved in the present invention are those measured at the GC analysis time point (usually 10min or 30 min).
Example 1
0.20g of Cu (acac)2And 0.1g Dimethylformamide (DMF) were mixed well. After vigorously stirring for 10min, 0.04g of polyvinylpyrrolidone (PVP), 0.015g of cetyltrimethylammonium bromide (CTAB), 0.04g of glucose, 20mL of a 30 wt% aqueous n-butylamine solution were added dropwise. The solution was sealed and heated at 160 ℃ for 10 h. Naturally cooling to room temperature, washing with ethanol to obtain Cu/Cu2And (3) an O catalyst.
And using KOH as an electrolyte, and carrying out COOR performance tests at different potentials in a flow cell reactor. at-0.7V vs RHE, C2+The maximum Faraday efficiency of the product in 2.0M KOH can reach 95%, and the Faraday efficiency of ethanol can reach 70%.
For prepared Cu/Cu2The O catalyst is characterized by a scanning electron microscope, and is Cu/Cu as shown in figure 12And (4) a catalyst micro-topography. For prepared Cu/Cu2The O catalyst is characterized by a transmission electron microscope, and is Cu/Cu as shown in figure 22200 crystal face of O catalyst Cu; FIG. 3 shows Cu/Cu2O catalyst Cu2The 111 crystal plane of O.
For prepared Cu/Cu2And carrying out infrared characterization on the O catalyst. As shown in FIG. 4, the infrared characterization spectrum is 3425cm-1And 2920cm-1Is in a strong infrared absorption band of 3425cm-1Is N-H telescopic vibration area, 2920cm-1Is C-H telescopic vibrationKinetic zone, showing surface butylamine at Cu/Cu2The O surface was successfully modified. FIG. 5 shows Cu/Cu2XRD patterns of O after 8 months and 16 months of fresh air exposure at room temperature show that Cu metal X-ray diffraction peaks are still quite distinct after 16 months, wherein Cu is due to Cu2The content of O is low, XRD diffraction peaks are not obvious, but a large number of CuO diffraction peaks do not appear, which shows that Cu/Cu modified by n-butylamine2O has good stability and does not change the original characteristic peak of the material.
Example 2
0.40g of Cu (acac)2And 0.16g Dimethylformamide (DMF) were mixed well. After vigorous stirring for 10min, 0.2g of polyvinylpyrrolidone (PVP), 0.04g of cetyltrimethylammonium bromide (CTAB), 0.04g of tannic acid, 20mL of a 35 wt% aqueous solution of octadecylamine were added dropwise. The solution was sealed and heated at 165 ℃ for 10 h. Naturally cooling to room temperature, washing with ethanol to obtain Cu/Cu2And (3) an O catalyst.
And using KOH as an electrolyte, and carrying out COOR performance tests at different potentials in a flow cell reactor. at-0.7V vs RHE, C2+The maximum faradaic efficiency of the product in 2.0M KOH can reach 90%, and the faradaic efficiency of the ethanol can reach 68%.
Example 3
0.50g of Cu (acac)2And 0.08g Dimethylformamide (DMF) were mixed well. After vigorous stirring for 10min, 0.13g of polyvinylpyrrolidone (PVP), 0.04g of cetyltrimethylammonium bromide (CTAB), 0.07g of sodium hypophosphite hydrate, 20mL of a 40 wt% aqueous solution of dimethylenediamine were added dropwise. The solution was sealed and heated at 160 ℃ for 10 h. Naturally cooling to room temperature, washing with ethanol to obtain Cu/Cu2And (3) an O catalyst.
And using KOH as an electrolyte, and carrying out COOR performance tests at different potentials in a flow cell reactor. at-0.7V vs RHE, C2+The maximum faradaic efficiency of the product in 2.0M KOH can reach 89%, and the faradaic efficiency of the ethanol can reach 67%.
Example 4
0.35g of Cu (acac)2And 0.12g Dimethylformamide (DMF) were mixed well. Drama (E)After vigorously stirring for 10min, 0.12g of polyvinylpyrrolidone (PVP), 0.03g of cetyltrimethylammonium bromide (CTAB), 0.04g of anti-hexamethylene tetramine, and 20mL of a 42 wt% aqueous solution of dodecyldimethyl tertiary amine were added dropwise. The solution was sealed and heated at 190 ℃ for 10 h. Naturally cooling to room temperature, washing with ethanol to obtain Cu/Cu2And (3) an O catalyst.
And using KOH as an electrolyte, and carrying out COOR performance tests at different potentials in a flow cell reactor. at-0.7V vs RHE, C2+The maximum faradaic efficiency of the product in 2.0M KOH can reach 87%, and the faradaic efficiency of the ethanol can reach 69%.
Example 5
4.5g of Cu (acac)2And 1.5g Dimethylformamide (DMF) were mixed well. After vigorous stirring for 15min, 1.5g of polyvinylpyrrolidone (PVP), 0.5g of cetyltrimethylammonium bromide (CTAB), 0.6g of ascorbic acid, 200mL of a 19 wt% aqueous solution of dodecylprimary amine were added dropwise. The solution was sealed and heated at 160 ℃ for 10 h. Naturally cooling to room temperature, washing with ethanol to obtain Cu/Cu2And (3) an O catalyst.
And using KOH as an electrolyte, and carrying out COOR performance tests at different potentials in a flow cell reactor. at-0.7V vs RHE, C2+The maximum faradaic efficiency of the product in 2.0M KOH can reach 93%, and the faradaic efficiency of the ethanol can reach 70%.
Example 6
25g of Cu (acac)2And 7g Dimethylformamide (DMF) were mixed well. After vigorous stirring for 10min, 8g of polyvinylpyrrolidone (PVP), 2g of cetyltrimethylammonium bromide (CTAB), 3g of sodium borohydride, 2L of a 28% strength by weight aqueous solution of triethylamine were added dropwise. The solution was sealed and heated at 160 ℃ for 10 h. Naturally cooling to room temperature, washing with ethanol to obtain Cu/Cu2And (3) an O catalyst.
And using KOH as an electrolyte, and carrying out COOR performance tests at different potentials in a flow cell reactor. at-0.7V vs RHE, C2+The maximum Faraday efficiency of the product in 2.0M KOH can reach 86%, and the Faraday efficiency of ethanol can reach 65%.
Example 7
0.30g of Cu(acac)2And 0.10g Dimethylformamide (DMF) were mixed well. After vigorous stirring for 10min, 0.10g of polyvinylpyrrolidone (PVP), 0.02g of cetyltrimethylammonium bromide (CTAB), 0.10g of citric acid, 20mL of a 16 wt% aqueous solution of aniline were added dropwise. The solution was sealed and heated at 140 ℃ for 10 h. Naturally cooling to room temperature, washing with ethanol to obtain Cu/Cu2And (3) an O catalyst.
And using KOH as an electrolyte, and carrying out COOR performance tests at different potentials in a flow cell reactor. at-0.7V vs RHE, C2+The maximum faradaic efficiency of the product in 2.0M KOH can reach 89%, and the faradaic efficiency of the ethanol can reach 68%.
Example 8
500g of Cu (acac)2And 80g Dimethylformamide (DMF) were mixed well. After vigorous stirring for 20min, 140g of polyvinylpyrrolidone (PVP), 140g of cetyltrimethylammonium bromide (CTAB), 170g of anticyclohexanetetramine, 20L of a 14% by weight aqueous solution of methylethylcyclopropylamine were added dropwise. The solution was sealed and heated at 160 ℃ for 10 h. Naturally cooling to room temperature, washing with ethanol to obtain Cu/Cu2And (3) an O catalyst.
And using KOH as an electrolyte, and carrying out COOR performance tests at different potentials in a flow cell reactor. at-0.7V vs RHE, C2+The maximum faradaic efficiency of the product in 2.0M KOH can reach 93%, and the faradaic efficiency of the ethanol can reach 69%.
Example 9
0.55g of Cu (acac)2And 0.08g Dimethylformamide (DMF) were mixed well. After vigorous stirring for 10min, 0.16g of polyvinylpyrrolidone (PVP), 0.10g of cetyltrimethylammonium bromide (CTAB), 0.18g of sodium borohydride, 20mL of 42 wt% aqueous diisopropylamine solution were added dropwise. The solution was sealed and heated at 160 ℃ for 10 h. Naturally cooling to room temperature, washing with ethanol to obtain Cu/Cu2And (3) an O catalyst.
And using KOH as an electrolyte, and carrying out COOR performance tests at different potentials in a flow cell reactor. at-0.7V vs RHE, C2+The maximum faradaic efficiency of the product in 2.0M KOH can reach 88%, and the faradaic efficiency of the ethanol can reach 67%.
Example 10
6kg of Cu (acac)2And 0.9kg of Dimethylformamide (DMF) were mixed well. After vigorous stirring for 25min, 1.7kg of polyvinylpyrrolidone (PVP), 1.1kg of cetyltrimethylammonium bromide (CTAB), 1.8kg of sodium borohydride, 200L of 22 wt% aqueous benzhydrylamine solution were added dropwise. The solution was sealed and heated at 180 ℃ for 10 h. Naturally cooling to room temperature, washing with ethanol to obtain Cu/Cu2And (3) an O catalyst.
And using KOH as an electrolyte, and carrying out COOR performance tests at different potentials in a flow cell reactor. at-0.7V vs RHE, C2+The maximum Faraday efficiency of the product in 2.0M KOH can reach 86%, and the Faraday efficiency of ethanol can reach 70%.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims.
Claims (10)
1. A catalyst for preparing ethanol by electrically reducing CO is characterized in that: the catalyst is Cu/Cu protected by alkylamine or unsaturated hydrocarbyl amine2O catalyst, Cu as core, Cu2O is a shell layer, and alkylamine or unsaturated alkyl amine is an outer protective layer.
2. The method for preparing the catalyst for preparing ethanol by electroreduction of CO according to claim 1, comprising the steps of:
1) mixing the raw material Cu (acac)2Evenly mixing the solution and a reaction solvent Dimethylformamide (DMF), and stirring to obtain a solution A;
2) dropwise adding a reducing agent, Cetyl Trimethyl Ammonium Bromide (CTAB), polyvinylpyrrolidone (PVP) and alkylamine or unsaturated alkyl amine aqueous solution B into the solution A, and stirring to obtain a solution C;
3) transferring the solution C into a high-pressure kettle, sealing, reacting at a certain temperature, filtering and collecting a solid catalyst, washing with an organic solvent, and drying to obtain the catalyst Cu/Cu2O。
3. The method of claim 2, wherein: in the step 1), the stirring is carried out for 3-30 min violently; in the step 2), the stirring time is 10-60 min.
4. The method of claim 2, wherein: in step 1), Cu (acac)2The mass ratio of the N-dimethylformamide to the N-dimethylformamide is 2-8: 1.
5. The method of claim 2, wherein: in the step 2), the concentration of the alkylamine or unsaturated alkylamine aqueous solution is 10 wt% to 45 wt%.
6. The method of claim 2, wherein: in the step 2), the reducing agent is one or more of hexamethylene tetramine, ascorbic acid, tannic acid, citric acid, sodium hypophosphite hydrate, glucose and sodium borohydride; the mass ratio of the reducing agent to the copper element is 1: 1-15.
7. The method of claim 2, wherein: in the step 2), the mass ratio of Cetyl Trimethyl Ammonium Bromide (CTAB) to copper element is 1: 2-15.
8. The method of claim 2, wherein: in the step 2), the mass ratio of polyvinylpyrrolidone (PVP) to copper element is 1: 0.5-5.
9. The method of claim 2, wherein: in the step 3), the certain temperature is 120-200 ℃.
10. The method of claim 2, wherein: in the step 3), the organic solvent is methanol, ethanol or cyclohexane.
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