CN114318378B - Catalyst for preparing ethanol by electric reduction of CO and preparation method thereof - Google Patents
Catalyst for preparing ethanol by electric reduction of CO and preparation method thereof Download PDFInfo
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Abstract
Catalyst for preparing ethanol by electric reduction of CO and preparation method thereof, wherein the catalyst is Cu/Cu protected by alkylamine or unsaturated alkylamine 2 O catalyst, cu is the inner core, cu 2 O is a shell layer. The preparation method comprises the following steps: 1) Raw Cu (acac) 2 Uniformly mixing 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 alkylamine into the solution A, and stirring to obtain a solution C; 3) Transferring the solution C into an autoclave, sealing, reacting at a certain temperature, filtering, collecting the solid catalyst, washing with an organic solvent, and drying to obtain the catalyst Cu/Cu 2 O. at-0.7V vs RHE, C 2+ The Faraday efficiency of the product reaches 95%, and the current density is 151mA cm ‑2 Wherein the faraday 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 electroreduction of CO and a preparation method thereof.
Background
Electrochemical reduction of carbon dioxide to fuel and chemicals may be a solution to mitigate dependency on fossil fuels and to mitigate the greenhouse gas effect. The production of single carbon products is relatively simple, e.g. CO 2 RR-generation CO is currently in commercial use. Containing two or more carbons (C 2+ Products), such as ethylene, acetic acid and ethanol, are of significant economic valueIs a useful chemical or fuel for the fuel. Thus, high efficiency reduction of carbon dioxide to C 2+ The product is very important. Copper-based catalysts have been demonstrated to be effective in converting carbon dioxide to C 2+ The product has obvious selectivity. However, research efforts have focused on reducing cathode overpotential and further increasing C 2+ Product selectivity aspects.
CO is considered to be the generation of C 2+ Key reaction intermediates of the compounds. A recent study has demonstrated that CO can be converted at a high rate, thus increasing attention has been paid to CO reduction reactions. Thus, CO is used as an intermediate raw material and is further converted into C by an electrochemical mode 2+ Has attractive development prospect.
It is reported that by optimizing the cathode structure, the diffusion of CO at the electrode and copper catalyst surfaces is promoted, and the Faraday Efficiency (FE) of CO reduction to ethylene is as high as 52.7%. In contrast, little research has been done on the reduction of CO to ethanol. Ethanol has high energy density, high market price and consistent global demand, and is therefore of particular concern. Unfortunately, the total current density is higher than 100mAcm -2 The best faradaic efficiency reported to date for the reduction of CO to ethanol is only 33% and the catalyst stability is poor. It remains a challenging task to explore catalysts with high catalytic activity, selectivity and stability in the CO reduction process to ethanol.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a catalyst for preparing ethanol by electric reduction of CO and a preparation method thereof, and the catalyst adopts a simple one-pot method to synthesize Cu/Cu 2 And the O catalyst improves the Faraday efficiency of the ethanol.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a catalyst for preparing ethanol by electric reduction of CO is Cu/Cu protected by alkylamine or unsaturated alkyl amine 2 O catalyst, cu is the inner core, cu 2 O is a shell layer, and alkylamine or unsaturated alkyl amine is an outer protective layer.
The invention relates to a preparation method of a catalyst for preparing ethanol by electric reduction of CO, which comprises the following steps:
1) Raw Cu (acac) 2 Evenly mixing with a reaction solvent Dimethylformamide (DMF), and stirring to obtain a solution A;
2) Dropwise adding an aqueous solution B containing a reducing agent, cetyl Trimethyl Ammonium Bromide (CTAB), polyvinylpyrrolidone (PVP) and alkylamine or unsaturated alkylamine into the solution A, and stirring to obtain a solution C;
3) Transferring the solution C into an autoclave, sealing, reacting at a certain temperature, filtering, collecting the solid catalyst, washing with an organic solvent, and drying to obtain the catalyst Cu/Cu 2 O。
In the step 1), the stirring is vigorous stirring for 3-30 min; in the step 2), the stirring time is 10-60 min.
In step 1), cu (acac) 2 The mass ratio of the catalyst to the dimethylformamide is 2-8:1.
In the step 2), the concentration of the aqueous solution of the alkylamine or the unsaturated alkyl amine is 10 to 45 weight percent.
In the step 2), the reducing agent is one or more of cyclohexamethylenetetramine, 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 beneficial effects that:
the invention adopts a simple one-pot method to synthesize Cu/Cu 2 O catalyst, alkyl amine or unsaturated alkyl amine is supported on the catalyst to make the hydrophobicity adjustable. Hydrophobic catalyst with proper alkyl amine or unsaturated alkyl amine layer capable of reducing water counter electrodeAffinity promotes diffusion of CO to water interface, thereby inhibiting surface H in CO saturated electrolyte to a certain extent 2 Is transformed by the above method. at-0.7V vs RHE, C 2+ The Faraday efficiency of the product reaches 95%, and the current density is 151mA cm -2 Wherein the faraday efficiency of ethanol is 70%. As with the previous description of CO 2 The faradaic efficiency of ethanol according to the invention is highest compared to the report of CO electroreduction.
Cu/Cu prepared in the present invention 2 The O catalyst consists of a metallic copper core and Cu 2 And the O shell layer is formed by coating a layer of alkylamine or unsaturated alkyl amine. The combination of reducing agent and stabilizer is successful in synthesizing Cu/Cu 2 The key of the O catalyst. The reducing agent may reduce Cu (II) to Cu (0) or Cu (I). At the same time, alkyl amine or unsaturated or alkyl amine is adsorbed on the surface of the catalyst, so that the surface energy is reduced and agglomeration is avoided. In addition, alkylamines or unsaturated alkylamines as stabilizers can inhibit Cu or Cu 2 Oxidation of O gives the catalyst its oxidation state good stability and can last for 16 months without any change under ambient conditions.
Drawings
FIG. 1 is Cu/Cu 2 SEM image of O catalyst;
FIG. 2 is Cu/Cu 2 One of the TEM images of the O catalyst;
FIG. 3 is Cu/Cu 2 A second TEM image of the O catalyst;
FIG. 4 is a Cu/Cu diagram 2 The surface of the O catalyst is wrapped with the infrared absorption spectrum of n-butylamine;
FIG. 5 is Cu/Cu 2 XRD patterns after 8 months and 16 months of fresh exposure of O to air at room temperature.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear and obvious, the invention is further described in detail below with reference to the accompanying drawings and embodiments.
In this example, the electrode was prepared as follows: 20mg Cu/Cu 2 O and 80. Mu.L of a 5wt% perfluorosulfonic acid solution were dispersed in 1mL of a water/ethanol (volume ratio of 4:1) solution and sonicated for 3 hours to prepare a catalyst ink.
Electrocatalytic activity performance test: the CO electroreduction performance was performed by a three-compartment electrochemical flow cell connected to an electrochemical workstation (CHI 760 e). The prepared electrode, ag/AgCl (saturated potassium chloride) and nickel foam material are respectively used as a working electrode, a reference electrode and an anode. 30mL KOH (0.5M, 1.0M or 2.0M) solution in deionized water was used as the electrolyte on both sides of the cathode and anode, and the cathode and anode chambers were separated by an anion exchange membrane (FFA-3 (Fumatech)). The CO gas flow was controlled to 20mL/min using a mass flow controller (SevenStar D07-7). At the same time, the electrolyte was circulated by a peristaltic pump at a flow rate of 5 mL/min. CO may diffuse to the interface between the cathode and the electrolyte. All potentials were measured using Ag/AgCl as reference electrode (saturated potassium chloride). The gas phase product is analyzed from the CO chamber outlet connected to Gas Chromatography (GC) during electrolysis, and the liquid phase product is passed through after electrolysis 1 H NMR analysis. The Faraday Efficiency (FE) is calculated by equation (1):
wherein n is procucts Is the amount (mol) of the product to be measured, n electrons Is from CO/H 2 The number of electrons O transfers to the product, F is the Faraday constant (C/mo 1). Q (Q) t＝0 Is the amount of charge passing through the injection point, Q t＝x Is the amount of charge (C) passed within x seconds before injection. x is the time required for CO to fill the GC (gas phase product) feed loop or the amount of catholyte to accumulate into 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 completed, the applied potential is subjected to ohmic drop correction by using the resistance measured by electrochemical impedance spectroscopy at the open circuit potential. The electrocatalytic reactions involved in the invention are all carried out at normal temperature and pressure, and the measurements involved in the invention are all corrected by adopting 85% ohmic resistance. The potential to which the present invention relates is a potential measured at a GC analysis time point (typically 10min or 30 min).
Example 1
0.20g of Cu (acac) 2 And 0.1g Dimethylformamide (DMF) were mixed well. After stirring vigorously for 10min, 0.04g polyvinylpyrrolidone (PVP), 0.015g cetyltrimethylammonium bromide (CTAB), 0.04g glucose, 20mL of 30wt% aqueous n-butylamine solution are added dropwise. The solution was sealed and heated at 160℃for 10h. Naturally cooling to room temperature, washing with ethanol to obtain Cu/Cu 2 And (3) an O catalyst.
And (3) taking KOH as electrolyte, and performing COOR performance tests under different potentials in a flow battery reactor. at-0.7V vs RHE, C 2+ The maximum Faraday efficiency of the product in 2.0M KOH can reach 95%, and the Faraday efficiency of ethanol can reach 70%.
For the prepared Cu/Cu 2 The O catalyst is subjected to scanning electron microscope characterization, and Cu/Cu is shown in FIG. 1 2 And (3) a microscopic morphology diagram of the O catalyst. For the prepared Cu/Cu 2 The O catalyst was subjected to transmission electron microscope characterization, as shown in FIG. 2 as Cu/Cu 2 The 200 crystal face of the O catalyst Cu; FIG. 3 is Cu/Cu 2 O catalyst Cu 2 The 111 crystal plane of O.
For the prepared Cu/Cu 2 The O catalyst was infrared characterized. As shown in FIG. 4, the infrared signature spectrum was at 3425cm -1 And 2920cm -1 The region is in the strong infrared absorption band of 3425cm -1 Is an N-H telescopic vibration area of 2920cm -1 Is a C-H telescopic vibration area, which shows that the surface butylamine is in Cu/Cu 2 The O surface was successfully modified. FIG. 5 is Cu/Cu 2 XRD patterns of O after 8 months and 16 months of fresh air exposure at room temperature, showing a significant Cu metal X-ray diffraction peak after 16 months, wherein due to Cu 2 The O content is low, the XRD diffraction peak is not obvious, but a large number of CuO diffraction peaks do not appear, which indicates that the Cu/Cu modified by n-butylamine 2 O has good stability and does not change the original characteristic peak of the material.
Example 2
0.40g of Cu (acac) 2 And 0.16g Dimethylformamide (DMF) were mixed well. After stirring vigorously for 10min, 0.2g polyvinylpyrrolidone (PVP) and 0.04g hexadecane were added dropwiseTrimethyl Ammonium Bromide (CTAB), 0.04g tannic acid, 20mL of a 35wt% aqueous solution of octadecylamine. The solution was sealed and heated at 165℃for 10h. Naturally cooling to room temperature, washing with ethanol to obtain Cu/Cu 2 And (3) an O catalyst.
And (3) taking KOH as electrolyte, and performing COOR performance tests under different potentials in a flow battery reactor. at-0.7V vs RHE, C 2+ The maximum Faraday efficiency of the product in 2.0M KOH can reach 90%, and the Faraday efficiency of ethanol can reach 68%.
Example 3
0.50g of Cu (acac) 2 And 0.08g of Dimethylformamide (DMF) were mixed well. After stirring vigorously for 10min, 0.13g polyvinylpyrrolidone (PVP), 0.04g cetyltrimethylammonium bromide (CTAB), 0.07g sodium hypophosphite hydrate, 20mL of 40wt% aqueous dimethylene diamine solution were added dropwise. The solution was sealed and heated at 160℃for 10h. Naturally cooling to room temperature, washing with ethanol to obtain Cu/Cu 2 And (3) an O catalyst.
And (3) taking KOH as electrolyte, and performing COOR performance tests under different potentials in a flow battery reactor. at-0.7V vs RHE, C 2+ The maximum Faraday efficiency of the product in 2.0M KOH can reach 89%, and the Faraday efficiency of ethanol can reach 67%.
Example 4
0.35g of Cu (acac) 2 And 0.12g of Dimethylformamide (DMF) were mixed well. After stirring vigorously for 10min, 0.12g polyvinylpyrrolidone (PVP), 0.03g cetyltrimethylammonium bromide (CTAB), 0.04g anti-cyclohexanetetramine, 20mL 42wt% aqueous solution of dodecyldimethyl tertiary amine were added dropwise. The solution was sealed and heated at 190℃for 10h. Naturally cooling to room temperature, washing with ethanol to obtain Cu/Cu 2 And (3) an O catalyst.
And (3) taking KOH as electrolyte, and performing COOR performance tests under different potentials in a flow battery reactor. at-0.7V vs RHE, C 2+ The maximum Faraday efficiency of the product in 2.0M KOH can reach 87%, and the Faraday efficiency of ethanol can reach 69%.
Example 5
4.5g Cu (acac) 2 And 1.5g of dimethylformamideAmine (DMF) was mixed well. After stirring vigorously for 15min, 1.5g polyvinylpyrrolidone (PVP), 0.5g cetyltrimethylammonium bromide (CTAB), 0.6g ascorbic acid, 200mL of a 19wt% aqueous solution of primary dodecylamine were added dropwise. The solution was sealed and heated at 160℃for 10h. Naturally cooling to room temperature, washing with ethanol to obtain Cu/Cu 2 And (3) an O catalyst.
And (3) taking KOH as electrolyte, and performing COOR performance tests under different potentials in a flow battery reactor. at-0.7V vs RHE, C 2+ The maximum Faraday efficiency of the product in 2.0M KOH can reach 93 percent, and the Faraday efficiency of ethanol can reach 70 percent.
Example 6
25g of Cu (acac) 2 And 7g of Dimethylformamide (DMF) were mixed uniformly. After vigorous stirring for 10min, 8g polyvinylpyrrolidone (PVP), 2g cetyltrimethylammonium bromide (CTAB), 3g sodium borohydride, 2L 28wt% aqueous triethylamine solution were added dropwise. The solution was sealed and heated at 160℃for 10h. Naturally cooling to room temperature, washing with ethanol to obtain Cu/Cu 2 And (3) an O catalyst.
And (3) taking KOH as electrolyte, and performing COOR performance tests under different potentials in a flow battery reactor. at-0.7V vs RHE, C 2+ 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) 2 And 0.10g of Dimethylformamide (DMF) were mixed well. After stirring vigorously for 10min, 0.10g polyvinylpyrrolidone (PVP), 0.02g cetyltrimethylammonium bromide (CTAB), 0.10g citric acid, 20mL 16wt% aniline in water were added dropwise. The solution was sealed and heated at 140℃for 10h. Naturally cooling to room temperature, washing with ethanol to obtain Cu/Cu 2 And (3) an O catalyst.
And (3) taking KOH as electrolyte, and performing COOR performance tests under different potentials in a flow battery reactor. at-0.7V vs RHE, C 2+ The maximum Faraday efficiency of the product in 2.0M KOH can reach 89%, and the Faraday efficiency of ethanol can reach 68%.
Example 8
500g Cu (acac) 2 And 80g of Dimethylformamide (DMF) were mixed uniformly. After vigorous stirring for 20min, 140g polyvinylpyrrolidone (PVP), 140g cetyltrimethylammonium bromide (CTAB), 170g anti-cyclohexanetetramine, 20L of 14wt% aqueous methyl ethyl cyclopropylamine solution were added dropwise. The solution was sealed and heated at 160℃for 10h. Naturally cooling to room temperature, washing with ethanol to obtain Cu/Cu 2 And (3) an O catalyst.
And (3) taking KOH as electrolyte, and performing COOR performance tests under different potentials in a flow battery reactor. at-0.7V vs RHE, C 2+ The maximum Faraday efficiency of the product in 2.0M KOH can reach 93 percent, and the Faraday efficiency of ethanol can reach 69 percent.
Example 9
0.55g Cu (acac) 2 And 0.08g of Dimethylformamide (DMF) were mixed well. After stirring vigorously for 10min, 0.16g polyvinylpyrrolidone (PVP), 0.10g cetyltrimethylammonium bromide (CTAB), 0.18g sodium borohydride, 20mL 42wt% aqueous diisopropylamine was added dropwise. The solution was sealed and heated at 160℃for 10h. Naturally cooling to room temperature, washing with ethanol to obtain Cu/Cu 2 And (3) an O catalyst.
And (3) taking KOH as electrolyte, and performing COOR performance tests under different potentials in a flow battery reactor. at-0.7V vs RHE, C 2+ The maximum Faraday efficiency of the product in 2.0M KOH can reach 88%, and the Faraday efficiency of ethanol can reach 67%.
Example 10
6kg Cu (acac) 2 And 0.9kg of Dimethylformamide (DMF) were uniformly mixed. After vigorous stirring for 25min, 1.7kg polyvinylpyrrolidone (PVP), 1.1kg cetyltrimethylammonium bromide (CTAB), 1.8kg sodium borohydride, 200L of 22wt% aqueous benzhydryl amine were added dropwise. The solution was sealed and heated at 180℃for 10h. Naturally cooling to room temperature, washing with ethanol to obtain Cu/Cu 2 And (3) an O catalyst.
And (3) taking KOH as electrolyte, and performing COOR performance tests under different potentials in a flow battery reactor. at-0.7V vs RHE, C 2+ The maximum Faraday efficiency of the product in 2.0M KOH can reach 86%, and the Faraday efficiency of ethanol can reach 70%.
The foregoing description is only illustrative of the preferred embodiments of the present invention and is not to be construed as limiting the scope of the invention, i.e., the invention is not to be limited to the details of the invention.
Claims (9)
1. A catalyst for preparing ethanol by electric reduction of CO is characterized in that: the catalyst is Cu/Cu protected by alkylamine or unsaturated alkyl amine 2 O catalyst, cu is the inner core, cu 2 O 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, as claimed in claim 1, which is characterized by comprising the following steps:
1) Raw Cu (acac) 2 Evenly mixing with a reaction solvent Dimethylformamide (DMF), and stirring to obtain a solution A;
2) Dropwise adding an aqueous solution B containing a reducing agent, cetyl Trimethyl Ammonium Bromide (CTAB), polyvinylpyrrolidone (PVP) and alkylamine or unsaturated alkylamine into the solution A, and stirring to obtain a solution C;
3) Transferring the solution C into an autoclave for sealing, reacting at 120-200 ℃, filtering and collecting a solid catalyst, washing with an organic solvent, and drying to obtain the catalyst Cu/Cu 2 O。
3. The method of manufacturing as claimed in claim 2, wherein: in the step 1), the stirring is vigorous stirring for 3-30 min; in the step 2), the stirring time is 10-60 min.
4. The method of manufacturing as claimed in claim 2, wherein: in step 1), cu (acac) 2 The mass ratio of the catalyst to the dimethylformamide is 2-8:1.
5. The method of manufacturing as claimed in claim 2, wherein: in the step 2), the concentration of the aqueous solution of the alkylamine or the unsaturated alkyl amine is 10 to 45 weight percent.
6. The method of manufacturing as claimed in claim 2, wherein: in the step 2), the reducing agent is one or more of cyclohexamethylenetetramine, 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 manufacturing as claimed in 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 manufacturing as claimed in 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 manufacturing as claimed in claim 2, wherein: in the step 3), the organic solvent is methanol, ethanol or cyclohexane.
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