CN114606521A - Phytic acid modified foamy copper electrode and application thereof in preparing aniline through electrocatalytic reduction of nitrobenzene - Google Patents
Phytic acid modified foamy copper electrode and application thereof in preparing aniline through electrocatalytic reduction of nitrobenzene Download PDFInfo
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- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 239000010949 copper Substances 0.000 title claims abstract description 67
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 66
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 235000002949 phytic acid Nutrition 0.000 title claims abstract description 54
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229940068041 phytic acid Drugs 0.000 title claims abstract description 52
- 239000000467 phytic acid Substances 0.000 title claims abstract description 52
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 title claims abstract description 37
- 230000009467 reduction Effects 0.000 title claims abstract description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- 238000002791 soaking Methods 0.000 claims abstract description 8
- 239000006260 foam Substances 0.000 claims description 31
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- -1 phytic acid modified copper Chemical class 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000003792 electrolyte Substances 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 230000010355 oscillation Effects 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 43
- 238000000034 method Methods 0.000 abstract description 8
- 238000002360 preparation method Methods 0.000 abstract description 4
- 230000035484 reaction time Effects 0.000 abstract description 4
- 238000000970 chrono-amperometry Methods 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 12
- 239000007772 electrode material Substances 0.000 description 10
- 238000001179 sorption measurement Methods 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000010531 catalytic reduction reaction Methods 0.000 description 4
- 150000001879 copper Chemical class 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000001453 impedance spectrum Methods 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
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- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 125000006414 CCl Chemical group ClC* 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- KFSUNTUMPUWCMW-UHFFFAOYSA-N ethanol;perchloric acid Chemical compound CCO.OCl(=O)(=O)=O KFSUNTUMPUWCMW-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000005181 nitrobenzenes Chemical class 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/09—Nitrogen containing compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B11/095—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one of the compounds being organic
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The invention discloses a phytic acid modified foamy copper electrode and application thereof in preparing aniline by electrocatalytic reduction of nitrobenzene, wherein the phytic acid modified foamy copper electrode is prepared by soaking pretreated foamy copper into a phytic acid aqueous solution and carrying out hydrothermal reaction for 10-15 hours at 100-180 ℃, and the phytic acid modified foamy copper electrode is simple in preparation method, low in cost, economic and environment-friendly, stable in electrocatalytic performance and recyclable; the method is used as a working electrode in a three-electrode system, a chronoamperometry method is adopted to drive the electrocatalysis reduction of nitrobenzene, and the nitrobenzene has high conversion rate, short reaction time and high aniline selectivity under the conditions of normal temperature and normal pressure, so the method has great commercial potential.
Description
Technical Field
The invention belongs to the technical field of electrocatalysis reduction, and particularly relates to an acid-modified foamy copper electrode and application of the electrode in preparing aniline through efficient electrocatalysis reduction of nitrobenzene.
Background
Anilines have important values in the industrial production of dyes, pharmaceuticals and other chemicals. The selective hydrogenation of nitrobenzene by means of thermocatalytic reaction is one of the important technologies for preparing aniline in modern chemical industry and synthetic chemistry, but the technology usually requires high temperature, high pressure and long reaction time, which not only brings safety hazard, but also easily destroys the associated groups of nitrobenzene derivatives (C-Cl, C-F, C ═ C, C ≡ N and the like). Compared with the traditional method, the electrocatalytic nitrobenzene reduction (NHR) technology has more mild conditions (room temperature, normal pressure, no toxic chemical reagent and the like) and better effects (high conversion rate, good selectivity, short reaction time and the like) (Acc. chem. Res.2018,51, 1711-. The practical efficiency and cost of this technology are highly dependent on the electrode catalyst used, and therefore it is of great importance to develop inexpensive, high performance NHR electrode materials.
Among the NHR electrode materials, transition metal copper has become the most promising candidate material due to its high abundance, low cost, environmental protection and strong ability to bind nitrobenzene substrates (electrochim. acta 1989, 34,439 and 445). More recently, Pescarmona et al (appl. Catal. B-environ.2014,147,330-339) used a dip annealing process to support copper/copper oxide nanoparticles on multi-walled carbon nanotubes, developing a series of NHR electrode materials. The electrode can efficiently catalyze and reduce nitrobenzene, the conversion rate of nitrobenzene in 52 hours is 44%, the conversion rate is 0.0064 mmol/hour, and the selectivity of aniline is 82%. Sheng et al (ChemElectrochem 2014,1, 1198-xO nanoparticles supported on activated carbon (Cu/AC (N) -H2). The electrode can efficiently catalyze and reduce nitrobenzene, the conversion rate of nitrobenzene in 52 hours is 51%, the conversion rate is 0.0074 mmol/hour, and the selectivity of aniline is 8%. Daems et al (appl.Catal.B-environ.2018, 226509-522) prepared a copper-based electrocatalyst (Cu-PANI-AC-A) from a composite material of activated carbon and polyaniline by a thermal cracking method. The electrode can efficiently catalyze and reduce nitrobenzene, the conversion rate of nitrobenzene in 52 hours is 54 percent, the conversion rate is 0.0078 mmol/hour, and the selectivity of aniline is 82 percent.
In summary, the following problems still exist with the existing copper-based NHR electrode materials: firstly, the catalytic efficiency still needs to be improved, and the reaction time is longer; secondly, if the catalytic performance is further improved, complex modification means such as micro-scale and nano-scale material structure design and the like are needed; furthermore, most catalysts do not completely reduce nitrobenzene to aniline. Therefore, how to develop a new copper-based NHR electrode material to improve the above problems remains a significant challenge.
Disclosure of Invention
The invention aims to provide a phytic acid modified foamy copper electrode which is simple in preparation method, low in cost, economic, environment-friendly, stable in electrochemical performance and capable of being recycled, and an application of the electrode in preparing aniline through efficient catalytic reduction of nitrobenzene.
In order to achieve the technical purpose, the phytic acid modified copper foam electrode is prepared by soaking pretreated copper foam into 1-5% phytic acid aqueous solution by mass and carrying out hydrothermal reaction at 100-180 ℃ for 10-15 hours.
Preferably, the phytic acid modified foamy copper electrode is prepared by soaking pretreated foamy copper into 2-3.5 mass percent phytic acid aqueous solution and carrying out hydrothermal reaction at 120-150 ℃ for 10-12 hours.
The preparation method of the pretreated foamy copper comprises the following steps: putting the foamy copper into hydrochloric acid, carrying out ultrasonic cleaning to remove an oxide layer and impurities on the surface, and then respectively carrying out ultrasonic oscillation treatment in ethanol, acetone and deionized water to remove redundant hydrochloric acid on the surface of the foamy copper to obtain pretreated foamy copper; the concentration of HCl in the hydrochloric acid is 0.3-1 mol/L.
The invention relates to an application of a phytic acid modified foamy copper electrode in preparing aniline through electrocatalytic reduction of nitrobenzene, which comprises the following specific steps: the phytic acid modified foamy copper electrode is used as a working electrode, the saturated calomel electrode is used as a reference electrode, the graphite electrode is used as a counter electrode, 0.3mol/L potassium perchlorate ethanol solution is used as electrolyte, nitrobenzene is added into the electrolyte, and the aniline is prepared by carrying out electrocatalytic reduction on the nitrobenzene under the condition of voltage of-0.7 to-1.1V vs.
The invention has the following beneficial effects:
the invention prepares the phytic acid modified foamy copper electrode by pretreating the foamy copper electrode with hydrochloric acid and then reacting with phytic acid. The modification of the phytic acid root in the electrode can promote the adsorption of the electrode material to protons, thereby effectively enhancing the catalytic performance. The electrode material disclosed by the invention is simple in preparation method, low in cost, environment-friendly, high in conversion efficiency when used for electrocatalytic reduction of nitrobenzene and good in recycling performance. Therefore, the invention provides a new way for efficiently preparing high-added-value fine chemical products.
Drawings
FIG. 1 is a scanning electron micrograph of the copper foam pretreated in example 1.
FIG. 2 is a scanning electron micrograph and an elemental distribution chart of the phytic acid-modified copper foam electrode prepared in example 1.
FIG. 3 is an infrared spectrum of the phytic acid modified copper foam electrode prepared in example 1.
FIG. 4 is a graph of current density versus voltage obtained with the phytic acid-modified copper foam electrode prepared in example 1 at a scan rate of 5mV/s with no and 0.15mol/L nitrobenzene added.
FIG. 5 is a bar graph of nitrobenzene conversion and aniline selectivity versus voltage for the catalytic reduction of the phytic acid modified copper foam electrode prepared in example 1 at different voltages.
FIG. 6 is a graph of the current density of the phytic acid modified copper foam electrode prepared in example 1, which is changed with time after 3 times of cycles, and the nitrobenzene conversion rate and aniline selectivity.
FIG. 7 is the electrochemical impedance spectrum (a) of the phytic acid-modified copper foam electrode (PA-CF) prepared in example 1 and the electrochemical impedance spectrum (b) of the blank copper foam electrode (CF).
FIG. 8 is a proton adsorption amount analysis of the phytic acid-modified copper foam electrode (PA-CF) and the blank copper foam electrode (CF) prepared in example 1.
FIG. 9 shows the nitrobenzene conversion, conversion rate and aniline selectivity at-0.8V vs. SCE for the phytic acid modified copper foam electrode (PA-CF) and the blank copper foam electrode (CF) prepared in example 1.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, but the scope of the present invention is not limited to these examples.
Example 1
Soaking 1cm × 3cm × 0.2cm of foamy copper in 0.3mol/L hydrochloric acid, ultrasonically cleaning for 20 minutes to remove an oxide layer and pollutants on the surface, and then respectively carrying out ultrasonic oscillation treatment in ethanol, acetone and deionized water to remove redundant hydrochloric acid on the surface to obtain the pretreated foamy copper. The pretreated copper foam electrode is tested by a scanning electron microscope, and as shown in figure 1, the surface of the pretreated copper foam is flat and smooth. Then 73mL of phytic acid aqueous solution with the mass fraction of 2% is poured into 100mL of polytetrafluoroethylene hydrothermal reaction kettle, the pretreated foamy copper is added, the hydrothermal reaction kettle is placed into an air-blowing drying oven, the reaction is carried out for 10 hours under the hydrothermal condition of 120 ℃, and the reaction kettle is cooled to the room temperature. And taking out the yellow foamy copper, repeatedly washing with deionized water and ethanol respectively under ultrasonic treatment, and drying at 60 ℃ to obtain the phytic acid modified foamy copper electrode. As can be seen from the figure 2, the surface of the phytic acid modified copper foam electrode is still flat and smooth, no obvious change is caused, and the element distribution diagram shows that the P element is uniformly distributed on the nickel foam. In addition, the infrared spectrum of the phytic acid modified nickel foam electrode is also tested, and a typical peak of phytate is marked in fig. 3, so that successful modification of the phytate on the electrode is further indicated.
A three-electrode system is adopted, the phytic acid modified foam copper electrode obtained in the embodiment is used as a working electrode, a saturated calomel electrode is used as a reference electrode, a graphite electrode is used as a counter electrode, 50mL of 0.3mol/L perchloric acid ethanol solution is used as electrolyte, Nitrobenzene (NB) is added into the electrolyte to enable the concentration of the nitrobenzene in the electrolyte to be 0.015mol/L, meanwhile, nitrobenzene is not added to be used as a control experiment, and the change condition of current density along with voltage is recorded on an electrochemical workstation (CHI760E, Shanghai Chenghua instruments company) under the condition that the scanning speed is 5 mV/s. As shown in FIG. 4, the catalytic electrode prepared by the method is added with 0.015mol/L nitrobenzene and then is added with 10mA cm-2The corresponding voltage is 1.21V vs. SCE which is far lower than the corresponding 1.42V vs. SCE when nitrobenzene is not added, and the potential difference is as high as 0.21V vs. SCE.
In order to further evaluate the performance of the phytic acid modified copper foam electrode in the electro-catalytic reduction of nitrobenzene, a graph of the nitrobenzene conversion rate obtained by reacting for 24 hours at different voltages and the voltage was recorded on an electrochemical workstation (CHI760E, shanghai chenhua instruments), the product was obtained by diluting the product to pH 7 with 1mol/L KOH and PBS buffer solution and filtering, and the nitrobenzene conversion rate was determined by a gas chromatography external standard method. As can be seen in FIG. 5, the nitrobenzene conversion and aniline selectivity varied with voltage (-0.4 to-1.1V vs. SCE). When the voltage is increased from-0.4V to-0.8V vs. SCE, the conversion rate of nitrobenzene is gradually increased, and under-0.8V, the conversion rate of nitrobenzene reaches 85 percent after 24 hours of reaction, the conversion rate is 0.0266 mmol/h, and the selectivity of aniline can reach 99 percent. However, increasing the voltage from-0.8V to-1.1V vs. SCE high potential, both nitrobenzene conversion and aniline selectivity decreased. This is probably due to the HER reaction occurring at high potential in 0.3mol/L perchloric acid in ethanol. Therefore, the electrode material can realize the efficient conversion of nitrobenzene to prepare aniline under low voltage, and has wide application prospect.
The cycling stability of the electric reduction of nitrobenzene at-0.8V vs. sce for the phytic acid modified foamy copper electrode was further investigated (as shown in fig. 6). In addition, the selectivity of the product aniline during the recycle was determined by gas chromatography-mass spectrometry (GC-MS). The results show that the nitrobenzene conversion is maintained at 80% and the aniline selectivity is maintained at substantially 99% after 3 cycles per 24 hours of reaction (FIG. 6). These results all confirm that the phytic acid modified foamy copper electrode can realize high-efficiency nitrobenzene electrochemical reduction, and the reaction activity and stability are excellent, so that an effective energy-saving way is provided for organic conversion.
Example 2
Soaking 1cm × 3cm × 0.2cm of foamy copper in 0.6mol/L hydrochloric acid, ultrasonically cleaning for 20 minutes to remove an oxide layer and pollutants on the surface, and then respectively carrying out ultrasonic oscillation treatment in ethanol, acetone and deionized water to remove redundant hydrochloric acid on the surface to obtain the pretreated foamy copper. Then pouring 74mL of 2.7 mass percent phytic acid aqueous solution into a 100mL polytetrafluoroethylene hydrothermal reaction kettle, adding pretreated foamy copper, putting the hydrothermal reaction kettle into an air-blowing drying oven, reacting for 12 hours under the hydrothermal condition of 150 ℃, and cooling the reaction kettle to room temperature. And taking out the yellow foamy copper, repeatedly washing with deionized water and ethanol respectively under ultrasonic treatment, and drying at 70 ℃ to obtain the phytic acid modified foamy copper electrode.
The phytic acid modified foamy copper electrode obtained in the embodiment is used as a working electrode, a saturated calomel electrode is used as a reference electrode, a graphite electrode is used as a counter electrode, 1mol/L potassium perchlorate ethanol solution is used as electrolyte, nitrobenzene is added into the electrolyte, the concentration of the nitrobenzene in the electrolyte is 0.015mol/L, and then the aniline is prepared by carrying out electrocatalytic reduction on the nitrobenzene at the room temperature under the condition that the voltage is-0.8V vs. The results showed that 24 hours of reaction gave 80% nitrobenzene conversion, 0.025 mmol/hour conversion and 99% aniline selectivity.
Example 3
Soaking 1cm × 3cm × 0.2cm of foamy copper in 0.6mol/L hydrochloric acid, ultrasonically cleaning for 20 minutes to remove an oxide layer and pollutants on the surface, and then respectively carrying out ultrasonic oscillation treatment in ethanol, acetone and deionized water to remove redundant hydrochloric acid on the surface to obtain the pretreated foamy copper. Then pouring 75mL of phytic acid aqueous solution with the mass fraction of 3.3% into a 100mL polytetrafluoroethylene hydrothermal reaction kettle, adding pretreated foamy copper, putting the hydrothermal reaction kettle into an air-blowing drying oven, reacting for 15 hours under the hydrothermal condition of 180 ℃, and cooling the reaction kettle to room temperature. Taking out the yellow foamy copper, respectively washing with deionized water and ethanol repeatedly under ultrasound, and drying at 80 ℃ to obtain the phytic acid modified foamy copper electrode.
A three-electrode system is adopted, the phytic acid modified foamy copper electrode obtained in the embodiment is used as a working electrode, a saturated calomel electrode is used as a reference electrode, a graphite electrode is used as a counter electrode, 1mol/L potassium perchlorate ethanol solution is used as electrolyte, nitrobenzene is added into the electrolyte, the concentration of the nitrobenzene in the electrolyte is 0.015mol/L, and then the nitrobenzene is subjected to electrocatalytic reduction by adopting a timing current method at room temperature under the condition that the voltage is-0.8V vs. The results showed that the nitrobenzene conversion was 75% at 24 hours of reaction, the conversion was 0.023 mmol/hour, and the aniline selectivity was 99%.
In order to prove the beneficial effects of the invention, a three-electrode system is adopted, a blank copper foam electrode, the phytic acid modified copper foam electrode prepared in example 1, a saturated calomel electrode are used as reference electrodes, a graphite electrode is used as a counter electrode, 0.3mol/L potassium perchlorate ethanol solution is used as electrolyte, nitrobenzene is added, the concentration of nitrobenzene in the electrolyte is 0.015mol/L, electrochemical impedance spectra (see figure 7) of the two working electrodes are represented by an electrochemical workstation (CHI760E, Shanghai Chenghua instruments company) and the adsorption condition of protons on the electrode surface is analyzed. The proton adsorption capacity of the blank copper foam electrode and the phytic acid modified copper foam electrode is compared with the proton adsorption capacity of the phytic acid modified copper foam electrode in the catalysis process by observing the integral of the proton adsorption capacity relative to the overpotential of the catalysis reaction (see figure 8). The result shows that the adsorption amount of the proton on the surface of the phytic acid modified foamy copper electrode is 2.36 times that of blank foamy copper, and the modification of the phytic acid radical can promote the adsorption of the proton on the surface of the electrode material. Further characterization of the catalytic performance of the phytic acid modified foamy copper electrode and the blank foamy copper electrode in catalytic reduction of nitrobenzene (see fig. 9) can obtain: the phytic acid modified foamy copper electrode is adopted for catalytic reaction for 24 hours, the conversion rate of nitrobenzene is 85 percent, the conversion rate is 0.0266 mmol/h, and the selectivity of aniline is 99 percent; a blank foamy copper electrode is adopted for catalytic reaction for 24 hours, the conversion rate of nitrobenzene is only 9.9 percent, the conversion efficiency is 0.0031 mmol/hour, and the selectivity of aniline is 25 percent. Therefore, the phytic acid root modification has the beneficial effect of improving the catalytic performance of the electrode material. Therefore, the phytic acid modified foamy copper electrode can be applied to preparing aniline by efficiently carrying out electrocatalytic reduction on nitrobenzene.
Claims (5)
1. A phytic acid modified foamy copper electrode is characterized in that: the electrode is prepared by soaking pretreated foamy copper into 1-5% phytic acid aqueous solution by mass percent and carrying out hydrothermal reaction for 10-15 hours at 100-180 ℃.
2. The phytic acid modified copper foam electrode according to claim 1, wherein: the electrode is prepared by soaking pretreated foamy copper into 2-3.5% phytic acid aqueous solution and carrying out hydrothermal reaction at 120-150 ℃ for 10-12 hours.
3. The phytic acid modified copper foam electrode according to claim 1 or 2, wherein: putting the foamy copper into hydrochloric acid, carrying out ultrasonic cleaning to remove an oxide layer and impurities on the surface, and then respectively carrying out ultrasonic oscillation treatment in ethanol, acetone and deionized water to remove redundant hydrochloric acid on the surface of the foamy copper to obtain pretreated foamy copper; the concentration of HCl in the hydrochloric acid is 0.3-1 mol/L.
4. The application of the phytic acid modified copper foam electrode in preparing aniline through electrocatalytic reduction of nitrobenzene according to claim 1.
5. The application of the phytic acid modified copper foam electrode in preparing aniline through electrocatalytic reduction of nitrobenzene according to claim 4, wherein the phytic acid modified copper foam electrode is characterized in that: the phytic acid modified foamy copper electrode is used as a working electrode, the saturated calomel electrode is used as a reference electrode, the graphite electrode is used as a counter electrode, 0.3mol/L potassium perchlorate ethanol solution is used as electrolyte, nitrobenzene is added into the electrolyte, and the aniline is prepared by carrying out electrocatalytic reduction on the nitrobenzene under the condition of voltage of-0.7 to-1.1V vs.
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| CN115414935A (en) * | 2022-09-20 | 2022-12-02 | 湖南工程学院 | Preparation method and application of catalyst for degrading nitrobenzene |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4203808A (en) * | 1976-07-14 | 1980-05-20 | Monsanto Company | Electroplating cathodes for electrochemical synthesis |
| CN103000906A (en) * | 2012-12-13 | 2013-03-27 | 天津大学 | Preparation method of foamy copper/carbon nanophase composite negative electrode material for lithium ion battery |
| CN107328835A (en) * | 2017-07-12 | 2017-11-07 | 黄河科技学院 | Reduced graphene modification ferronickel oxyhydroxide electrode and preparation method thereof, application |
| CN109698071A (en) * | 2017-10-24 | 2019-04-30 | 王文建 | A kind of preparation method and high specific volume capacitor of Fabrication of High Specific Capacitance integrated electrode |
| CN111403182A (en) * | 2020-04-08 | 2020-07-10 | 福州大学 | Graphene oxide hybrid polyaniline-based flexible electrode material and preparation method and application thereof |
| US20210078865A1 (en) * | 2017-12-29 | 2021-03-18 | Sixonia Tech Gmbh | Method for producing a functionalized semiconductor or conductor material and use thereof |
| CN112908717A (en) * | 2021-01-21 | 2021-06-04 | 西南大学 | Preparation method of composite electrode material and product thereof |
| CN113353906A (en) * | 2021-05-06 | 2021-09-07 | 江苏大学 | Preparation method of amorphous iron-doped nickel phosphate-carbon composite nanospheres and application of nanospheres to electrode catalyst |
| CN113862709A (en) * | 2021-11-23 | 2021-12-31 | 西北工业大学 | Method for catalytic oxidation of benzyl alcohol based on phytic acid modified nickel foam electrode |
| CN113926477A (en) * | 2020-06-29 | 2022-01-14 | 台州学院 | Ruthenium-loaded phosphorus-doped activated carbon catalyst, preparation method thereof, electrode and application thereof |
-
2022
- 2022-03-01 CN CN202210192763.5A patent/CN114606521B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4203808A (en) * | 1976-07-14 | 1980-05-20 | Monsanto Company | Electroplating cathodes for electrochemical synthesis |
| CN103000906A (en) * | 2012-12-13 | 2013-03-27 | 天津大学 | Preparation method of foamy copper/carbon nanophase composite negative electrode material for lithium ion battery |
| CN107328835A (en) * | 2017-07-12 | 2017-11-07 | 黄河科技学院 | Reduced graphene modification ferronickel oxyhydroxide electrode and preparation method thereof, application |
| CN109698071A (en) * | 2017-10-24 | 2019-04-30 | 王文建 | A kind of preparation method and high specific volume capacitor of Fabrication of High Specific Capacitance integrated electrode |
| US20210078865A1 (en) * | 2017-12-29 | 2021-03-18 | Sixonia Tech Gmbh | Method for producing a functionalized semiconductor or conductor material and use thereof |
| CN111403182A (en) * | 2020-04-08 | 2020-07-10 | 福州大学 | Graphene oxide hybrid polyaniline-based flexible electrode material and preparation method and application thereof |
| CN113926477A (en) * | 2020-06-29 | 2022-01-14 | 台州学院 | Ruthenium-loaded phosphorus-doped activated carbon catalyst, preparation method thereof, electrode and application thereof |
| CN112908717A (en) * | 2021-01-21 | 2021-06-04 | 西南大学 | Preparation method of composite electrode material and product thereof |
| CN113353906A (en) * | 2021-05-06 | 2021-09-07 | 江苏大学 | Preparation method of amorphous iron-doped nickel phosphate-carbon composite nanospheres and application of nanospheres to electrode catalyst |
| CN113862709A (en) * | 2021-11-23 | 2021-12-31 | 西北工业大学 | Method for catalytic oxidation of benzyl alcohol based on phytic acid modified nickel foam electrode |
Non-Patent Citations (3)
| Title |
|---|
| GAO, YUANFENG: "Phytate Coordination-Enhanced Electrocatalytic Activity of Copper for Nitroarene Hydrogenation through Concerted Proton-Coupled Electron Transfer", ACS APPLIED MATERIALS & INTERFACES, vol. 14, no. 12, pages 14202 - 14209 * |
| 贾颖萍, 王为清: "同多酸和杂多酸修饰电极", 大连大学学报, no. 06, pages 20 - 23 * |
| 郭娜;类延华;刘涛;常雪婷;尹衍升;: "植酸水溶液中聚吡咯涂层在Cu基体上的制备及其在腐蚀防护中的应用", 中国腐蚀与防护学报, no. 02, pages 140 - 146 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115414935A (en) * | 2022-09-20 | 2022-12-02 | 湖南工程学院 | Preparation method and application of catalyst for degrading nitrobenzene |
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