CN114606521B - Copper foam electrode modified by phytic acid and application of copper foam electrode in preparing aniline by electrocatalytic reduction of nitrobenzene - Google Patents
Copper foam electrode modified by phytic acid and application of copper foam electrode in preparing aniline by 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 122
- 239000010949 copper Substances 0.000 title claims abstract description 77
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 75
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000006260 foam Substances 0.000 title claims abstract description 59
- 235000002949 phytic acid Nutrition 0.000 title claims abstract description 57
- 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 46
- 230000009467 reduction Effects 0.000 title claims abstract description 19
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- -1 potassium perchlorate ethanol Chemical compound 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 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 9
- 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
- 238000000034 method Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 230000010355 oscillation Effects 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 45
- 238000002360 preparation method Methods 0.000 abstract description 6
- 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
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000001453 impedance spectrum Methods 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000000137 annealing Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000126 substance Substances 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010531 catalytic reduction reaction 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
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 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
- KFSUNTUMPUWCMW-UHFFFAOYSA-N ethanol;perchloric acid Chemical compound CCO.OCl(=O)(=O)=O KFSUNTUMPUWCMW-UHFFFAOYSA-N 0.000 description 1
- XOCMLLQOZSDGRB-UHFFFAOYSA-N ethyl perchlorate Chemical compound CCOCl(=O)(=O)=O XOCMLLQOZSDGRB-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
- 239000012467 final product Substances 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
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 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
- 150000005181 nitrobenzenes Chemical class 0.000 description 1
- 229920000767 polyaniline Chemical class 0.000 description 1
- 230000008569 process Effects 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
Classifications
-
- 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
Abstract
The invention discloses a phytic acid modified foam copper electrode and an application of the phytic acid modified foam copper electrode in preparing aniline by electrocatalytic reduction of nitrobenzene, wherein the phytic acid modified foam copper electrode is prepared by immersing pretreated foam copper in a phytic acid aqueous solution and carrying out hydrothermal reaction for 10-15 hours at 100-180 ℃, and the phytic acid modified foam copper electrode is simple in preparation method, low in cost, economical and environment-friendly, and stable in electrocatalytic performance and can be recycled; the three-electrode system is used as a working electrode, and the electrocatalytic reduction of nitrobenzene is driven by adopting a chronoamperometry, so that the nitrobenzene has high conversion rate, short reaction time and high aniline selectivity under the condition of normal temperature and normal pressure, and therefore, the three-electrode system has great commercial potential.
Description
Technical Field
The invention belongs to the technical field of electrocatalytic reduction, and particularly relates to a copper foam electrode modified by phytic acid and application of the electrode in preparing aniline by efficiently electrocatalytic reduction of nitrobenzene.
Background
Aniline has important value in the industrial production of dyes, medicines and other chemicals. The realization of selective hydrogenation of nitrobenzene by thermal catalytic reaction is one of the important technologies for preparing aniline in modern chemical industry and synthetic chemistry, but the technology generally requires high temperature, high pressure and long reaction time, which not only brings about potential safety hazards, but also easily damages the associated groups (C-Cl, C-F, C =c, c≡n, etc.) of nitrobenzene derivatives. Compared with the traditional method, the electrocatalytic nitrobenzene reduction (NHR) technology has milder conditions (room temperature, normal pressure, no toxic chemical reagents, and the like) and better effects (high conversion rate, good selectivity, short reaction time, and the like) (Acc.chem.Res.2018, 51, 1711-1721), thereby having great development potential. The practical efficiency and cost of this technology is highly dependent on the electrode catalyst used, so the development of inexpensive, high performance NHR electrode materials is of great significance.
Among a plurality of NHR electrode materials, transition metal copper is the most developed candidate material (electrochromic. Acta 1989,34,439-445) due to the characteristics of high abundance, low cost, environmental protection and strong nitrobenzene substrate binding capacity. Recently, a series of NHR electrode materials have been developed by PearMona et al (appl. Catalyst. B-environ.2014,147, 330-339) using dip annealing to support copper/copper oxide nanoparticles on multi-walled carbon nanotubes. The electrode can efficiently catalyze and reduce nitrobenzene, the nitrobenzene conversion rate is 44% in 52 hours, the conversion efficiency is 0.0064 mmol/hour, and the aniline selectivity is 82%. Preparation of highly dispersed and very small Cu-Cu by Hydrogen annealing by Shing et al (chemElectrochem 2014,1,1198-1210) x O nanoparticles supported on activated carbon (Cu/AC (N) -H 2 ). The electrode can efficiently catalyze and reduce nitrobenzene, the nitrobenzene conversion rate is 51% in 52 hours, the conversion efficiency is 0.0074 mmol/hour, and the aniline selectivity is 8%. Daems et al (appl. Catalyst. B-environ.2018, 226-509-522) prepared copper-based electrocatalyst (Cu-PANI-AC-A) using thermal cracking from activated carbon and polyaniline composites. The electrode can efficiently catalyze and reduce nitrobenzene, the nitrobenzene conversion rate is 54% in 52 hours, the conversion efficiency is 0.0078 mmol/hour, and the aniline selectivity is 82%.
Overall, the existing copper-based NHR electrode materials still have the following problems: firstly, the catalytic efficiency still needs to be improved, and the reaction time is long; secondly, if the catalytic performance is required to be further improved, complex modification means such as micro-scale and nano-scale material structural design and the like are needed; furthermore, most catalysts do not fully reduce nitrobenzene to aniline. Therefore, how to develop a novel copper-based NHR electrode material to improve the above-mentioned problems remains a significant challenge.
Disclosure of Invention
The invention aims to provide a phytic acid modified foam copper electrode which is simple in preparation method, low in cost, economical, environment-friendly, stable in electrochemical performance and capable of being recycled, and an application of the electrode in preparing aniline by efficiently catalyzing and reducing nitrobenzene.
In order to achieve the technical aim, the phytic acid modified copper foam electrode is prepared by immersing pretreated copper foam into 1-5% of phytic acid aqueous solution and performing hydrothermal reaction for 10-15 hours at 100-180 ℃.
Preferably, the phytic acid modified foam copper electrode is prepared by immersing pretreated foam copper into 2-3.5% of phytic acid aqueous solution by mass percent and carrying out hydrothermal reaction for 10-12 hours at 120-150 ℃.
The preparation method of the pretreated foamy copper comprises the following steps: placing the foamy copper into hydrochloric acid, ultrasonically cleaning to remove an oxide layer and impurities on the surface, and respectively performing ultrasonic oscillation treatment in ethanol, acetone and deionized water to remove superfluous 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 phytic acid modified foam copper electrode in preparing aniline by electrocatalytic reduction of nitrobenzene, which comprises the following specific steps: the method comprises the steps of using a phytic acid modified foam copper electrode as a working electrode, using a saturated calomel electrode as a reference electrode, using a graphite electrode as a counter electrode, using a 0.3mol/L potassium perchlorate ethanol solution as an electrolyte, adding nitrobenzene into the electrolyte, and performing electrocatalytic reduction on nitrobenzene at room temperature under the voltage of-0.7 to-1.1V vs.
The beneficial effects of the invention are as follows:
the invention prepares the phytic acid modified foam copper electrode by the reaction of hydrochloric acid and phytic acid after the pretreatment of the foam copper electrode. The modification of the phytate radical in the electrode can promote the adsorption of the electrode material to protons, thereby effectively enhancing the catalytic performance. The electrode material has the advantages of simple preparation method, low cost, environmental protection, high conversion efficiency and good recycling performance when being used for electrocatalytic reduction of nitrobenzene. 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 pretreated copper foam of example 1.
FIG. 2 is a scanning electron micrograph and an elemental distribution of a phytic acid modified copper foam electrode prepared in example 1.
FIG. 3 is an infrared spectrum of a phytic acid modified copper foam electrode prepared in example 1.
FIG. 4 is a graph showing the current density vs. voltage obtained for the phytic acid modified copper foam electrode prepared in example 1 at a scan rate of 5mV/s without the addition and addition of 0.15mol/L nitrobenzene.
FIG. 5 is a bar graph of nitrobenzene conversion and aniline selectivity versus voltage for the phytic acid modified copper foam electrode prepared in example 1 that was catalytically reduced at different voltages.
FIG. 6 is a graph showing the current density of the reaction of the phytic acid modified foam copper electrode prepared in example 1 after 3 cycles with time, nitrobenzene conversion and aniline selectivity.
FIG. 7 is an electrochemical impedance spectrum (a) of a phytic acid modified copper foam electrode (PA-CF) and an electrochemical impedance spectrum (b) of a blank copper foam electrode (CF) prepared in example 1.
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 nitrobenzene conversion, conversion rate and aniline selectivity at-0.8V vs. SCE for the phytic acid modified copper foam electrode (PA-CF) and the bare 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 multiplied by 3cm multiplied by 0.2cm foamy copper in 0.3mol/L hydrochloric acid, ultrasonically cleaning for 20 minutes, removing an oxide layer and pollutants on the surface, and then respectively performing ultrasonic oscillation treatment in ethanol, acetone and deionized water to remove superfluous hydrochloric acid on the surface to obtain pretreated foamy copper. The pretreated foamy copper electrode is tested by a scanning electron microscope, and the pretreated foamy copper electrode has a flat and smooth surface as shown in figure 1. Then 73mL of phytic acid aqueous solution with mass fraction of 2% is poured into a 100mL polytetrafluoroethylene hydrothermal reaction kettle, the pretreated foamy copper is put into a blast drying box, the hydrothermal reaction kettle is reacted for 10 hours under the hydrothermal condition of 120 ℃, and the reaction kettle is cooled to room temperature. Taking out yellow foamy copper, repeatedly washing with deionized water and ethanol respectively under ultrasound, and drying at 60 ℃ to obtain the phytic acid modified foamy copper electrode. As can be seen from fig. 2, the surface of the phytic acid modified foam copper electrode is still smooth, no obvious change exists, and the element distribution diagram shows that the P element is uniformly distributed on the foam nickel. In addition, the infrared spectra of the phytic acid modified foam nickel electrode were also tested, and typical peaks of phytate are shown in fig. 3, further indicating successful modification of phytate on the electrode.
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, so that the concentration of nitrobenzene in the electrolyte is 0.015mol/L, meanwhile, no nitrobenzene is added as a control experiment, and under the condition of 5mV/s of scanning rate, the change condition of current density along with voltage is recorded on an electrochemical workstation (CHI 760E, shanghai Chen Hua instruments). As shown in FIG. 4, the catalytic electrode prepared by the method was prepared by adding 0.015mol/L nitrobenzene at 10mA cm -2 The corresponding voltage is 1.21V vs. SCE, which is far lower than 1.42V vs. SCE when nitrobenzene is not added, and the potential difference is as high as 0.21V vs. SCE.
To further evaluate the performance of the phytic acid modified foam copper electrode in electrocatalytic reduction of nitrobenzene, a graph of nitrobenzene conversion versus voltage obtained by reaction at different voltages for 24 hours was recorded on an electrochemical workstation (CHI 760E, shanghai Chen Hua instruments Co.), and the product was obtained after dilution to ph=7 with 1mol/L KOH and PBS buffer and filtration, and the nitrobenzene conversion was determined by gas chromatography external standard method. As can be seen in FIG. 5, nitrobenzene conversion and aniline selectivity differ with voltage change (-0.4 to-1.1V vs. SCE). When the voltage is increased from-0.4V to-0.8V vs. SCE, the nitrobenzene conversion rate is gradually increased, the nitrobenzene conversion rate reaches 85% after 24 hours of reaction under-0.8V, the conversion efficiency is 0.0266 mmol/hour, and the aniline selectivity can reach 99%. However, at high potentials of-1.1V vs. sce, the voltage was increased from-0.8V, and both nitrobenzene conversion and aniline selectivity decreased. This is probably due to the HER reaction taking place at high potential in 0.3mol/L ethanol perchlorate solution. 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 phytic acid modified copper foam electrode at-0.8 v vs. sce for nitrobenzene electroreduction was further studied (as shown in figure 6). In addition, the selectivity of the product aniline during the cycle was determined by gas chromatography-mass spectrometry (GC-MS). The results showed that after 3 cycles of reaction for 24 hours, nitrobenzene conversion remained 80% and aniline selectivity remained essentially 99% (figure 6 inset). The results prove that the electrochemical reduction of high-efficiency nitrobenzene can be realized by utilizing the phytic acid to modify the foam copper electrode, and the reaction activity and the stability are excellent, so that an effective energy-saving way is provided for organic conversion.
Example 2
Soaking 1cm multiplied by 3cm multiplied by 0.2cm foamy copper in 0.6mol/L hydrochloric acid, ultrasonically cleaning for 20 minutes, removing an oxide layer and pollutants on the surface, and then respectively performing ultrasonic oscillation treatment in ethanol, acetone and deionized water to remove superfluous hydrochloric acid on the surface to obtain pretreated foamy copper. Then, 74mL of phytic acid aqueous solution with the mass fraction of 2.7% is poured into a 100mL polytetrafluoroethylene hydrothermal reaction kettle, the pretreated foamy copper is put into the hydrothermal reaction kettle, the hydrothermal reaction kettle is put into a blast drying box for reaction for 12 hours under the hydrothermal condition of 150 ℃, and the reaction kettle is cooled to the room temperature. Taking out yellow foamy copper, repeatedly washing with deionized water and ethanol respectively under ultrasound, and drying at 70deg.C to obtain the final product.
The 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, 1mol/L potassium perchlorate ethanol solution is used as an electrolyte, nitrobenzene is added into the electrolyte, so that the concentration of nitrobenzene in the electrolyte is 0.015mol/L, and then a timing current method is adopted to perform electrocatalytic reduction on nitrobenzene at room temperature under the condition of voltage of-0.8V vs. The results showed 80% nitrobenzene conversion, 0.025 mmol/hr conversion and 99% aniline selectivity at 24 hours.
Example 3
Soaking 1cm multiplied by 3cm multiplied by 0.2cm foamy copper in 0.6mol/L hydrochloric acid, ultrasonically cleaning for 20 minutes, removing an oxide layer and pollutants on the surface, and then respectively performing ultrasonic oscillation treatment in ethanol, acetone and deionized water to remove superfluous hydrochloric acid on the surface to obtain pretreated foamy copper. Then 75mL of phytic acid aqueous solution with the mass fraction of 3.3% is poured into a 100mL polytetrafluoroethylene hydrothermal reaction kettle, the pretreated foamy copper is put into the hydrothermal reaction kettle, the hydrothermal reaction kettle is put into a blast drying box for reaction for 15 hours under the hydrothermal condition of 180 ℃, and the reaction kettle is cooled to the room temperature. Taking out yellow foamy copper, repeatedly washing with deionized water and ethanol respectively under ultrasound, and drying at 80deg.C to obtain the phytic acid modified foamy copper electrode.
The 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, 1mol/L potassium perchlorate ethanol solution is used as electrolyte, nitrobenzene is added into the electrolyte, the concentration of nitrobenzene in the electrolyte is 0.015mol/L, and then a timing current method is adopted to perform electrocatalytic reduction on nitrobenzene at room temperature under the condition of voltage of-0.8V vs. SCE to prepare aniline. The results showed 75% nitrobenzene conversion at 24 hours of reaction, 0.023 mmol/hr conversion and 99% aniline selectivity.
In order to prove the beneficial effects of the invention, a three-electrode system is adopted, a blank foam copper electrode, the phytic acid modified foam copper electrode prepared in the embodiment 1 are respectively used as reference electrodes, a saturated calomel electrode is used as a counter electrode, 0.3mol/L potassium perchlorate ethanol solution is used as electrolyte, nitrobenzene is added to ensure that the concentration of nitrobenzene in the electrolyte is 0.015mol/L, and an electrochemical workstation (CHI 760E, shanghai Chen Hua instrument company) is utilized to characterize the electrochemical impedance spectrums of the two working electrodes (see figure 7) and analyze the adsorption condition of protons on the surface of the electrodes. The adsorption amount of protons in the catalytic process was compared with that of a blank copper foam electrode and a phytic acid modified copper foam electrode by examining the integral of proton adsorption capacitance with respect to the overpotential of the catalytic reaction (see fig. 8). The result shows that the proton adsorption quantity of the surface of the phytic acid modified foam copper electrode is 2.36 times that of the blank foam copper, and the modification of the phytate can promote the adsorption of protons on the surface of the electrode material. Further by characterizing the catalytic performance of the phytic acid modified foam copper electrode and the blank foam copper electrode for catalytic reduction of nitrobenzene (see figure 9), the following can be obtained: the phytic acid modified foam copper electrode is adopted for catalytic reaction for 24 hours, the nitrobenzene conversion rate is 85%, the conversion efficiency is 0.0266 mmol/hour, and the aniline selectivity is 99%; the reaction is catalyzed by a blank foam copper electrode for 24 hours, the nitrobenzene conversion rate is only 9.9%, the conversion efficiency is 0.0031 mmol/hour, and the aniline selectivity is 25%. Therefore, the modification of the phytate has the beneficial effect of improving the catalytic performance of the electrode material. Therefore, the phytic acid modified foam copper electrode can be applied to the preparation of aniline by high-efficiency electrocatalytic reduction of nitrobenzene.
Claims (3)
1. The application of the phytic acid modified foam copper electrode in preparing aniline by electrocatalytic reduction of nitrobenzene is characterized in that: the method comprises the steps of using a phytic acid modified foam copper electrode as a working electrode, using a saturated calomel electrode as a reference electrode, using a graphite electrode as a counter electrode, using a 0.3mol/L potassium perchlorate ethanol solution as an electrolyte, adding nitrobenzene into the electrolyte, and performing electrocatalytic reduction on nitrobenzene at room temperature under the condition that the voltage is-0.7 to-1.1V vs. SCE to prepare aniline;
the phytic acid modified foam copper electrode is prepared by immersing pretreated foam copper into a phytic acid aqueous solution with the mass fraction of 1% -5%, and carrying out hydrothermal reaction for 10-15 hours at the temperature of 100-180 ℃.
2. The application of the phytic acid modified foam copper electrode in preparing aniline by electrocatalytic reduction of nitrobenzene, according to claim 1, is characterized in that: the phytic acid modified foam copper electrode is prepared by immersing pretreated foam copper into 2-3.5% of phytic acid aqueous solution, and performing hydrothermal reaction at 120-150 ℃ for 10-12 hours.
3. The use of the phytic acid modified foam copper electrode according to claim 1 or 2 for preparing aniline by electrocatalytic reduction of nitrobenzene, which is characterized in that: placing the foamy copper into hydrochloric acid, ultrasonically cleaning to remove an oxide layer and impurities on the surface, and respectively performing ultrasonic oscillation treatment in ethanol, acetone and deionized water to remove superfluous 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.
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|---|---|---|---|
| CN202210192763.5A CN114606521B (en) | 2022-03-01 | 2022-03-01 | Copper foam electrode modified by phytic acid and application of copper foam electrode in preparing aniline by electrocatalytic reduction of nitrobenzene |
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|---|---|---|---|
| CN202210192763.5A CN114606521B (en) | 2022-03-01 | 2022-03-01 | Copper foam electrode modified by phytic acid and application of copper foam electrode in preparing aniline by electrocatalytic reduction of nitrobenzene |
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