CN113862709B - Method for catalyzing and oxidizing benzyl alcohol based on phytic acid modified foam nickel electrode - Google Patents
Method for catalyzing and oxidizing benzyl alcohol based on phytic acid modified foam nickel electrode Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 184
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 title claims abstract description 180
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 92
- 239000006260 foam Substances 0.000 title claims abstract description 87
- 235000002949 phytic acid Nutrition 0.000 title claims abstract description 61
- 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 60
- 235000019445 benzyl alcohol Nutrition 0.000 title claims abstract description 60
- 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 58
- 229940068041 phytic acid Drugs 0.000 title claims abstract description 58
- 239000000467 phytic acid Substances 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 27
- 230000001590 oxidative effect Effects 0.000 title abstract description 6
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 20
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 54
- 238000006243 chemical reaction Methods 0.000 claims description 38
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- 230000003647 oxidation Effects 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000003792 electrolyte Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-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
- 238000001035 drying Methods 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 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
- 238000005406 washing Methods 0.000 claims description 5
- 230000010355 oscillation Effects 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000000970 chrono-amperometry Methods 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 23
- 238000002360 preparation method Methods 0.000 abstract description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 12
- 239000007772 electrode material Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000005711 Benzoic acid Substances 0.000 description 6
- 235000010233 benzoic acid Nutrition 0.000 description 6
- SESFRYSPDFLNCH-UHFFFAOYSA-N benzyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC1=CC=CC=C1 SESFRYSPDFLNCH-UHFFFAOYSA-N 0.000 description 6
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- -1 phytic acid modified nickel Chemical class 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 229960002903 benzyl benzoate Drugs 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000012847 fine chemical Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 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
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000006056 electrooxidation reaction Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 239000011165 3D composite Substances 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052956 cinnabar Inorganic materials 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram 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
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
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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
- C25B3/07—Oxygen 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
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
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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
- 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
- C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
-
- 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
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/061—Metal or alloy
-
- 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
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/085—Organic compound
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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
- C25B3/20—Processes
- C25B3/23—Oxidation
Abstract
The invention discloses a method for catalyzing and oxidizing benzyl alcohol based on a phytic acid modified foam nickel electrode. The phytic acid modified foam nickel electrode provided by the invention has high catalytic activity and high selectivity for benzyl alcohol oxidation reaction, and the preparation method is simple, low in cost and environment-friendly, so that the phytic acid modified foam nickel electrode has extremely high potential commercial value.
Description
Technical Field
The invention belongs to the technical field of electrocatalysis, and particularly relates to a method for catalyzing and oxidizing benzyl alcohol based on a phytic acid modified foam nickel electrode.
Background
The selective oxidation of benzyl alcohol is one of the most important problems in modern chemical industry and synthetic chemistry, since the corresponding product benzaldehyde is an important raw material for the pharmaceutical, dye, perfume and resin industries, and can also be used as a solvent, plasticizer, low temperature lubricant, etc., which is widely used in the synthesis of pharmaceuticals and fine chemicals as an important organic intermediate. The electrochemical oxidation of benzyl alcohol (BEOR) process has unique advantages over conventional thermochemical oxidation processes in that it avoids the common problems of conventional processes, namely high temperature, high pressure, low conversion, long reaction times, high separation costs, or the involvement of toxic oxidants, etc. (chem. Rev. 2007, 251, 2367), and thus has great potential for development. The core of the method is the catalytic electrode material that is activated. However, most of the commonly used electrode materials are composed of noble metals (such as gold, platinum, palladium, etc.) or complexes thereof, and their BEOR catalytic performance is good, but the cost is too high, which is disadvantageous for industrial production (adv. Function. Mater. 2017, 1704169). Therefore, the development of a novel efficient and low-cost catalytic electrode material has great significance for the development of BEOR methods.
The nickel-based material is expected to be developed into the novel BEOR catalytic electrode material (J. Mater. Chem. A., 2016, 4, 24) because of the high abundance, low cost and environmental protection and the high intrinsic catalytic activity of the nickel-based material to alcohol oxidation. Recently, sun et al (ACS catalyst., 2017, 7, 4564-4570) have used electrodeposition to obtain three-dimensional layered porous nickel-based catalytic electrode materials which can efficiently catalyze the oxidation of benzyl alcohol with a benzyl alcohol conversion rate of up to 100% and a conversion rate of up to 28.57 mmol.L in 0.35 hours -1 ·h -1 The yield of the product benzoic acid was 98%. In addition, the catalytic electrode has high catalytic stability, and the Faraday efficiency can still be kept at 96% -98% after 5 times of catalytic cycles under the condition of 1.423V vs. RHE, and the yield of the benzoic acid is kept at about 98%. In addition, wang et al (Green chem., 2019, 21, 578-588) fabricated a three-dimensional composite electrode material by loading defective nickel hydroxide nanoplatelets on carbon fibers by hydrothermal synthesis. The electrode can be used for efficiently catalyzing and oxidizing benzyl alcohol, the benzyl alcohol conversion rate can reach 99.5% within 130 minutes, and the conversion rate can reach 18.43 mmol.L -1 ·h -1 The benzoic acid yield was 99.1%. In addition, the electrode material has excellent catalytic stability, and is catalyzed for 10 timesAfter recycle, benzyl alcohol conversion may still be maintained at 98.0% and benzoic acid yield may be maintained at 97.0%.
Compared with the traditional method, the following problems still exist with the current nickel-based electrode material BEOR: (1) The catalytic efficiency still needs to be improved, and the reaction time is long; (2) 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; (3) Most catalysts can only oxidize benzyl alcohol to benzoic acid completely, and intermediate products such as benzaldehyde and benzyl benzoate cannot be obtained, and benzaldehyde is an important fine chemical intermediate, and industrial value is higher than that of benzoic acid. Therefore, how to develop a novel nickel-based BEOR catalytic electrode material to improve the above-mentioned problems remains a significant challenge.
Disclosure of Invention
The invention aims to provide a method for preparing benzaldehyde by electrocatalytic oxidation of benzyl alcohol based on a phytic acid modified foam nickel electrode.
In order to achieve the above object, the method adopted by the invention comprises the following steps:
step 1: immersing the pretreated foam nickel into a phytic acid aqueous solution with the mass fraction of 1% -5%, performing hydrothermal reaction for 10-15 hours at the temperature of 100-180 ℃, cooling to room temperature after the reaction is finished, taking out the foam nickel, and performing ultrasonic washing and drying to obtain a phytic acid modified foam nickel electrode;
step 2: the method comprises the steps of using a phytic acid modified foam nickel electrode as a working electrode, using a saturated calomel electrode as a reference electrode, using a graphite electrode as a counter electrode, using a 1 mol/L potassium hydroxide aqueous solution as an electrolyte, adding benzyl alcohol into the electrolyte, and performing electrocatalytic oxidation on the benzyl alcohol to prepare benzaldehyde at room temperature under the condition of voltage of 1.40-1.55V by adopting a chronoamperometry.
In the step 1, the pretreated foam nickel is preferably immersed in an aqueous solution of phytic acid with a mass fraction of 2% -3.5%, and subjected to hydrothermal reaction at 120-150 ℃ for 10-12 hours.
In the step 1, the pretreatment method of the foam nickel comprises the following steps: placing the foam nickel 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 foam nickel to obtain pretreated foam nickel; the concentration of HCl in the hydrochloric acid is 0.3-1 mol/L.
In the above step 2, it is further preferable to perform electrocatalytic oxidation of benzyl alcohol to prepare benzaldehyde under a voltage of 1.40 to 1.45 and V.
The beneficial effects of the invention are as follows:
the invention prepares the phytic acid modified foam nickel electrode by the reaction of hydrochloric acid and phytic acid after the pretreatment of the foam nickel electrode, and then adopts the phytic acid modified foam nickel as a working electrode to construct a three-electrode system for electrocatalytic oxidation of benzyl alcohol. The method can promote the adsorption of electrode material to benzyl alcohol, and has high catalytic activity and selectivity to benzyl alcohol oxidation reaction at room temperature, and can realize complete conversion of benzyl alcohol in 2 hr at conversion rate up to 10.00 mmol.L -1 ·h -1 And the yield of the reaction product benzaldehyde can reach more than 88 percent. The method is simple, low in cost and environment-friendly, the electrode conversion rate is high, the recycling stability is good, the efficient conversion of benzyl alcohol to produce benzaldehyde is realized, and a new way is provided for efficiently preparing high-added-value fine chemical products.
Drawings
FIG. 1 is a scanning electron micrograph of the nickel foam pretreated in example 1.
FIG. 2 is a scanning electron micrograph and elemental distribution of a phytic acid modified nickel foam electrode prepared based on example 1.
FIG. 3 is an infrared spectrum (ATR-IR) of a phytic acid modified foam nickel electrode prepared based on example 1.
FIG. 4 is a graph showing the catalytic current versus voltage obtained at a sweep rate of 5 mV/s for the phytic acid modified foam nickel electrode prepared based on example 1 without and with 0.02 mol/L benzyl alcohol.
FIG. 5 is a plot of selectivity of benzaldehyde and benzyl benzoate products obtained by catalytic oxidation of benzyl alcohol at different voltages for the phytic acid modified foam nickel electrode prepared based on example 1 versus applied voltage.
FIG. 6 is a graph showing the catalytic current density versus time after 6 cycles of the phytic acid modified foam nickel electrode prepared based on example 1.
FIG. 7 is a graph showing the relationship between the yield of benzaldehyde and the Faraday efficiency and the number of cycles in the recycling process of the phytic acid modified foam nickel electrode prepared in example 1.
FIG. 8 is a contact angle characterization of a Blank foam nickel electrode (Blank NF) and a phytic acid modified foam nickel electrode (PA/NF) against benzyl alcohol solution.
FIG. 9 is a graph showing the catalytic current density versus voltage for a Blank foam nickel electrode (Blank NF), a phytic acid modified foam nickel electrode (PA/NF), and an electrode (NF-phytate) obtained by immersing the Blank foam nickel electrode in a 1.0 mol/L aqueous solution of phytic acid for 12 h in the presence of 0.02 mol/L benzyl alcohol, respectively, at a sweep rate of 5 mV/s.
FIG. 10 is a comparison of catalytic performance of a Blank foam nickel electrode (Blank NF), a phytic acid modified foam nickel electrode (PA/NF), and an electrode (NF-phytate) obtained after soaking the Blank foam nickel electrode in a 1.0 mol/L phytic acid aqueous solution for 12 h to catalyze the oxidation of benzyl alcohol under the same conditions.
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
Step 1: soaking 1 cm multiplied by 3 multiplied by cm multiplied by 0.2 cm foam nickel in 0.3 mol/L salt for ultrasonic cleaning for 20 minutes, removing an oxide layer and pollutants on the surface, and then respectively carrying out ultrasonic oscillation treatment in ethanol, acetone and deionized water to remove superfluous hydrochloric acid on the surface, thereby obtaining the pretreated foam nickel. As shown in FIG. 1, the pretreated foam nickel has a smooth and flat surface. Then pouring the water solution of the phytic acid with the mass fraction of 73-mL being 2% into a 100-mL polytetrafluoroethylene hydrothermal reaction kettle, placing the pretreated foam nickel into the hydrothermal reaction kettle, placing the hydrothermal reaction kettle into a blast drying box, reacting for 10 h under the hydrothermal condition of 120 ℃, and cooling the reaction kettle to the room temperature. Taking out silver foam nickel, repeatedly washing with deionized water and ethanol respectively under ultrasonic treatment, and drying at 60deg.C to obtain phytic acid modified foam nickel electrode (PA/NF). As can be seen from fig. 2, the surface of the phytic acid modified foam nickel 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, ATR-IR spectra of phytic acid modified foam nickel electrodes were also tested, with typical peaks for phytate being shown in fig. 3, further indicating successful modification of phytate on the electrodes.
Step 2: the method comprises the steps of adopting a three-electrode system, taking the phytic acid modified foam nickel electrode obtained in the step 1 as a working electrode, taking a saturated calomel electrode as a reference electrode, taking a graphite electrode as a counter electrode, taking 1 mol/L potassium hydroxide aqueous solution as electrolyte, adding Benzyl Alcohol (BA) into the electrolyte to ensure that the concentration of the benzyl alcohol in the electrolyte is 0.02 mol/L, taking no benzyl alcohol as a control experiment, and recording the change condition of current density along with voltage on an electrochemical workstation (CHI 760E, shanghai Chen Hua instrument company) under the condition of a scanning rate of 5 mV/s. As shown in FIG. 4, the foam nickel electrode was modified with phytic acid, and 0.02 mol/L benzyl alcohol was added thereto at 10 mA/cm 2 The corresponding voltage is 1.307V which is far lower than 1.473V when no benzyl alcohol is added, and the potential difference is as high as 0.166V. The minimum value of the nickel-based electrocatalyst reported in the literature is only 1.35V (ACS catalyst, 2017, 7, 4564-4570), which is higher than the catalytic electrode reported in the literature. Meanwhile, the relation between the conversion rate of benzyl alcohol and the voltage is recorded on an electrochemical workstation (CHI 760E, shanghai Chen Hua instrument Co.) for reaction 2 h under different voltages, the benzaldehyde product is extracted from the electrolyte by ethyl acetate, and the yield of the benzaldehyde is measured by adopting a Gas Chromatography (GC) external standard method. As can be taken from fig. 5, the yield of benzaldehyde gradually increases with voltage (1.25 to 1.55, V). Under the working voltage of 1.40V, the catalytic effect is optimal, the conversion rate of the corresponding benzyl alcohol can reach 100 percent, and the conversion rate can reach 10.00 mmol.L -1 ·h -1 The yield of the product benzaldehyde can reach 88%, and the yield of benzyl benzoate is 12%. However, at a high potential of 1.45V, the yield of benzaldehyde is slightly reduced, probably due to oxygen evolution reaction in water at a high potential. Therefore, the catalyst can realize the short-time and high-efficiency conversion of benzyl alcohol under low voltage and is appliedHas wide prospect.
The cycling stability of the phytic acid modified foam nickel electrode at 1.40. 1.40V to electrocatalytically oxidize benzyl alcohol was further studied (as shown in fig. 6). After 6 cycles, a gradual increase in oily product on the electrolyte surface was observed (inset in fig. 6). In addition, the yield and Faraday efficiency of the product benzaldehyde during the cycle were determined by gas chromatography-mass spectrometry (GC-MS). The results showed that the benzaldehyde yield and Faradaic Efficiency (FE) were maintained at substantially 88.28% and 87% (as shown in fig. 7), and the benzyl alcohol conversion was maintained at 100%. These results all prove that the high-efficiency benzyl alcohol electrochemical oxidation can be realized by utilizing the phytic acid modified foam nickel electrode, and the reaction activity and the stability are excellent.
Example 2
Step 1: soaking 1 cm multiplied by 3 multiplied by cm multiplied by 0.2 cm foam nickel in 0.6 mol/L hydrochloric acid for ultrasonic cleaning for 20 minutes, removing an oxide layer and pollutants on the surface, and then respectively carrying out ultrasonic oscillation treatment in ethanol, acetone and deionized water to remove superfluous hydrochloric acid on the surface, thereby obtaining the pretreated foam nickel. Then, the water solution of phytic acid with the mass fraction of 74. 74 mL being 2.7% is poured into a 100 mL polytetrafluoroethylene hydrothermal reaction kettle, the pretreated foam nickel is put into the hydrothermal reaction kettle, the reaction kettle is put into a blast drying box to react under the hydrothermal condition of 150 ℃ for 12 h, and the reaction kettle is cooled to the room temperature. Taking out silver foam nickel, repeatedly washing with deionized water and ethanol respectively under ultrasound, and drying at 70deg.C to obtain the final product.
Step 2: adopting a three-electrode system, taking the phytic acid modified foam nickel electrode obtained in the step 1 as a working electrode, a saturated calomel electrode as a reference electrode, a graphite electrode as a counter electrode, taking 1 mol/L potassium hydroxide aqueous solution as electrolyte, adding benzyl alcohol into the electrolyte to ensure that the concentration of the benzyl alcohol in the electrolyte is 0.02 mol/L, and then adopting a timing current method to prepare the benzaldehyde by electrocatalytically oxidizing the benzyl alcohol under the condition of voltage of 1.40V at room temperature. The result shows that the conversion rate of benzyl alcohol can reach 9.92 mmol.L -1 ·h -1 The yield of benzaldehyde was 85.13%.
Example 3
Step 1: soaking 1 cm multiplied by 3 multiplied by cm multiplied by 0.2 cm foam nickel in 0.6 mol/L salt, ultrasonically cleaning for 20 minutes, removing an oxide layer and pollutants on the surface, and then respectively performing ultrasonic vibration treatment in ethanol, acetone and deionized water to remove superfluous hydrochloric acid on the surface, thereby obtaining the pretreated foam nickel. Then, 75. 75 mL mass percent of water solution of phytic acid with the mass percent of 3.3 percent is poured into a 100 mL polytetrafluoroethylene hydrothermal reaction kettle, the pretreated foam nickel is put into the hydrothermal reaction kettle, the reaction kettle is put into a blast drying box and reacts for 15 h under the hydrothermal condition at 180 ℃, and the reaction kettle is cooled to the room temperature. Taking out silver foam nickel, repeatedly washing with deionized water and ethanol respectively under ultrasound, and drying at 80deg.C to obtain the phytic acid modified foam nickel electrode.
Step 2: adopting a three-electrode system, taking the phytic acid modified foam nickel electrode obtained in the step 1 as a working electrode, a saturated calomel electrode as a reference electrode, a graphite electrode as a counter electrode, taking 1 mol/L potassium hydroxide aqueous solution as electrolyte, adding benzyl alcohol into the electrolyte to ensure that the concentration of the benzyl alcohol in the electrolyte is 0.02 mol/L, and then adopting a timing current method to prepare benzaldehyde by electrocatalytic oxidation of the benzyl alcohol under the condition of voltage of 1.40V at room temperature. The result shows that the conversion rate of benzyl alcohol can reach 9.84 mmol.L -1 ·h -1 The yield of benzaldehyde was 83.42%.
In order to prove the beneficial effects of the invention, first, contact angles of the blank foam nickel electrode and the phytic acid modified foam nickel electrode against benzyl alcohol solution are respectively compared, and the result is shown in fig. 8. The results show that the contact angle of the blank foam nickel electrode to benzyl alcohol is about 87.8 degrees, and the contact angle of the phytic acid modified foam nickel electrode to benzyl alcohol is almost 0, which shows that the phytic acid modified foam nickel electrode can infiltrate into benzyl alcohol more quickly than the blank foam nickel electrode, and the adsorption effect of the phytic acid can be further improved by the modification of the phytate. Adopting a three-electrode system, respectively taking a blank foam nickel electrode, the phytic acid modified foam nickel electrode prepared in the embodiment 1, a foam nickel electrode (J. Mater. Chem. A, 2016, 4, 9486-9495) which is soaked in a water solution of 1.0 mol/L phytic acid as a working electrode, a saturated calomel electrode as a reference electrode, a graphite electrode as a counter electrode, taking a water solution of 1 mol/L potassium hydroxide as an electrolyte, adding0.02 In the case of mol/L benzyl alcohol, the change in current density with voltage was recorded on an electrochemical workstation (CHI 760E, shanghai Chen Hua instruments Co.) using a 5 mV/s scan rate. As shown in FIG. 9, 0.02 mol/L benzyl alcohol was added to the method of modifying a foam nickel electrode with phytic acid, 10 mA cm -2 The voltage is 1.307V, which is far lower than the voltage corresponding to the method (1.537V) of using blank foam nickel (1.681V) or using a foam nickel electrode after soaking 12 h with phytic acid. The method for modifying the foam nickel electrode by the phytic acid is shown to have a relatively high degree of catalytic conversion performance.
To further compare the actual conversion of benzyl alcohol by electrocatalytic oxidation using three working electrodes, the benzyl alcohol conversion was recorded on an electrochemical workstation (CHI 760E, shanghai cinnabar instruments) for 2 h reactions at 1.40 and V. As can be seen from FIG. 10, the total conversion rate of the blank foam nickel electrode to benzyl alcohol was 42.87%, and the conversion rate was 4.29 mmol.L -1 ·h -1 The benzaldehyde yield was 36.44%, the total conversion rate of the phytic acid modified foam nickel electrode to benzyl alcohol was 100%, and the conversion rate was 10.00 mmol.L -1 ·h -1 Wherein the benzaldehyde yield was 88.28%. The total conversion rate of the foam nickel electrode after being soaked in the water solution of 1.0 mol/L phytic acid for 12 h to benzyl alcohol is only 65.17%, and the conversion rate is 6.52 mmol.L -1 ·h -1 Wherein the benzaldehyde yield is 56.04%, and the performance of the foam nickel electrode modified by the phytic acid is greatly different. Therefore, the phytic acid modified foam nickel electrode prepared by the method can realize the preparation of benzaldehyde by high-efficiency electrocatalytic oxidation of benzyl alcohol, and has great application significance.
Claims (3)
1. The method for electrocatalytic oxidation of benzyl alcohol based on phytic acid modified foam nickel electrode is characterized by comprising the following steps:
step 1: placing foam nickel into hydrochloric acid, wherein the concentration of HCl in the hydrochloric acid is 0.3-1 mol/L, 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 to obtain pretreated foam nickel; immersing the pretreated foam nickel into a phytic acid aqueous solution with the mass fraction of 1% -5%, carrying out hydrothermal reaction for 10-15 hours at the temperature of 100-180 ℃, cooling to room temperature after the reaction is finished, taking out the foam nickel, and carrying out ultrasonic washing and drying to obtain the phytic acid modified foam nickel electrode;
step 2: the method comprises the steps of using a phytic acid modified foam nickel electrode as a working electrode, using a saturated calomel electrode as a reference electrode, using a graphite electrode as a counter electrode, using a 1 mol/L potassium hydroxide aqueous solution as an electrolyte, adding benzyl alcohol into the electrolyte, and performing electrocatalytic oxidation on the benzyl alcohol to prepare benzaldehyde at room temperature under the condition of voltage of 1.40-1.55V by adopting a chronoamperometry.
2. The method for electrocatalytic oxidation of benzyl alcohol based on a phytic acid modified foam nickel electrode according to claim 1, wherein: in the step 1, the pretreated foam nickel is immersed in a phytic acid aqueous solution with the mass fraction of 2-3.5%, and the foam nickel is subjected to hydrothermal reaction for 10-12 hours at 120-150 ℃.
3. The method for electrocatalytic oxidation of benzyl alcohol based on a phytic acid modified foam nickel electrode according to claim 1 or 2, wherein: in the step 2, the benzaldehyde is prepared by electrocatalytic oxidation of benzyl alcohol under the condition of voltage of 1.40-1.45V.
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| CN104746096A (en) * | 2015-02-27 | 2015-07-01 | 河南科技大学 | Preparation method of nickel-base catalytic electrode for electrocatalytic oxidation of urea |
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