CN116043259A - Based on Ni (OH) 2 Method for preparing formic acid and hydrogen by converting PET waste plastics through redox medium - Google Patents
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Abstract
The invention provides a Ni (OH) -based alloy 2 A method for preparing formic acid and hydrogen by converting PET waste plastics through redox media. The Ni (OH) 2 The preparation method of the electrode comprises the following steps: a1, dissolving nickel salt in water to form a solution A; a2, dissolving sodium carbonate in water to form a solution B; a3, diluting the solution A into the solution B to form a solution C, immersing the electrodeposited conductive substrate into the solution C, and performing an electrodepositing reaction; to obtain Ni (OH) 2 An electrode. The invention also provides a Ni (OH) -based alloy 2 Method for preparing formic acid and hydrogen by converting PET waste plastics through redox medium by Ni (OH) 2 The electrode is used as an anode and a cathode hydrogen evolution catalytic electrode to be assembled into an electrolytic system, water reduction is realized at the cathode to generate hydrogen, nickel hydroxide is oxidized into nickel oxyhydroxide, and then the NiOOH electrode is placed in PET waste plastic alkaline hydrolysate, and the nickel oxyhydroxide is reduced into nickel hydroxide.
Description
Technical Field
The invention belongs to the technical field of electrocatalysis, relates to a technology for recycling waste plastics by electrocatalytic upgrading, and in particular relates to a catalyst based on Ni (OH) 2 A method for preparing formic acid and hydrogen by converting PET waste plastics through redox media.
Background
With the continuous development of industrialization process, a series of environmental pollution and energy crisis problems are caused by the massive consumption of traditional fossil energy sources such as traditional coal, petroleum and natural gas. In this large background, the development and development of clean and efficient environmental remediation technologies and the exploration of clean and sustainable energy supplies are currently facing and in need of solution in countries around the world. Plastics are an important class of polymer products, and since the first report of synthetic phenolic plastics in 1907, plastics have been widely used in daily life due to their light weight, durability, ease of processing, and the like. However, the unreasonable disposal and accumulation of a large amount of waste plastics not only causes serious pollution to the environment and endangers the health and safety of the earth and human beings, but also causes serious waste of carbon resources because a large amount of waste plastics cannot be reasonably recycled. In view of this, development and utilization of clean and efficient environmental energy catalytic technology for upgrading recovery processing waste plastics to produce high value chemicals is of great importance.
At present, scientists in all countries are actively exploring and developing a cleaning technology capable of recycling waste plastics. Among them, as a technology that can be performed at normal temperature and pressure, an electrocatalytic conversion technology that can be driven by green renewable electric energy is widely used in the fields of energy storage and conversion. It is notable that plastics are generally polymeric products obtained by polycondensation or polyaddition reactions, which are rich in carbon, hydrogen and oxygen elements. Among them, polyethylene terephthalate (PET) plastics can be converted into terephthalate and ethylene glycol monomers by alkaline hydrolysis due to the abundant ester groups. Recently, researchers have attempted to apply electrocatalytic technology to the conversion of PET waste plastics, successfully achieving the preparation of formate from the anodic oxidation hydrolysis product ethylene glycol, while simultaneously achieving co-production of hydrogen at the cathode. Therefore, the electrocatalytic technology is of great significance in the recovery and preparation of high-added-value chemicals and fuels from waste plastics.
Notably, in the electrocatalytic conversion of PET with co-production of formic acid and hydrogen, in order to avoid diffusion of the product to the counter electrode to be consumed, the electrolyzer is generally divided into two compartments, a male compartment and a female compartment, by means of an expensive ion exchange membrane. However, the use of the ion exchange membrane not only increases the cost of electrocatalytically converting PET waste plastics, but also greatly increases the internal resistance of the system due to the slow ion transmission capacity of the ion exchange membrane, thereby increasing the energy consumption of the conversion system. Therefore, the development of a membraneless electrolysis technology for conversion and utilization of PET waste plastics has important significance for reducing cost investment and energy consumption. Nickel hydroxide, which has excellent charge storage capacity and redox cycle stability, has been applied by researchers to the decoupling water splitting reaction (patent application number: 201510799110.3), and in the absence of ion exchange membranes, has been achieved to split the anodic water oxidation and cathodic hydrogen evolution reactions in different time and space. However, the anodic water oxidation half reaction not only requires higher energy consumption, but also has lower product utilization value. The invention oxidizes the hydroxyl oxygen nickel electrode in the electrocatalytic hydrogen evolution process, is directly applied to converting PET plastic hydrolysate, realizes high-selectivity conversion of the hydrolysate into formic acid without any external energy input, and simultaneously avoids high-energy-consumption water oxidation reaction. The method utilizes nickel hydroxide redox medium to co-produce formic acid and hydrogen by electro-catalytic conversion of PET, and successfully cuts the PET into different time and space, thereby realizing upgrading and recycling of PET waste plastics in a membraneless device.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for preparing formic acid and hydrogen by converting PET waste plastics based on Ni (OH) 2 redox medium.
The aim of the invention can be achieved by the following technical scheme:
first aspect:
ni (OH) 2 The preparation method of the electrode comprises the following steps:
a1, dissolving nickel salt in water to form a solution A;
a2, dissolving sodium carbonate in water to form a solution B;
a3, diluting the solution A into the solution B to form a solution C, immersing the electrodeposited conductive substrate into the solution C, and performing an electrodepositing reaction; ni (OH) 2 An electrode.
The nickel salt comprises at least one of nickel nitrate, nickel sulfate and nickel chloride.
In the solution A, the concentration of nickel ions is 0.1-1M.
In the solution B, the concentration of sodium carbonate is 1-2M.
In the solution C, the concentration of nickel ions is 0.5-2mM.
The electrodeposition voltage is 1.3V-2V, and the electrodeposition time is 15-20min.
The invention adopts the integrated electrode prepared by an in-situ anodic electrodeposition method, and the prepared electrode has better structure and circulation stability without using a binder and a coating process; in addition, the invention can effectively regulate and control the electrode material loading capacity by regulating and controlling the electrodeposition voltage and time, and is beneficial to industrial production and use.
The Ni (OH) 2 The electrode has higher proton-electron storage capacity and better redox reversibility, ni (OH) 2 The electrode preparation method can adopt an electrochemical deposition method, a hydrothermal synthesis method or a coating method and the like.
The electrochemical deposition method comprises a cathodic deposition method and an anodic deposition method.
Second aspect:
the invention provides a Ni (OH) -based alloy 2 Method for preparing formic acid and hydrogen by converting PET waste plastics through redox medium, wherein Ni (OH) is adopted in the method 2 The electrode is used as a proton-electron storage medium, and PET is converted in steps in a membraneless electrolytic tank to prepare formic acid and hydrogen; the method specifically comprises the following steps:
S1、Ni(OH) 2 the electrode is used as an anode and a cathode hydrogen evolution catalytic electrode to be assembled into an electrolytic system, water reduction is realized at the cathode to generate hydrogen, and nickel hydroxide is oxidized into nickel oxyhydroxide to obtain a NiOOH electrode;wherein the electrolyte is an alkaline solution, and the alkaline solution comprises KOH or NaOH; in view of the fact that the anode is only Ni (OH) 2 Oxidation to NiOOH, no oxygen evolution reaction occurs, so it can be carried out in a single-tank membraneless electrolytic cell;
s2, placing the NiOOH electrode in the PET waste plastic alkaline hydrolysate, reducing the nickel oxyhydroxide into nickel hydroxide, and oxidizing ethylene glycol in the PET hydrolysate into formic acid.
Which is Ni (OH) in the electrochemical hydrogen production process 2 The electrode is used as an anode and a cathode hydrogen evolution catalytic electrode to be assembled into an electrolytic system, water reduction is realized at the cathode to generate hydrogen, nickel hydroxide is oxidized into nickel oxyhydroxide, the process has no oxygen evolution reaction, and an ion exchange membrane can be avoided; then, placing the NiOOH electrode obtained by oxidation in the electrochemical hydrogen production process in PET waste plastic alkaline hydrolysate, reducing nickel oxyhydroxide into nickel hydroxide, and oxidizing glycol in the PET hydrolysate into formic acid; the two steps can be performed by using Ni (OH) 2 The NiOOH redox intermediate is cycled alternately as a proton-electron storage medium.
In the electrochemical hydrogen evolution process, ni (OH) 2 The electrode and the cathode hydrogen evolution electrode can carry out electrolytic hydrogen production in an electrolytic tank with a chamber, and an ion exchange membrane is not required to isolate cathode-anode half reaction. The cell pressure should be capable of driving the cathodic hydrogen evolution reaction and the oxidation reaction of the anodic nickel hydroxide electrode while avoiding the occurrence of water oxidation reaction.
In sodium carbonate solution containing nickel ions, adopting a three-electrode system, taking foam nickel, foam copper, carbon cloth or carbon paper as an electrodeposited conductive substrate, and preparing Ni (OH) by using a constant potential or constant current anodic oxidation electrodeposition method 2 An electrode.
The catalyst material of the cathode hydrogen evolution catalytic electrode comprises noble metal-based materials based on Pt, pd and the like; or carbide, phosphide, sulfide, selenide-based materials; or based on elemental or compound materials of iron, cobalt, nickel, copper, molybdenum, tungsten.
The alkali solubility used in the PET waste plastic alkaline hydrolysate comprises at least one of KOH, naOH, carbonate and bicarbonate.
The applied voltage of the electrolytic cell is 1.3V-1.8V.
The invention is based on Ni (OH) 2 The method for preparing formic acid and hydrogen by converting PET waste plastics through redox media comprises the following two steps of electrochemical hydrogen production and spontaneous oxidation of PET waste plastics:
in the electrochemical hydrogen production process of step 1, ni (OH) 2 As an anode electrode and a cathode hydrogen evolution catalytic electrode are assembled into an electrolytic system, ni (OH) 2 The loss of protons and electrons as anode reactants are oxidized to NiOOH, and accordingly, the protons and electrons recombine at the cathode catalytic electrode to produce hydrogen. In this step, only Ni (OH) is generated at the anode 2 The oxidation reaction of (2) avoids the occurrence of oxygen evolution reaction, has no problem of mixing hydrogen and oxygen, and does not need to use an ion exchange membrane, thereby being capable of being carried out in a membraneless electrolytic tank.
After the electrochemical hydrogen evolution process of the step 1 is finished, the NiOOH electrode obtained by oxidation is moved into the PET waste plastic alkaline hydrolysis liquid for the step 2, and no external energy input is needed. The NiOOH and glycol in the PET hydrolysate undergo oxidation-reduction reaction, the glycol is oxidized to break C-C bond to generate formic acid, and the NiOOH obtains proton and electron which are reduced into Ni (OH) 2 . The electrochemical hydrogen evolution process of the step 1 and the spontaneous chemical reaction conversion PET hydrolysate process of the step 2 can be alternately and circularly carried out through a nickel-based redox medium. As one embodiment, the electrochemical hydrogen evolution system of step 1 is operated to electrolyze the cell at a pressure in the range of 1.3 to 1.8V.
As one embodiment, the electrolyte in the electrochemical hydrogen evolution system of the step 1 is 0.1-10M alkaline solution (KOH, naOH, na 2 CO 3 、K 2 CO 3 Etc.).
As one embodiment, the concentration of the alkaline hydrolysis liquid of the PET waste plastics in the step 2 is 0.01-1M. The alkali solution comprises KOH, naOH, na 2 CO 3 Or K 2 CO 3 Etc.; preferably the alkali solution has a concentration of 1-3M.
The invention adopts the spontaneous oxidation of NiOOH and glycol in PET hydrolysateReduction chemistry, the oxidation of ethylene glycol to formic acid by NiOOH, the reduction of NiOOH to Ni (OH) 2 The process is different from the traditional electrolytic hydrolysis coupling mode, and an external power supply and equipment are not needed in the process.
The invention provides a Ni (OH) -based alloy 2 The method for preparing formic acid and hydrogen by converting PET waste plastics through redox media can simplify the device for recycling PET waste plastics through electrocatalytic reaction, avoid using an ion exchange membrane with high price, reduce the energy consumption for preparing hydrogen through electrocatalytic reduction of water, and obtain chemicals with high added value.
Compared with the prior art, the invention has the following beneficial effects:
the present invention is achieved by utilizing Ni (OH) with proton-electron storage capability 2 The electrode is used as an auxiliary electrode, so that high-purity hydrogen is prepared in a single-tank electrolytic cell without an ion exchange membrane, and simultaneously, the conversion of ethylene glycol which is difficult to separate in PET hydrolysate into formic acid is realized by using NiOOH obtained by oxidation in the electrochemical hydrogen evolution process under the condition of no external energy consumption. The invention utilizes Ni (OH) 2 The redox medium organically combines the electrochemical hydrogen evolution process with the chemical oxidation conversion of PET waste plastics, avoids using an ion exchange membrane which is expensive and has been consumed, is beneficial to reducing the economic cost and improving the economic benefit in the recovery process of PET waste plastics, and is more beneficial to industrialized application.
Drawings
Other features, objects and advantages of the present invention will become more apparent upon reading of the detailed description of non-limiting embodiments, given with reference to the accompanying drawings in which:
FIG. 1 is Ni (OH) 2 The electrode assists and converts PET waste plastics to produce formic acid and hydrogen system schematic diagram;
FIG. 2 is Ni (OH) 2 SEM image of the electrode;
FIG. 3 is Ni (OH) 2 And an optical diagram of a NiOOH electrode, wherein the right diagram is the NiOOH electrode; the left picture is Ni (OH) 2 An electrode;
FIG. 4 is Ni (OH) 2 Cyclic voltammogram in 1M KOH solution;
FIG. 5 is Ni (OH) 2 At 1MConstant current charge-discharge curve in KOH solution;
FIG. 6 is a nuclear magnetic spectrum of PET hydrolysate before and after placement of NiOOH electrodes.
Detailed Description
The present invention will be described in detail with reference to examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that several modifications and improvements can be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
The invention is based on Ni (OH) 2 The method for preparing formic acid and hydrogen by converting PET waste plastics through redox media comprises two steps of electrochemical hydrogen production and spontaneous oxidation of PET waste plastics as shown in figure 1:
in the electrochemical hydrogen production process of step 1, ni (OH) 2 As an anode electrode and a cathode hydrogen evolution catalytic electrode are assembled into an electrolytic system, ni (OH) 2 The loss of protons and electrons as anode reactants are oxidized to NiOOH, and accordingly, the protons and electrons recombine at the cathode catalytic electrode to produce hydrogen. After the electrochemical hydrogen evolution process of the step 1 is finished, the NiOOH electrode obtained by oxidation is moved into PET hydrolysate to carry out the step 2, the NiOOH and glycol in the PET hydrolysate are subjected to oxidation-reduction reaction, the glycol is oxidized to break C-C bonds to generate formic acid, and the NiOOH is reduced into Ni (OH) by protons and electrons 2 . The electrochemical hydrogen evolution process of the step 1 and the spontaneous chemical reaction conversion PET hydrolysate process of the step 2 can be alternately and circularly carried out through a nickel-based redox medium. The chemical reaction equations in step 1 and step 2 are as follows:
step 1:
anode Ni (OH) 2 -e - +OH - →NiOOH+H 2 O(1)
And (3) cathode:
step 2:
6NiOOH + C 2 H 6 O 2 + 2H 2 O → 6Ni(OH) 2 + 2HCOOH (3)
example 1
Redox mediator Ni (OH) 2 Anodic oxidation electrodeposition preparation of electrodes
1. Adding 20ml of deionized water into a 50ml beaker, and adding sodium carbonate to make the concentration of the solution be 2mol/L to form a solution A;
2. adding 20ml of deionized water into a 50ml beaker, and adding nickel nitrate to ensure that the concentration of a nickel nitrate solution is 0.1mol/L to form a solution B;
3. adding the solution B into the solution A to enable the concentration of nickel nitrate in the solution to be 0.001mol/L, and forming a solution C as an electrodeposition solution;
4. placing a three-electrode system with a working electrode of foam nickel, a counter electrode of platinum net and a reference electrode of saturated calomel electrode into a solution C for electrodeposition to prepare Ni (OH) 2 An electrode. The voltage was applied at 1.4V for 15min. And taking out the electrode after the electrodeposition is finished, washing the electrode, and drying the electrode at room temperature to serve as an auxiliary electrode for electrochemical hydrogen evolution and PET oxidation conversion.
FIG. 2 is Ni (OH) 2 SEM image of electrode, from which it can be seen that Ni (OH) was prepared 2 The electrode shows a three-dimensional multi-level nano-sheet structure and is uniformly distributed on the foam nickel conductive substrate.
FIG. 3 is Ni (OH) 2 And the optical diagram of the NiOOH electrode, it can be seen from the diagram that the oxidized NiOOH electrode is shown in the right diagram and Ni (OH) 2 The electrodes are shown in the left figure.
Analysis in combination with the above data demonstrates successful preparation of Ni (OH) on foamed nickel conductive substrates 2 A material. Ni (OH) with three-dimensional multi-stage nano-sheet structure 2 The electrode will facilitate sufficient exposure of more reactive sites and increase the passage and rate of mass transfer.
Example 2
Ni (OH) obtained in example 1 2 The electrodes are respectively used as proton electron storage media to convert PET waste plastics to co-produce formic acid and hydrogen, and respectively perform electrochemical hydrogen evolution test and PET oxidation product selectivity test, wherein the test system is shown in figure 1, and the specific steps are as follows:
the electrochemical hydrogen evolution step was tested using a two electrode system, the anode electrode being Ni (OH) 2 The electrode, the cathode electrode is a platinum catalytic electrode, and the effective areas of the catalytic electrodes are respectively 1cm 2 . The electrolyte was a solution containing 1M KOH. The scan rate for the LSV test was 10mV s –1 . The experimental test temperature was 25.+ -. 2 ℃. The performance test of the NiOOH oxidized PET hydrolysate is qualitatively analyzed by adopting a nuclear magnetic resonance hydrogen spectrometry.
In Ni (OH) 2 In the electrode-assisted electrocatalytic hydrogen evolution step, ni (OH) 2 The redox activity and reversibility of the electrode were subjected to CV testing. As shown in FIG. 4, ni (OH) was prepared 2 The electrode shows a pair of reversible oxidation-reduction peaks, which indicates that the electrode prepared by the anodic electrodeposition method can have higher oxidation-reduction activity and reversibility. When the voltage exceeds 1.35V, the system current increases extremely, indicating that the anode Ni (OH) can occur under the condition of lower potential 2 Oxidation and cathodic hydrogen evolution of the electrode, during which the anode Ni (OH) 2 No bubbles were generated on the electrode, indicating that no oxygen evolution reaction occurred. In addition, for Ni (OH) 2 The electrode was subjected to charge and discharge testing, as shown in FIG. 5, and the electrode exhibited a relatively high charge storage capacity of about 5C/cm 2 。
Soaking the NiOOH electrode obtained by oxidation in the electrochemical hydrogen evolution process in the PET hydrolysate, and rapidly changing the color of the electrode from black brown to light yellow brown, which shows that the NiOOH electrode is reduced to Ni (OH) by glycol in the PET hydrolysate 2 An electrode. Analysis of the reacted PET hydrolysate by nmr hydrogen spectroscopy showed formic acid formation in the solution with a corresponding reduction in ethylene glycol as shown in fig. 6. The results show that the NiOOH electrode can oxidize ethylene glycol, which is difficult to separate in PET hydrolysate, to formic acid product.
The above results indicate the use of Ni (OH) 2 The electrode can combine electrochemical hydrogen evolution reaction with chemical oxidation conversion of PET hydrolysate, so that high-purity hydrogen can be prepared in the membraneless electrolytic tank, and selective conversion of PET waste plastics can be realized at normal temperature and normal pressure without any additional energy input.
In summary, the present invention (1) prepares Ni (OH) with multi-stage nano-sheet structure by anodic oxidation electrodeposition 2 The electrode is used as a redox medium to selectively convert PET waste plastics to prepare formic acid and hydrogen; (2) The method is used for converting PET waste plastics to prepare formic acid and hydrogen and avoiding the use of an ion exchange membrane which is expensive and easy to consume; (3) The process of converting PET waste plastics into formic acid by the method does not need any external energy input; (4) The method organically combines electrochemical hydrogen evolution and chemical oxidation of PET waste plastics. The invention utilizes Ni (OH) 2 The electrode realizes the selective conversion of PET waste plastics into formic acid with high added value and high-purity hydrogen fuel in a membraneless reactor under mild conditions.
The foregoing describes specific embodiments of the present invention. It is to be understood that the invention is not limited to the particular embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the claims without affecting the spirit of the invention.
Claims (10)
1. Ni (OH) 2 The preparation method of the electrode is characterized by comprising the following steps:
a1, dissolving nickel salt in water to form a solution A;
a2, dissolving sodium carbonate in water to form a solution B;
a3, diluting the solution A into the solution B to form a solution C, immersing the electrodeposited conductive substrate into the solution C, and performing an electrodepositing reaction; to obtain Ni (OH) 2 An electrode.
2. The method according to claim 1, wherein in step A1, the nickel salt comprises at least one of nickel nitrate, nickel sulfate, and nickel chloride.
3. The method according to claim 1, wherein the concentration of nickel ions in the solution a is 0.1 to 1M.
4. The method of claim 1, wherein the concentration of sodium carbonate in solution B is 1-2M.
5. The method of claim 1, wherein the concentration of nickel ions in solution C is 0.5-2mM.
6. The method according to claim 1, wherein the electrodeposition voltage is 1.3V to 2V and the electrodeposition time is 15 to 20min.
7. Ni (OH) -based 2 A process for preparing formic acid and hydrogen from PET waste plastics by redox mediator conversion, characterized in that Ni (OH) is prepared by the preparation process as claimed in any one of claims 1 to 6 2 The electrode is used as a proton-electron storage medium, and PET is converted in steps in a membraneless electrolytic tank to prepare formic acid and hydrogen; the method specifically comprises the following steps:
S1、Ni(OH) 2 the electrode is used as an anode and a cathode hydrogen evolution catalytic electrode to be assembled into an electrolytic system, water reduction is realized at the cathode to generate hydrogen, and nickel hydroxide is oxidized into nickel oxyhydroxide to obtain a NiOOH electrode; wherein the electrolyte is an alkaline solution, and the alkaline solution comprises KOH or NaOH;
s2, placing the NiOOH electrode in the PET waste plastic alkaline hydrolysate, reducing the nickel oxyhydroxide into nickel hydroxide, and oxidizing ethylene glycol in the PET hydrolysate into formic acid.
8. Ni (OH) -based alloy according to claim 7 2 The method for preparing formic acid and hydrogen by converting PET waste plastics through redox media is characterized in that the catalyst material of the cathode hydrogen evolution catalytic electrode comprises noble metal-based materials based on Pt, pd and the like; or carbide, phosphide, sulfide, selenide-based materials; or based on elemental or compound materials of iron, cobalt, nickel, copper, molybdenum, tungsten.
9. Ni (OH) -based alloy according to claim 7 2 Preparation of formic acid by converting PET waste plastics through redox mediumThe hydrogen method is characterized in that the alkali solubility used in the PET waste plastic alkaline hydrolysate comprises at least one of KOH, naOH, carbonate and bicarbonate.
10. Ni (OH) -based alloy according to claim 7 2 The method for preparing formic acid and hydrogen by converting PET waste plastics through redox media is characterized in that the voltage applied to an electrolytic cell is 1.3V-1.8V.
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| CN114774960A (en) * | 2022-04-28 | 2022-07-22 | 江西八六三实业有限公司 | Efficient OER electrochemical active catalyst |
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| CN114774960A (en) * | 2022-04-28 | 2022-07-22 | 江西八六三实业有限公司 | Efficient OER electrochemical active catalyst |
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