CN114044502B - Monoclinic phase zinc pyrophosphate, preparation method and application thereof - Google Patents
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Abstract
The invention discloses monoclinic phase zinc pyrophosphate, a preparation method and application thereof, wherein zinc nitrate hexahydrate and ammonium dihydrogen phosphate are respectively used as a zinc source and a phosphorus source, citric acid monohydrate is used as a complexing agent, and the monoclinic phase zinc pyrophosphate with a typical scandium yttrium stone structure is prepared by a sol-gel and high-temperature calcination method. The preparation method of the invention has simple operation, easily obtained raw materials, low preparation cost, short reaction period and large-scale high-yield preparation. The material can be used as a low-cost and high-efficiency electrocatalyst for the conversion reaction of carbon dioxide to carbon monoxide under industrial-grade current, and the CO local current density in a flow reaction tank is as high as-441 mA cm ‑2 under the potential of 870 mV. When the material is applied to a zero-gap electrolytic cell, the full cell energy efficiency of the material reaches 58% at most, and the material has excellent catalytic performance in the field of preparing CO by electrocatalytic reduction CO 2.
Description
Technical Field
The invention relates to a preparation method and application of monoclinic phase zinc pyrophosphate, which is prepared by adopting a sol-gel and high-temperature calcination method, and the zinc pyrophosphate has excellent performance in the aspect of preparing CO by electrocatalytic reduction of CO 2 as a catalyst and has potential application value in the fields of other energy development and environmental protection.
Background
Fossil fuels drive the growth of economy, reduce poverty by creating employment opportunities, improve the living standard of most residents in the world, and simultaneously, the use of fossil fuels also increases the artificial emission of CO 2, which leads to climate change which is difficult to reverse. In pursuing zero carbon emissions, the utilization of wind or solar energy to provide electrical energy in a sustainable manner, and then the electrochemical decomposition of water has become one of the promising approaches to convert renewable energy sources into hydrogen fuels, but its availability has limited their widespread use while storage and supply of renewable energy sources also presents challenges. The concentration of CO 2 in the atmosphere is now over 407ppm and we need to go to solve this problem more rapidly and all the way. Thus, it is recognized that the utilization of innovative technologies to combat CO 2 emissions at the source and at the various levels of the supply chain is another effective approach to mitigating CO 2 emissions.
Many strategies have been developed to reduce CO 2 emissions. The first approach is to increase the efficiency of transportation and industrial production, reduce the input of energy, and thus reduce the emission of CO 2. At the same time, carbon Capture and Storage (CCS) is also considered a potential solution that can capture CO 2 from post-combustion exhaust gas and store it in underground abandoned natural gas and oil fields. However CCS technology is also controversial in that it faces additional environmental risks such as groundwater pollution and leakage problems. Recently, some prior art technologies have also been claimed to convert CO 2 waste into value-added chemicals. For example, the sabatier reaction is a well known and well-studied thermochemical process that can reduce CO 2 to methane, but this technology requires the use of hydrogen, while requiring higher operating temperatures and pressures. There is a particular technology that has shown great potential to solve the problem of CO 2 being emitted to the atmosphere, namely the electrocatalytic reduction of CO 2 to valuable fuels and chemicals such as formic acid, methanol, ethanol, ethylene and CO. The yields of electrocatalytic reduction CO 2 are higher compared to photocatalytic and photoelectrochemical reactions. The CO 2 reduction reaction is typically carried out at ambient temperature and pressure and driven by electricity, which may be from renewable energy sources such as solar and wind energy. In fact, the CO 2 reduction reaction has the ability to store intermittent renewable energy sources in the form of chemical fuels, which also helps solve the problem of storage of CO 2 in transition to renewable resources. In addition, the value added fuels and chemicals produced by the reduction reaction of CO 2 can be further applied to power generation, transportation fuels or chemical raw materials.
Disclosure of Invention
The invention aims to provide a sol-gel of a monoclinic phase zinc pyrophosphate electrocatalyst, a high-temperature calcination preparation method and application thereof. The catalyst has the advantages of simple preparation method, low cost, excellent selectivity of CO 2 in electrocatalytic reduction and CO production and industrial current density. Complex instruments are not needed in the synthesis process, the operation is convenient, and the method is beneficial to large-scale industrial application.
In order to achieve the above purpose, the invention adopts the following technical scheme:
The monoclinic phase zinc pyrophosphate with typical scandium yttrium stone structure is prepared through sol-gel and high temperature calcination process with zinc nitrate hexahydrate and ammonium dihydrogen phosphate as zinc source and phosphorus source and citric acid monohydrate as complexing agent.
The invention also provides a preparation method of the monoclinic phase zinc pyrophosphate, which comprises the following steps:
(1) 0.8-2.8 g of zinc nitrate hexahydrate and 0.4-1.6 g of ammonium dihydrogen phosphate are dissolved in deionized water and fully stirred to form suspension. Then adding 0.2-1.0 g of citric acid monohydrate, stirring until the suspension is clear, and then placing in a baking oven at 100-140 ℃ for baking;
(2) Transferring the material obtained in the step (1) into a crucible, and placing the crucible in a muffle furnace to calcine the material for 1 to 6 hours at the temperature of 500 to 900 ℃ at the heating rate of 5 ℃/min, thus obtaining gray monoclinic phase zinc pyrophosphate with a typical scandium yttrium stone structure.
Further, the entire structure of monoclinic phase zinc pyrophosphate having a typical scandium yttrium stone structure is composed of pyrophosphoric tetrahedra alternating with zinc atom layers, exhibiting 5 nearest neighbor oxygen atoms surrounding a coordination number 5 zinc site (distorted structure) and a coordination number 6 zinc site (regular octahedron), exhibiting 3.3 andTwo types of Zn-Zn bond lengths; the two pyrophosphoric acid tetrahedra share an oxygen atom, and the P-O-P bond angle is 130 degrees.
The invention also provides application of the monoclinic phase zinc pyrophosphate as a catalyst for preparing CO by electrocatalytic reduction of CO 2.
Further, the application method of the monoclinic phase zinc pyrophosphate as the electrocatalytic reduction CO 2 for preparing CO is as follows:
(1) In a flow reaction tank, 1.0-2.0M KOH solution is used as electrolyte, a gas diffusion electrode loaded with zinc pyrophosphate and carbon black is used as a working electrode, a silver/silver chloride electrode is used as a reference electrode, foam nickel is used as a counter electrode, and the test temperature is 0-40 ℃; when the applied current density is-300 mA cm -2, the Faraday efficiency of CO reaches 90-100%; when the applied current density is-500 mA cm -2, the potential is as low as 0.87V vs. RHE, and meanwhile, the local current density of the CO product reaches-415 to-465 mA cm -2;
(2) In a zero-gap electrolytic cell, 1.0-2.0M KOH solution is used as electrolyte, a gas diffusion electrode loaded with zinc pyrophosphate and carbon black is used as a working electrode, nickel-iron layered double hydroxide supported by foam nickel is used as an anode, and the test temperature is 0-40 ℃; when the applied current density is-100 mA cm -2, the Faraday efficiency of CO reaches 90-95%, and the energy efficiency of the full battery reaches 50-58%.
The invention has the beneficial effects that:
(1) Simple sol-gel and high-temperature calcination methods are adopted to synthesize monoclinic zinc pyrophosphate, the synthesis method is simple to operate, raw materials are easy to obtain, the preparation cost is low, the reaction period is short, complex instruments are not needed in the synthesis process, and the monoclinic zinc pyrophosphate can be synthesized in a large scale, so that the method is beneficial to large-scale industrial application;
(2) The monoclinic phase zinc pyrophosphate is used as a catalyst for electrocatalytic reduction of CO 2, and the result shows that the catalyst has excellent selectivity and activity for preparing CO by electrocatalytic reduction of CO 2, when the current density is applied in a flow reaction cell and is-500 mA cm -2, the potential is as low as 0.87V vs. RHE, and meanwhile, the local current density for producing CO reaches-415 to-465 mA cm -2; when the current density is-100 mA cm -2 in the zero-gap electrolytic cell, the Faraday efficiency of CO reaches 90-95%, and the energy efficiency of the full cell reaches 50-58%;
(3) In the preparation process, all reagents are commercial products, and no further treatment is needed;
(4) The synthesis method is simple, the obtained material is easy to apply, is favorable for popularization and application in industrial production, and has potential application value in the fields of other energy development and environmental protection.
Drawings
FIG. 1 is a digital photograph of monoclinic phase zinc pyrophosphate prepared in example 1;
FIG. 2 is an X-ray diffraction pattern of monoclinic phase zinc pyrophosphate prepared in example 1;
FIG. 3 is a structural model of monoclinic phase zinc pyrophosphate prepared in example 1;
FIG. 4 is an X-ray absorption fine spectrum of monoclinic phase zinc pyrophosphate prepared in example 1;
FIG. 5 is a Fourier transform infrared spectrum of monoclinic phase zinc pyrophosphate prepared in example 1;
FIG. 6 is a scanning electron microscope image of monoclinic phase zinc pyrophosphate prepared in example 1;
FIG. 7 is a transmission electron microscopic view of monoclinic phase zinc pyrophosphate prepared in example 1;
FIG. 8 is a graph showing the Faraday efficiencies and corresponding potential diagrams of the products of the monoclinic phase zinc pyrophosphate prepared in example 1 at different current densities in a flow reaction cell with 2.0M KOH as electrolyte;
FIG. 9 is a graph showing the Faraday efficiency of the monoclinic phase zinc pyrophosphate prepared in example 1 at different current densities for CO in a zero gap cell with 1.0M KOH as the electrolyte;
FIG. 10 is a graph of the energy efficiency and corresponding cell voltage for CO at different current densities for monoclinic phase zinc pyrophosphate prepared in example 1 with 1.0M KOH as electrolyte in a zero gap cell.
Detailed Description
The following describes the embodiments of the present invention in further detail with reference to the drawings and examples, but should not be construed as limiting the scope of the invention.
"Range" is disclosed herein in the form of lower and upper limits. There may be one or more lower limits and one or more upper limits, respectively. The given range is defined by selecting a lower limit and an upper limit. The selected lower and upper limits define the boundaries of the particular ranges. All ranges that can be defined in this way are inclusive and combinable, i.e., any lower limit can be combined with any upper limit to form a range. For example, ranges of 60 to 120 and 80 to 110 are listed for specific parameters, with the understanding that ranges of 60 to 110 and 80 to 120 are also contemplated. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum ranges 3,4 and 5 are listed, the following ranges are all contemplated: 1 to 2, 1 to 4, 1 to 5, 2 to 3, 2 to 4 and 2 to 5.
In the present invention, unless otherwise indicated, the numerical ranges "a-b" represent shorthand representations of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" have been listed throughout, and "0-5" is only a shorthand representation of a combination of these values.
In the present invention, all the embodiments mentioned herein and the preferred embodiments may be combined with each other to form new technical solutions, if not specifically described.
In the present invention, all technical features mentioned herein and preferred features may be combined with each other to form new technical solutions, if not specifically stated.
Preferred embodiments of the present invention will be specifically described below with reference to specific embodiments, but it should be understood that reasonable variations, modifications and combinations of these embodiments can be made by those skilled in the art without departing from the scope of the present invention as defined in the appended claims, thereby obtaining new embodiments, and these new embodiments obtained by variations, modifications and combinations are also included in the scope of protection of the present invention.
Example 1
Step one, preparation of monoclinic phase zinc pyrophosphate
1.78G of zinc nitrate hexahydrate and 1.04g of ammonium dihydrogen phosphate were dissolved in deionized water, and the mixture was sufficiently stirred to form a suspension. Then 0.63g citric acid monohydrate was added and stirred until the suspension was clear, followed by drying in an oven at 120 ℃. The material was transferred to a crucible and calcined in a muffle furnace at a temperature increase rate of 5 ℃/min for 1 hour at 700 ℃ to give a gray monoclinic phase zinc pyrophosphate having a typical scandium yttrium stone structure.
Step two, performance characterization test
Through a CHI660 electrochemical workstation, a standard three-electrode system is adopted in a flow reaction tank, a 2.0M KOH solution is used as electrolyte, a gas diffusion electrode loaded with zinc pyrophosphate and carbon black is used as a working electrode, a silver/silver chloride electrode is used as a reference electrode, and foam nickel is used as a counter electrode; in a zero-gap electrolytic cell, monoclinic phase zinc pyrophosphate and carbon black are loaded on a gas diffusion electrode to serve as a working electrode, nickel-iron layered double hydroxide supported by foam nickel is used as an anode, and the testing temperature is room temperature. The gas products of the CO 2 electroreduction were analyzed by gas chromatography (RAMIN, GC2060, GC on-line test) with a flame ionization detector (FID, detection of CO, CH 4,C2H4) and a thermal conductivity detector (TCD, detection of H 2), ar being used as a carrier.
FIG. 1 is a digital photograph of the product prepared in example 1, and it can be seen that monoclinic zinc pyrophosphate was prepared as a gray powder.
FIG. 2 is an X-ray diffraction pattern of monoclinic phase zinc pyrophosphate prepared in example 1, a scanning speed of 3℃min -1, a scanning range of 10℃to 80℃and a diffraction peak of the material which is seen to correspond well to the monoclinic phase of zinc pyrophosphate (PDF#97-005-6297) without any impurity.
FIG. 3 is a schematic diagram of the structure of monoclinic zinc pyrophosphate prepared in example 1, which has a typical scandium yttrium stone structure in which pyrophosphate groups are staggered, including two pyrophosphoric acid tetrahedra sharing one oxygen atom, and having a P-O-P bond angle of 130 °. The complete structure consists of pyrophosphoric tetrahedra alternating with zinc atom layers, and is represented by 5 zinc sites with coordination number 5 (distorted structure) and 6 (regular octahedra) surrounded by nearest neighbor oxygen atomsAnd/>Two Zn-Zn bond lengths.
FIG. 4 is an X-ray absorption fine spectrum of monoclinic phase zinc pyrophosphate prepared in example 1, wherein: curve 1 is the standard sample metallic zinc foil, curve 2 is the standard sample zinc oxide, and curve 3 is the monoclinic phase zinc pyrophosphate prepared in example 1. As is clear from FIG. 4, the bulk phase of monoclinic zinc pyrophosphate maintains the +2 valence, and both Zn-O bonds and Zn-P bonds are present.
FIG. 5 is a Fourier transform infrared spectrum of monoclinic phase zinc pyrophosphate prepared in example 1, further confirming the presence of symmetrical P-O bonds, asymmetrical P-O bonds and P-O-P bonds in monoclinic phase zinc pyrophosphate prepared in example 1.
FIG. 6 is a scanning electron microscope image of monoclinic phase zinc pyrophosphate prepared in example 1, and the material is irregularly stacked nanoparticles as can be seen by observing the morphology of the sample.
FIG. 7 is a transmission electron microscopy image of monoclinic phase zinc pyrophosphate prepared in example 1, and the interconnected nanoparticles were observed, and the corresponding selective electron diffraction patterns confirmed the (22-2), (20-8) and (42-10) crystal planes present in monoclinic phase zinc pyrophosphate.
FIG. 8 is a graph showing the Faraday efficiency and the corresponding potential of the product of monoclinic phase zinc pyrophosphate prepared in example 1 under different current densities in a flow reaction cell with 2.0M KOH as electrolyte, under standard three-electrode system, monoclinic phase zinc pyrophosphate and carbon black supported on a gas diffusion electrode as working electrode, silver-silver chloride electrode as reference electrode, and nickel foam as counter electrode at room temperature. The faraday efficiency of the CO 2 reduction product measured on GC2060 gas chromatograph when a constant overpotential was applied by CHI660 electrochemical workstation showed that the faraday efficiency of CO reached 99% when current density of-300 mA cm -2 was applied; when a current density of-500 mA cm -2 was applied, the overpotential was as low as 0.87V vs. RHE, while the CO-producing local current density reached-441 mA cm -2.
FIG. 9 is a graph showing the Faraday efficiency of CO at different current densities of 1.0M KOH as an electrolyte in a zero-gap electrolytic cell for monoclinic phase zinc pyrophosphate prepared in example 1, wherein monoclinic phase zinc pyrophosphate and carbon black are supported on a gas diffusion electrode as working electrodes, nickel-iron layered double hydroxide supported by foam nickel is used as an anode, and the test temperature is room temperature. The faraday efficiency of the CO product, as measured on GC2060 gas chromatograph, showed 94% faraday efficiency of CO when a constant overpotential was applied by the CHI660 electrochemical workstation at an applied current density of-100 mAcm -2.
FIG. 10 is a graph of the energy efficiency of CO and the corresponding cell voltage at different current densities for the monoclinic phase zinc pyrophosphate prepared in example 1 with 1.0M KOH as electrolyte in a zero gap cell, with a cell voltage as low as 2.15V and a full cell energy efficiency of 58% for the CO product when a current density of-100 mA cm -2 is applied.
Compared with the existing preparation method of materials for producing CO by electrocatalytic reduction of CO 2, the invention has the following advantages: the material synthesis operation is simple, and the large-scale preparation can be realized; the raw material has rich earth reserves, low cost and excellent CO selectivity and activity of electrocatalytic production, and can realize efficient CO 2 -to-CO conversion under the conditions of low energy transmission and industrial-grade current.
Example 2
0.8G of zinc nitrate hexahydrate and 0.4g of ammonium dihydrogen phosphate were dissolved in deionized water and thoroughly stirred to form a suspension. Then 0.2g citric acid monohydrate was added and stirred until the suspension was clear, followed by drying in an oven at 120 ℃. Calcining in a muffle furnace at a heating rate of 5 ℃/min for 1 hour at 700 ℃ to obtain gray monoclinic phase zinc pyrophosphate with a typical scandium yttrium stone structure. Features and properties were similar to those of example 1.
Example 3
2.8G of zinc nitrate hexahydrate and 1.6g of ammonium dihydrogen phosphate were dissolved in deionized water and thoroughly stirred to form a suspension. Then 1.0g citric acid monohydrate was added and stirred until the suspension was clear, followed by drying in an oven at 130 ℃. Calcining in a muffle furnace at a heating rate of 5 ℃/min for 1 hour at 700 ℃ to obtain gray monoclinic phase zinc pyrophosphate with a typical scandium yttrium stone structure. Features and properties were similar to those of example 1.
The material obtained by the invention is applied to the electrocatalytic reduction of CO 2 to generate CO. The preparation of monoclinic phase zinc pyrophosphate is applied to electrocatalytic reduction of CO 2 to generate CO at normal temperature and normal pressure, and a KOH solution with the concentration of 1.0-2.0M is used as electrolyte. A standard three-electrode system is used in a flow reaction cell, wherein a gas diffusion electrode loaded with monoclinic phase zinc pyrophosphate and carbon black is used as a working electrode, a silver-silver chloride electrode is used as a reference electrode, and foamed nickel is used as a counter electrode; a gas diffusion electrode loaded with monoclinic phase zinc pyrophosphate and carbon black is used as a working electrode in a zero-gap reaction tank, and nickel-iron layered double hydroxide loaded with foam nickel is used as an anode. The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (2)
1. A method for preparing monoclinic phase zinc pyrophosphate, comprising the following steps:
(1) Dissolving 0.8-2.8 g of zinc nitrate hexahydrate and 0.4-1.6 g of ammonium dihydrogen phosphate in deionized water, and fully stirring to form suspension; then adding 0.2-1.0 g of citric acid monohydrate, stirring until the suspension is clear, and then placing in a baking oven at 100-140 ℃ for baking;
(2) Transferring the material obtained in the step (1) into a crucible, and placing the crucible in a muffle furnace to calcine the material for 1 to 6 hours at a temperature rising rate of 5 ℃/min at a temperature of 700 to 900 ℃ to obtain gray monoclinic phase zinc pyrophosphate with a typical scandium yttrium stone structure.
2. The method for producing monoclinic zinc pyrophosphate according to claim 1 wherein the entire structure of said monoclinic zinc pyrophosphate having a typical scandium yttrium stone structure is composed of pyrophosphoric tetrahedra alternating with zinc atom layers, exhibiting 5 nearest neighbor oxygen atoms surrounding a zinc site having a coordination number of 5 and a zinc site having a coordination number of 6, exhibiting 3.3 andTwo types of Zn-Zn bond lengths.
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| CN113416316A (en) * | 2021-06-28 | 2021-09-21 | 福建师范大学 | MOFs-zinc material and preparation method and application thereof |
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