CN115074757A - Preparation method of carbon fiber-loaded copper-cobalt nano-alloy nitrate transamination catalyst - Google Patents
Preparation method of carbon fiber-loaded copper-cobalt nano-alloy nitrate transamination catalyst Download PDFInfo
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Abstract
The invention discloses a preparation method of a carbon fiber loaded copper-cobalt nano-alloy nitrate-based transaminase catalyst, belonging to the technical field of preparation of cathode electro-catalysis nitrate-8 electron reduction reaction catalysts. The copper-cobalt nano alloy catalyst loaded with the excellent nitrate transamination catalytic active carbon fiber is successfully synthesized by using carbon fiber paper as a substrate and using a mixed aqueous solution of copper nitrate trihydrate and cobalt nitrate hexahydrate as a precursor solution through a carbon thermal impact method technology. The preparation method has the outstanding advantages of simplicity, environmental protection, low cost and the like, provides an idea for the research of a nitrate radical transamination green energy system, and provides reference significance for the rational design and synthesis of the cathode electrocatalysis carbon-supported metal catalyst.
Description
Technical Field
The invention belongs to polycrystalline copper Nitrate (NO) loaded by carbon nano-fiber 3 - ) The technical field of preparation of transamination catalyst, and relates to cathode electrocatalytic nitrate 8 electron reduction reaction (NO) 3 RR) catalyst, in particular to a preparation method of a copper-based binary alloy nitrate transamination catalyst loaded by carbon fiber.
Background
To reduce the accumulation of nitrate, the nitrate can be reduced to useful materials such as ammonia, hydroxylamine, and the like by effective processing methods. Electroreduction of nitrate is considered to be an ideal treatment, and pH, nitrate concentration, electrode material and applied potential are all control conditions that affect the reduction product. The process of electrocatalytic reduction of nitrate is complex, and the evolution process of electrocatalytic reduction of nitrate can be deeply understood by capturing intermediates and exploring the relationship among reactants, products, intermediates and electrode surfaces.
N 2 And NH 3 Is two main ideal products of the electrocatalytic nitrate reduction process, one is low-pollution, and the other is useful. Recent studies have reported the incorporation of NO 3 - (particularly from nitrate-rich waste streams) to NH 3 /NH 4 + Is expected to slow down the production of NH by the energy intensive Haber-Bosch process 3 The requirements of (a). Therefore, electrochemical reduction of nitrate to ammonia not only helps to solve environmental problems, but also reduces energy consumption in the process of producing ammonia. The synthesis of ammonia by electro-reduction of nitrate is an 8-electron transfer process, and the reaction formula in an acidic solution is as follows:
NO 3 - +8e - +10H + →3H 2 O+NH 4 + (1)
from virtually NO 3 - Conversion to NH 4 + The process of (A) is complex, involving a number of intermediates and a series of intermediate reactions, and related studies indicate Nitrite (NO) 2 -) and gaseous Nitric Oxide (NO) may be two important reaction intermediates. The rate-determining step (RDS) of the entire reaction process is considered to be that of the first two electronsThe reduction process, i.e. the reduction of nitrate to nitrite, is given by the following formula:
NO 3 - +2H + +2e - →NO 2 - +H 2 O (2)
then NO 2 - Is reduced to NO by an electron transfer process, as follows:
NO 2 - +2H + +e - →NO+H 2 O (3)
NO adsorbed on the electrode surface is reduced to the final product ammonia by a faster 5 electron transfer process as follows:
NO+5H + +5e - →NH 3 +H 2 O (4)
the above 5 electron transfer process is in fact three hydrogenation processes, as follows:
NO+H + +e - →2HNO (5)
HNO+H + +e - →H 2 NO (6)
H 2 NO+3H + +3e - →NH 3 +H 2 O (7)
direct protonation of the adsorbed NO brings the NO to equilibrium with HNO intermediates. And HNO to H 2 An electronic process of NO conversion becomes the rate-determining step, and finally occurs faster from H 2 NO to NH 3 The three electron transfer process of (1).
The carbothermic shock method (Carbothermal shock) is a synthesis method which is created by the subject of the professor of the improved soldiers of the university of maryland in the United states and can regulate and control the characteristics of alloy nanoparticles containing various metal elements, such as appearance, size, components, entropy value and the like. The crystal phase, size, metal coordination, surface atom arrangement and the like of the high-entropy solid solution target catalyst can be regulated and controlled by changing factors such as a carrier, temperature, impact time, heating/cooling rate and the like. WOO-BINJUNG of Harvard university in USA and HYEONSUJEONG, HEE-TAEJUNG of Korea institute of science and technology evaluate the carbon thermal shock method as one of the simplest synthetic methods for preparing mono-multi metal nanoparticles. According to the method, the metal precursor is simply loaded on the carbon substrate, and the temperature of the sample can be instantly increased by passing current for a short time, so that the nano particles are generated. Currently, a number of metals have been explored for use in the electro-reductive nitrate transamination system, where copper, either alone or in combination with other metals, exhibits excellent electro-catalytic nitrate reduction performance. Based on the above, the invention reduces copper ions and cobalt ions in the aqueous solution into the copper-cobalt nano alloy loaded on the carbon nano fibers by the carbon thermal impact technology, and the copper-cobalt nano alloy is used in a reaction system for electro-reducing nitrate into ammonia.
Disclosure of Invention
The invention solves the technical problem of providing a preparation method of a carbon fiber loaded copper-cobalt nano alloy nitrate radical transamination catalyst with simple process, low cost and excellent performance, which takes conventional carbon fiber paper as a substrate and contains copper nitrate trihydrate (Cu (NO) with a certain concentration 3 ) 2 ·3H 2 O) and cobalt nitrate hexahydrate (Co (NO) 3 ) 2 ·6H 2 O) mixed aqueous solution is used as a metal precursor impregnation solution, and a carbon thermal impact technology is adopted to successfully synthesize the carbon fiber loaded copper-cobalt nano alloy nitrate radical transamination catalyst.
The invention adopts the following technical scheme for solving the technical problems, and the preparation method of the carbon fiber loaded copper-cobalt nano alloy nitrate radical transaminase catalyst is characterized by comprising the following specific steps of:
step S1: cutting the carbon fiber paper into a rectangle of 1cm multiplied by 0.5cm, and placing the rectangle in an alcohol lamp for heating for 1-2 min for later use;
step S2: the molar concentration of the total metal atoms is prepared to be 0.1mol L -1 Cu (NO) of 3 ) 2 ·3H 2 O and Co (NO) 3 ) 2 ·6H 2 A mixed aqueous solution of O, namely a metal precursor solution, is reserved, wherein the molar ratio of copper nitrate trihydrate to cobalt nitrate hexahydrate is 1: 1-5: 1;
step S3: soaking the carbon paper preheated in the step S1 in the metal precursor solution obtained in the step S2 for 10-20 min, then placing the carbon paper under an infrared lamp to bake the surface of the carbon paper, placing the carbon paper soaked with the metal precursor solution in Joule heating equipment, and synthesizing carbon by a carbon thermal impact methodThe carbon fiber loaded copper-cobalt nano alloy nitrate radical transaminase catalyst has the advantages that inductive gas molecules used in the carbon thermal impact process are hydrogen, argon or mixed gas of hydrogen and argon, the continuous heating time is 1-60 s, the catalyst is placed in cold ethanol liquid immediately after being heated and is rapidly cooled to room temperature, and the carbon fiber loaded copper-cobalt nano alloy nitrate radical transaminase catalyst can be obtained, the Cu content in copper-cobalt nano alloy is 1.21at.%, the Co content is 0.95at.%, the O content is 6.35at.%, and the C content is 91.49at.%, the carbon fiber loaded copper-cobalt nano alloy nitrate radical transaminase catalyst has excellent nitrate radical transaminase activity and stability, the Faraday efficiency can reach 94.40%, and the ammonia yield is 136.4 mu mol h -1 cm -2 。
Further preferably, the molar ratio of copper nitrate trihydrate to cobalt nitrate hexahydrate in step S2 is 2.5: 1.
More preferably, in step S3, the inducing gas molecules are a mixture of argon and hydrogen, and the heating duration is 30 seconds.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the carbon thermal impact method related by the invention has simple and convenient preparation process, time saving and high efficiency, avoids the complex processes of high-temperature pyrolysis, hydrothermal reaction and the like usually related by the conventional preparation of nitrate radical transamination catalyst, and selects cheap and easily obtained Cu (NO) 3 ) 2 ·3H 2 O、Co(NO 3 ) 2 ·6H 2 O is metal precursor salt, and the high-activity carbon fiber loaded copper-cobalt nano alloy nitrate radical transaminase electrocatalyst can be obtained by a simple carbon thermal impact method in one step.
2. The invention optimizes Cu (NO) in the electrodeposition process 3 ) 2 ·3H 2 O and Co (NO) 3 ) 2 ·6H 2 And O is used in a ratio to obtain the Cu-Co nano alloy catalyst rich in Cu (111), Cu (100), Co (111) and Co (100) crystal planes. Wherein, related research shows that Cu crystal face is more beneficial to realizing NO 3 - Inverted NO 2 - The deoxidation process of conversion, and Co crystal face is more easy to produce hydrogen free radical, thereby promoting NOTo NH 3 And (4) hydrogenation process of conversion. Therefore, the copper-cobalt nano alloy catalyst with enhanced copper-cobalt synergistic effect developed by the invention is used for constructing high-performance NO 3 - Reduction of NH 3 An efficient strategy for electrocatalysts.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) electron micrograph of a pure carbon fiber sample E1(a, b), carbon fiber supported monometallic copper E2(c, d), carbon fiber supported copper cobalt nanoalloys E3-E5(E-j), and carbon fiber supported monometallic cobalt E6(k, l) nitrate nitrogen transamination catalyst prepared in examples 1-6;
FIG. 2 is X-ray diffraction (XRD) pattern (a), X-ray photoelectron spectroscopy (XPS) pattern (b), and high resolution Cu2p (c) and Co2p (d) patterns of pure carbon fiber sample E1, carbon fiber supported monometallic copper E2, carbon fiber supported copper cobalt nano-alloy E3-E5, and carbon fiber supported monometallic cobalt E6 nitrate transaminase prepared in examples 1-6;
FIG. 3 is a Linear Sweep Voltammetry (LSV) curve (a), an LSV curve (b) of E4 in different electrolytes, a Tafel slope (c) of E1-E6, an Electrochemical Impedance Spectroscopy (EIS) graph (d) of E1-E6, an Faraday efficiency (E) of nitrate transamination obtained by E4 at different reaction potentials, and E4 in examples 1-6 for pure carbon fiber sample E1, carbon fiber supported monometallic copper E2, carbon fiber supported copper cobalt nano-alloy E3-E5, and carbon fiber supported monometallic cobalt E6 nitrate transamination catalyst (A), an LSV curve (b) of E4 in different electrolytes, an EIS curve (d) of E1-E6, an EIS curve (d) graph (E4) in different reaction potentials, and a Faraday efficiency (E4) in E3652 14/15 Nuclear magnetic resonance obtained after reaction in N nitrate radical solution 1 H NMR) spectrum (f).
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above subject matter of the present invention belong to the scope of the present invention.
Example 1
The method comprises the following steps: cutting the carbon fiber paper into a rectangle of 1cm multiplied by 0.5cm, and placing the rectangle outside an alcohol lamp to heat for about 1min to obtain a pure carbon fiber catalyst (a control sample) E1;
example 2
Step S1: cutting carbon fiber paper into a rectangle of 1cm multiplied by 0.5cm, and heating the rectangle by putting the rectangle outside an alcohol lamp for about 1min for later use;
step S2: the molar concentration of the total metal atoms is prepared to be 0.1mol L -1 Cu (NO) of 3 ) 2 ·3H 2 O water solution, namely metal precursor solution, is reserved;
step S3: and (2) dipping the preheated carbon paper in a metal precursor solution for 10min, then placing the carbon paper under an infrared lamp to bake the surface of the carbon paper, then placing the carbon paper dipped with the metal precursor solution in Joule heating equipment, and synthesizing the carbon fiber-loaded copper-cobalt nano alloy nitrate-based transaminase catalyst by a carbon thermal impact method. And inducing gas molecules used in the carbon thermal impact process are mixed gas of hydrogen and argon, the continuous heating time is 30s, the mixture is immediately placed in cold ethanol liquid after being heated, and the mixture is rapidly cooled to room temperature, so that the carbon fiber-supported single-metal copper nitrate radical transaminase E2 can be obtained. The Cu content was 1.37 at.%, the O content was 4.79 at.%, and the C content was 93.84 at.%.
Example 3
Step S1: cutting carbon fiber paper into a rectangle of 1cm multiplied by 0.5cm, and heating the rectangle by putting the rectangle outside an alcohol lamp for about 1min for later use;
step S2: preparing the total metal atom molar concentration of 0.1mol L -1 Cu (NO) of 3 ) 2 ·3H 2 O and Co (NO) 3 ) 2 ·6H 2 O mixed aqueous solution, i.e. metal precursor solution, for standby use, Cu (NO) 3 ) 2 ·3H 2 O and Co (NO) 3 ) 2 ·6H 2 The molar ratio of O is 5: 1;
step S3: and (2) dipping the preheated carbon paper in a metal precursor solution for 10min, then placing the carbon paper under an infrared lamp to bake the surface of the carbon paper, then placing the carbon paper dipped with the metal precursor solution in Joule heating equipment, and synthesizing the carbon fiber-loaded copper-cobalt nano alloy nitrate-based transaminase catalyst by a carbon thermal impact method. Inductive gas molecules used in the carbon thermal impact process are mixed gas of hydrogen and argon, the continuous heating time is 30s, the mixture is placed in cold ethanol liquid immediately after being heated, and the mixture is rapidly cooled to the room temperature, so that the carbon fiber loaded copper-cobalt nano-alloy nitrate-based transaminase E3 can be obtained. The Cu content is 0.92 at.%, the Co content is 0.4 at.%, the O content is 2.9 at.%, and the C content is 95.78 at.%.
Example 4
Step S1: cutting carbon fiber paper into small rectangles with the size of 1cm multiplied by 0.5cm, and placing the rectangles outside an alcohol lamp to heat for about 1min for later use;
step S2: preparing the total metal atom molar concentration of 0.1mol L -1 Cu (NO) of 3 ) 2 ·3H 2 O and Co (NO) 3 ) 2 ·6H 2 O mixed aqueous solution, namely metal precursor solution, is reserved, and the ratio of the O mixed aqueous solution to the metal precursor solution is 2.5: 1;
step S3: and (3) soaking the preheated carbon paper in the material A for 10min, then placing the carbon paper under an infrared lamp to bake the surface of the carbon paper, then placing the carbon paper soaked with the metal precursor solution in Joule heating equipment, and synthesizing the carbon fiber-loaded copper-cobalt nano alloy nitrate-nitrogen-based transaminase catalyst by a carbon thermal impact method. And inducing gas molecules used in the carbon thermal impact process are hydrogen-argon mixed gas, the continuous heating time is 30s, the carbon thermal impact process is immediately placed in cold ethanol liquid after heating, and the carbon fiber loaded copper-cobalt nano alloy nitrate-based transaminase catalyst E4 can be obtained after the carbon thermal impact process is rapidly cooled to the room temperature. The Cu content is 1.21at.%, the Co content is 0.95at.%, the O content is 6.35at.%, and the C content is 91.49 at.%. The carbon fiber loaded copper-cobalt nano alloy nitrate radical transamination catalyst has excellent nitrate radical transamination activity and stability, the Faraday efficiency can reach 94.40%, and the ammonia yield is 136.4 mu mol h -1 cm -2 。
Example 5
Step S1: cutting carbon fiber paper into a rectangle of 1cm multiplied by 0.5cm, and heating the rectangle by putting the rectangle outside an alcohol lamp for about 1min for later use;
step S2: the molar concentration of the total metal atoms is prepared to be 0.1mol L -1 Cu (NO) of 3 ) 2 ·3H 2 O and Co (NO) 3 ) 2 ·6H 2 O mixed aqueous solution, i.e. metal precursor solution, for standby use, Cu (NO) 3 ) 2 ·3H 2 O and Co (NO) 3 ) 2 ·6H 2 The molar ratio of O is 1: 1;
step S3: and (2) dipping the preheated carbon paper in a metal precursor solution for 10min, then placing the carbon paper under an infrared lamp to bake the surface of the carbon paper, then placing the carbon paper dipped with the metal precursor solution in Joule heating equipment, and synthesizing the carbon fiber-loaded copper-cobalt nano alloy nitrate-based transaminase catalyst by a carbon thermal impact method. And inducing gas molecules used in the carbon thermal impact process are mixed gas of hydrogen and argon, the continuous heating time is 30s, the mixture is immediately placed in cold ethanol liquid after being heated, and the mixture is rapidly cooled to room temperature, so that the carbon fiber loaded copper-cobalt nano alloy nitrate-nitrogen-based transaminase E5 can be obtained. The Cu content is 1.39 at.%, the Co content is 1.81 at.%, the O content is 5.82 at.%, and the C content is 90.98 at.%.
Example 6
Step S1: cutting carbon fiber paper into a rectangle of 1cm multiplied by 0.5cm, and heating the rectangle by putting the rectangle outside an alcohol lamp for about 1min for later use;
step S2: preparing the total metal atom molar concentration of 0.1mol L -1 Co (NO) of 3 ) 2 ·6H 2 O water solution, namely metal precursor solution, is reserved;
step S3: and (2) dipping the preheated carbon paper in a metal precursor solution for 10min, then placing the carbon paper under an infrared lamp to bake the surface of the carbon paper, then placing the carbon paper dipped with the metal precursor solution in Joule heating equipment, and synthesizing the carbon fiber-loaded copper-cobalt nano alloy nitrate-based transaminase catalyst by a carbon thermal impact method. And inducing gas molecules used in the carbon thermal impact process are mixed gas of hydrogen and argon, the continuous heating time is 30s, the mixture is immediately placed in cold ethanol liquid after being heated, and the mixture is rapidly cooled to room temperature, so that the carbon fiber-supported single-metal cobalt nitrate nitrogen transamination catalyst E6 can be obtained. The Co content is 1.65 at.%, the O content is 4.03 at.%, and the C content is 94.32 at.%.
NO 3 RR activity assay procedure: the prepared NO is 3 RR electrocatalyst (E1/E2/E3/E4/E5/E6) is placed in a Pt sheet electrode clamp and used as a working electrode, a Saturated Calomel Electrode (SCE) is used as a reference electrode, a Pt sheet is used as a counter electrode, and 0.5mo is usedl L - 1 Na 2 SO 4 +0.1mol L -1 KNO 3 The mixed aqueous solution is used as electrolyte to form a three-electrode testing system. Firstly, introducing argon into the electrolyte for saturation, and then carrying out an LSV test to obtain an LSV polarization curve of the E1-E6 catalyst, wherein the sweep rate is 5mV s -1 The potential interval is-0.65 to-1.4V; at 0.5mol L -1 Na 2 SO 4 EIS test is carried out in the solution to obtain the electrochemical impedance value of the E1-E6 catalyst, and the test frequency is 10-10 6 And (4) MHz. At 0.5mol L -1 Na 2 SO 4 +0.1mol L -1 KNO 3 And performing a timing current response test on the mixed aqueous solution to obtain a timing current curve of the E4 catalyst under different reaction potentials, wherein the reaction time is 1800s, and the reaction potentials are-0.05V, -0.15V and-0.25V vs. And (3) performing indophenol blue test on the electrolyte obtained at different reaction potentials by using an ultraviolet visible spectrophotometer to obtain an ultraviolet visible spectral curve of the E4 catalyst at different reaction potentials.
NO of samples E1-E6 prepared in examples 1-6 3 RR catalytic performance was as follows: as shown in FIG. 3 (a), the limiting reaction current of the E4 sample was maximized from the LSV curve of the E1-E6 samples, demonstrating that the E4 sample had the most excellent NO 3 RR activity; as shown in FIG. 3 (b), the E4 samples were separately in blank solution (pure Na) 2 SO 4 Solution), NaNO 2 +Na 2 SO 4 Solution and KNO 3 +Na 2 SO 4 When tested in solution, different responses were obtained, among which in KNO 3 +Na 2 SO 4 The reaction current in solution is maximum; as shown in FIG. 3 (c), the Tafel slope of the E4 sample was the smallest among the E1-E5 samples, demonstrating that the E4 sample has faster mass transfer kinetics, although the Tafel slope of the E6 sample is smaller than that of the E4 sample, the E6 sample was analyzed in KNO in combination with LSV curve 3 +Na 2 SO 4 NO appears in the solution 3 RR reduction peak, which is presumed to exhibit a smaller Tafel slope associated with hydrogen evolution reaction; as shown in fig. 3 (d), the EIS value of the E4 sample was the smallest among the E1-E6 samples, demonstrating that the E4 sample has the most excellent conductivity and a faster mass transfer process; such asAs shown in FIG. 3 (E), the E4 sample shows higher Faraday efficiency (94.40% -96.29%) and ammonia yield (114-164. mu. mol h) under three different reaction potentials -1 cm -2 ) It is well demonstrated that the E4 sample has excellent NO 3 RR catalytic active area; when used separately as shown in FIG. 3 (f) 14N KNO 3 And 15N KNO 3 as a reaction nitrogen source, and then performing nuclear magnetic resonance test on the electrolyte after reaction to obtain the electrolyte 1 H NMR spectrum, the result showed that when the nitrogen source was 14N KNO 3 When the ammonia product is 14N NH 3 When the nitrogen source is 15N KNO 3 When the ammonia product is 15N NH 3 It is fully shown that the ammonia product obtained after the reaction is really from KNO 3 And (3) reacting the raw materials.
The foregoing embodiments illustrate the principles, principal features and advantages of the invention, and it will be understood by those skilled in the art that the invention is not limited to the foregoing embodiments, which are merely illustrative of the principles of the invention, and that various changes and modifications may be made therein without departing from the scope of the principles of the invention.
Claims (3)
1. A preparation method of a carbon fiber loaded copper-cobalt nano alloy nitrate aminotransferase catalyst is characterized by comprising the following specific steps:
step S1: cutting the carbon fiber paper into a rectangle of 1cm Í 0.5.5 cm, and placing the rectangle in an alcohol burner to heat for 1-2 min for later use;
step S2: preparing the total metal atom molar concentration of 0.1mol L -1 The mixed aqueous solution of copper nitrate trihydrate and cobalt nitrate hexahydrate is a metal precursor solution for standby, wherein the molar ratio of the copper nitrate trihydrate to the cobalt nitrate hexahydrate is 1: 1-5: 1;
step S3: soaking the carbon paper preheated in the step S1 in the metal precursor solution obtained in the step S2 for 10-20 min, then placing the carbon paper under an infrared lamp to bake the surface of the carbon paper, placing the carbon fiber paper soaked with the metal precursor solution in Joule heating equipment, and synthesizing carbon fiber negative ions by a carbon thermal impact methodThe loaded copper-cobalt nano alloy nitrate radical transaminase catalyst has the advantages that inductive gas molecules used in the carbon thermal impact process are hydrogen, argon or mixed gas of hydrogen and argon, the continuous heating time is 1-60 s, the catalyst is immediately placed in cold ethanol liquid after being heated and is rapidly cooled to room temperature, and the carbon fiber loaded copper-cobalt nano alloy nitrate radical transaminase catalyst can be obtained, the Cu content in the copper-cobalt nano alloy is 1.21at.%, the Co content is 0.95at.%, the O content is 6.35at.%, and the C content is 91.49at.%, the carbon fiber loaded copper-cobalt nano alloy nitrate radical transaminase catalyst has excellent nitrate radical transaminase activity and stability, the Faraday efficiency can reach 94.40%, and the ammonia yield is 136.4 mu mol h -1 cm -2 。
2. The method for preparing carbon fiber supported copper-cobalt nanoalloy nitrate-ammonia-transfer catalyst according to claim 1, characterized in that: the molar ratio of copper nitrate trihydrate to cobalt nitrate hexahydrate in step S2 was 2.5: 1.
3. The method for preparing carbon fiber supported copper-cobalt nanoalloy nitrate-ammonia-transfer catalyst according to claim 1, characterized in that: in step S3, the inducing gas molecules are a mixture of argon and hydrogen, and the heating time is 30S.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116393138A (en) * | 2023-04-20 | 2023-07-07 | 河南师范大学 | Preparation method of copper-nickel-tin nano metal glass catalyst for nitrate reduction ammonia conversion |
| CN117026257A (en) * | 2023-10-10 | 2023-11-10 | 河南师范大学 | Preparation method of zinc-nitrate radical battery based on high-entropy oxide |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116393138A (en) * | 2023-04-20 | 2023-07-07 | 河南师范大学 | Preparation method of copper-nickel-tin nano metal glass catalyst for nitrate reduction ammonia conversion |
| CN116393138B (en) * | 2023-04-20 | 2024-04-05 | 河南师范大学 | Preparation method of copper-nickel-tin nano metal glass catalyst for nitrate reduction ammonia conversion |
| CN117026257A (en) * | 2023-10-10 | 2023-11-10 | 河南师范大学 | Preparation method of zinc-nitrate radical battery based on high-entropy oxide |
| CN117026257B (en) * | 2023-10-10 | 2024-01-09 | 河南师范大学 | Preparation method of zinc-nitrate radical battery based on high-entropy oxide |
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