CN113913861A - Ce-Bi for nitrate radical reduction2WO6Electrocatalyst and method of making - Google Patents

Ce-Bi for nitrate radical reduction2WO6Electrocatalyst and method of making Download PDF

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CN113913861A
CN113913861A CN202111074601.3A CN202111074601A CN113913861A CN 113913861 A CN113913861 A CN 113913861A CN 202111074601 A CN202111074601 A CN 202111074601A CN 113913861 A CN113913861 A CN 113913861A
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nitrate
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molar ratio
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CN113913861B (en
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叶伟
徐梦秋
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Hangzhou Normal University
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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
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/27—Ammonia
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Abstract

The invention relates to the technical field of catalysts, and discloses Ce-Bi for nitrate radical reduction2WO6An electrocatalyst and a method of making the same. The raw material of the electrocatalyst comprises Na with the molar ratio of 1:1-2:0.05-0.152WO4•2H2O，Bi(NO3)3•5H2O and Ce (NO)3)3•6H2O; the Ce atom is in Bi2WO6The crystal lattice is a substitutional atom, and the doping percentage of Ce is 5% -13%, which is used for nitrate radical reduction. Ce-Bi of the present invention2WO6The electrocatalyst has high catalytic efficiency and shows excellent structural and electrochemical durability; the synthesis method has the advantages of simple process, low energy consumption, mild conditions and good product appearance, and is suitable for large-scale productionThe application is as follows.

Description

Ce-Bi for nitrate radical reduction2WO6Electrocatalyst and method of making
Technical Field
The invention relates to the technical field of catalysts, in particular to Ce-Bi for nitrate radical reduction2WO6An electrocatalyst and a method of making the same.
Background
Although it can pass electrochemical nitrogen (N) under ambient conditions2) The reduction reaction (NRR) produces ammonia, but the reaction rate and faradaic efficiency are generally low due to the large bond energy of the nitrogen-nitrogen triple bond (941 kJ/mol). In sharp contrast, the reduction of nitrate (nitrate) to ammonia requires only 204 kJ/mol, so the nitrate reduction reaction (NO)3RR) has attracted considerable attention as a more efficient and energy efficient ammonia production strategy. However, ammonia of NO3RRThe productivity is still much lower than the Harbour route due to the lack of a powerful electrocatalyst to generate high current density (4200mA cm)-2) And well inhibits the competitive Hydrogen Evolution Reaction (HER). Low temperature electrified ammonia production powered by renewable energy as an alternative to the haber process may reduce fossil fuel usage and carbon dioxide emissions. The electrocatalytic conversion of nitrate nitrogen to ammonia involves 9 protons and 8 electrons (NO)3 −+ 9 H++ 8 e−→NH3+ 3H2O) is a slow kinetic eight electron transfer process with various by-products (i.e. nitrogen dioxide, N)2And N2H4). For this reason, there have been a great deal of effort to develop different metal-based electrocatalysts (i.e., Cu, Ru, Ag, Fe, Au, Ti) to promote the conversion of nitrates to ammonia. Therefore, rational design and development of high NO3RR activity, an electrocatalyst that inhibits HER well is highly urgent.
Due to the worldwide use of nitrogenous fertilizers and pesticides, nitrate is abundant in nature. It is well known that nitrate in drinking water causes diseases such as methemoglobinemia and non-hodgkin's lymphoma. Converting nitrate to ammonia by electrocatalysis may provide a good solution to energy and environmental problems. It was found that ammonia gas was produced on a large scale by the Haber-Bosch process. Such an industry N2The yield of reduction reaction (NRR) is generally less than 200 mmolegcat−1h−1The process is energy intensive because it is carried out at high temperatures of 400-. Aqueous-based electrocatalytic NRR at ambient conditions is a more sustainable ammonia production process. However, these reaction rates and partial current densities are typically less than 10 mmolegcat, respectively−1h−1And 1 mA cm−2. And N2Compared to 941 kJ/mol needed to break the NN triple bonds, nitrates can be decomposed to much lower deoxy species with an energy of 204 kJ/mol. From an energy perspective, it is of great interest to explore the electrocatalytic nitric acid reduction reaction (NITRR) as a promising tool for low temperature ammonia synthesis. NRR occurs at the solid-liquid interface with a lower reaction energy barrier than the solid-gas-liquid interface of NRR. It is also advantageous in selectivitySince the kinetics of NITRR can be optimized for competing Hydrogen Evolution Reactions (HER).
Publication No. CN108452851A discloses a supported bismuth tungstate photocatalyst for air purification and a preparation method thereof. A, mixing, roasting and grinding prepared bismuth tungstate powder and cerium nitrate to prepare cerium-doped bismuth tungstate composite photocatalyst powder; b. immersing the polyether sulfone microporous membrane activated by formaldehyde into a chitosan solution, and reacting to obtain a polyether sulfone microporous membrane with a surface modified by chitosan; c. and (3) dipping the polyether sulfone microporous membrane into silica sol dispersed by the composite photocatalyst powder, and carrying out film coating to obtain the polyether sulfone microporous membrane loaded cerium-doped bismuth tungstate composite photocatalyst. However, the catalyst used in the present invention is hardly applicable to nitrate reduction electrocatalysis.
Disclosure of Invention
In order to solve the above technical problems, the present invention provides Ce-Bi for nitrate radical reduction2WO6An electrocatalyst and a method for preparing the same, having high catalytic efficiency, exhibiting excellent structural and electrochemical durability; the synthesis method has the advantages of simple process, low energy consumption, mild conditions and good product appearance, and is suitable for large-scale production and application.
The specific technical scheme of the invention is that the Ce-Bi2WO6An electrocatalyst, the electrocatalyst raw material comprises Na with a molar ratio of 1:1-2:0.05-0.152WO4•2H2O，Bi(NO3)3•5H2O and Ce (NO)3)3•6H2O; the Ce atom is in Bi2WO6The crystal lattice is a substitutional atom, and the doping percentage of Ce is 5-13%.
The invention introduces and adjusts Bi by adjusting the quantity of Ce dopant2WO6Crystal defects in the host lattice, effect catalytic reduction of nitrate. The Ce-Bi provided by the invention2WO6The catalyst performance is superior to most of the previously reported electrocatalysts for nitric acid reduction in double-base and W-base aqueous solutions, the adsorption configuration of nitrate in nitric acid reduction can be changed, a Ce-W bond is generated, and two metals are electronegativeDifferent, the charge difference exists, which is beneficial to the absorption and desorption of the nitric acid. Bi2WO6As one of binary transition metal oxides, it is possible to provide a reactant with abundant active sites due to the change of the electronic structure, and in addition, Bi2WO6Is an Aurivillius type compound with a layered structure, and Bi is shown by Density Functional Theory (DFT) calculation2WO6Crystal defects of (2) enhance NO3 -Adsorption and activation. The catalyst also exhibits excellent structural and electrochemical durability by doping Ce atoms to generate crystal defects in a host. The synthesis method provided by the invention has the characteristics of simple process, low energy consumption, mild conditions, good product appearance and the like, and is suitable for large-scale production and application. However, when the doping amount is too large, the activity of the catalyst is lowered because excess Ce does not substitute W to form a Ce-W bond but a Ce-Ce bond, so that the addition of excess does not promote the improvement of the performance.
Preferably, the Ce-Bi2WO6Has a layered structure.
Preferably, the particle size of the electrocatalyst is 0.25 to 0.3 nm.
The smaller the particle size, the larger the specific surface area of the catalyst, and the higher the catalytic efficiency.
The invention also provides a preparation method of the electrocatalyst, which comprises the following steps:
(1) mixing Na2WO4·2H2Dissolving O in a solvent to prepare a solution A; adding Bi (NO)3)3·5H2Dissolving O in a solvent to prepare a solution B;
(2) adding solution A to solution B, and then adding Ce (NO)3)3·6H2O, Na in the obtained mixed solution after uniform mixing2WO4、Bi(NO3)3With Ce (NO)3)3The molar ratio of (1: 1) - (2: 0.05) - (0.13);
(3) the mixed solution is hydrothermally synthesized for 24-36h under the conditions of 150 ℃ and 180 ℃, and after the reaction is finished, the Ce-Bi is obtained by separation, cleaning and drying2WO6An electrocatalyst.
Step (ii) of(2) In the method, the order of adding the solution A to the solution B is fixed, and the better Bi formation can be obtained only by the adding order2WO6 Bi cannot be formed when the order is changed2WO6。
Preferably, in the step (1), the mass fraction of the solution A is 0.67wt% to 1.3wt%, the mass fraction of the solution B is 2.6wt% to 3.2wt%, and the solvent is water.
Preferably, in the step (2), the uniform mixing mode is one or more of magnetic stirring, ultrasonic mixing and mechanical stirring.
Preferably, in the step (3), the separation mode is centrifugal separation, the centrifugal rotation speed is 3000-4000r/min, and the centrifugal time is 60-120 min.
Preferably, in the step (3), the cleaning manner is to alternately clean with deionized water and ethanol.
Preferably, in the step (3), the drying mode is drying for 24-30h in vacuum at 60-70 ℃.
The invention also provides the Ce-Bi2WO6The electrocatalyst is used for nitrate reduction.
Compared with the prior art, the invention has the beneficial effects that:
1. the catalyst has high catalytic efficiency, excellent structure and good electrochemical durability;
2. the synthesis method has the advantages of simple process, low energy consumption, mild conditions and good product appearance, and is suitable for large-scale production and application.
Drawings
FIG. 1 is a TEM image of example 2 of the present invention;
FIG. 2 is an XRD pattern for example 2 of the present invention;
FIG. 3 is a graph of operating voltage versus ammonia production activity and Faraday efficiency for example 2 of the present invention;
figure 4 is a graph of the percent Ce doping of the electrocatalyst according to the invention as a function of ammonia production activity and faraday efficiency.
Detailed Description
The present invention will be further described with reference to the following examples. The devices, reagents and methods referred to in the present invention are those known in the art unless otherwise specified.
Example 1
Ce-Bi2WO6The preparation method of the electrocatalyst is characterized by comprising the following steps of:
(1) mixing Na2WO4·2H2O is prepared into an aqueous solution A with the mass fraction of 1.0 wt%; adding Bi (NO)3)3·5H2O is prepared into an aqueous solution B with the mass fraction of 3.0 wt%;
(2) adding the solution A into the solution B, and uniformly mixing the solution A and the solution B by magnetic stirring to obtain mixed solution containing Na2WO4、Bi(NO3)3With Ce (NO)3)3In a molar ratio of 1:1: 0.05;
(3) the mixed solution is hydrothermally synthesized for 24-36h at the temperature of 150-2WO6An electrocatalyst.
Example 2
Ce-Bi2WO6The preparation method of the electrocatalyst is characterized by comprising the following steps of:
(1) mixing Na2WO4·2H2O is prepared into an aqueous solution A with the mass fraction of 1.0 wt%; adding Bi (NO)3)3·5H2O is prepared into an aqueous solution B with the mass fraction of 3.0 wt%;
(2) adding the solution A into the solution B, and uniformly mixing the solution A and the solution B by magnetic stirring to obtain mixed solution containing Na2WO4、Bi(NO3)3With Ce (NO)3)3In a molar ratio of 1:1: 0.1;
(3) the mixed solution is hydrothermally synthesized for 24-36h at the temperature of 150-2WO6An electrocatalyst.
Example 3
A kind ofCe-Bi2WO6The preparation method of the electrocatalyst is characterized by comprising the following steps of:
(1) mixing Na2WO4·2H2O is prepared into an aqueous solution A with the mass fraction of 1.0 wt%; adding Bi (NO)3)3·5H2O is prepared into an aqueous solution B with the mass fraction of 3.0 wt%;
(2) adding the solution A into the solution B, and uniformly mixing the solution A and the solution B by magnetic stirring to obtain mixed solution containing Na2WO4、Bi(NO3)3With Ce (NO)3)3In a molar ratio of 1:1: 0.13;
(3) the mixed solution is hydrothermally synthesized for 24-36h at the temperature of 150-2WO6An electrocatalyst.
Comparative example 1
Bi2WO6The preparation method of the electrocatalyst is characterized by comprising the following steps of:
(1) mixing Na2WO4·2H2O is prepared into an aqueous solution A with the mass fraction of 1.0 wt%; adding Bi (NO)3)3·5H2O is prepared into an aqueous solution B with the mass fraction of 3.0 wt%;
(2) adding the solution A into the solution B, and uniformly mixing the solution A and the solution B by magnetic stirring to obtain mixed solution containing Na2WO4、Bi(NO3)3In a molar ratio of 1: 1;
(3) the mixed solution is hydrothermally synthesized for 24-36h at the temperature of 150-2WO6An electrocatalyst.
Comparative example 2
Ce-Bi2WO6The preparation method of the electrocatalyst is characterized by comprising the following steps of:
(1) mixing Na2WO4·2H2O is prepared into mass fraction1.0wt% aqueous solution a; adding Bi (NO)3)3·5H2O is prepared into an aqueous solution B with the mass fraction of 3.0 wt%;
(2) adding the solution A into the solution B, and uniformly mixing the solution A and the solution B by magnetic stirring to obtain mixed solution containing Na2WO4、Bi(NO3)3With Ce (NO)3)3In a molar ratio of 1:1: 0.15;
(3) the mixed solution is hydrothermally synthesized for 24-36h at the temperature of 150-2WO6An electrocatalyst.
Performance testing
The final products of examples 1-3 and comparative examples 1-2 were weighed to obtain 4mg, and 750. mu.L of deionized water, 200. mu.L of isopropyl alcohol and 50. mu.L of naphthol were added to prepare a catalyst solution, and 30. mu.L of the catalyst solution was dropped onto 1cm by 1cm carbon paper to measure the reducing activity.
The test method is as follows:
the test adopts a three-electrode system, carbon paper is clamped by an electrode clamp to be used as a working electrode, a silver/silver chloride electrode is used as a reference electrode, a platinum net is used as a counter electrode, 1mol/L potassium hydroxide and 1mol/L potassium nitrate mixed solution is used as an electrolyte solution, an electrochemical workstation is used for providing a power supply, the applied voltage range is-0.5 to-1 v, and the test duration is 1 hour. Testing
As can be seen from the TEM of FIG. 1, Ce-Bi obtained by the inventive example 22WO6The electrocatalyst has a laminated structure and the particle size is 0.25-0.3 nm;
as can be seen from FIG. 2, Ce-Bi obtained by the present invention in example 2 was used2WO6XRD pattern of the electrocatalyst shows that Bi is2WO6The main peaks can be well matched.
As can be seen from FIG. 3, Ce-Bi produced by the inventive example 22WO6The metal nano-layered structure electrocatalyst has the highest ammonia production activity and Faraday efficiency under the voltage of-1V. The reason is that when the applied voltage is large, water is cracked faster, charge is transferred faster, and the reaction efficiency is higher.
From the figure4, it is understood that Ce-Bi according to the present invention2WO6The metal nano-layered structure electrocatalyst has the highest nitric acid reduction activity and Faraday efficiency when the doping percentage of Ce is 10%. The performance of examples 1-3 is better than that of comparative example 2, and the performance change of examples 1-3 is not a single linear change, which shows that the optimal Ce doping ratio exists, and the excessive Ce cannot further improve the performance, probably because the activity of the catalyst is reduced when the doping ratio is larger than the range defined by the invention, and the excessive Ce cannot replace W to form Ce-W bonds to form Ce-Ce bonds. It can be seen by comparing examples 1-3, comparative example 2 and comparative example 1 that, although too large a Ce doping ratio leads to a decrease in performance, the addition of Ce is still beneficial to the enhancement of the nitrate reduction catalytic effect.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.

Claims (10)

1. Ce-Bi for nitrate radical reduction2WO6The electrocatalyst is characterized in that the raw material of the electrocatalyst comprises Na with the molar ratio of 1:1-2:0.05-0.152WO4•2H2O，Bi(NO3)3•5H2O and Ce (NO)3)3•6H2O; the Ce atom is in Bi2WO6The crystal lattice is a substitutional atom, and the doping percentage of Ce is 5-13%.
2. The electrocatalyst according to claim 1, wherein the Ce-Bi is2WO6Has a layered structure.
3. The electrocatalyst according to claim 1 wherein the particle size of the electrocatalyst is from 0.25 to 0.3 nm.
4. A Ce-Bi as claimed in any one of claims 1 to 32WO6Preparation of electrocatalystsThe method is characterized by comprising the following steps:
(1) mixing Na2WO4·2H2Dissolving O in a solvent to prepare a solution A; adding Bi (NO)3)3·5H2Dissolving O in a solvent to prepare a solution B;
(2) adding solution A to solution B, and then adding Ce (NO)3)3·6H2O, Na in the obtained mixed solution after uniform mixing2WO4、Bi(NO3)3With Ce (NO)3)3The molar ratio of (1: 1) - (2: 0.05) - (0.13);
(3) the mixed solution is hydrothermally synthesized for 24-36h under the conditions of 150 ℃ and 180 ℃, and after the reaction is finished, the Ce-Bi is obtained by separation, cleaning and drying2WO6An electrocatalyst.
5. The method according to claim 4, wherein in the step (1), the mass fraction of the solution A is 0.67wt% to 1.3wt%, the mass fraction of the solution B is 2.6wt% to 3.2wt%, and the solvent is water.
6. The method according to claim 4, wherein in the step (2), the uniform mixing is performed by one or more of magnetic stirring, ultrasonic mixing and mechanical stirring.
7. The method according to claim 4, wherein in the step (3), the separation is performed by centrifugation at 3000-4000r/min for 60-120 min.
8. The method according to claim 4, wherein in the step (3), the cleaning is performed by alternately cleaning with deionized water and ethanol.
9. The method according to claim 4, wherein in the step (3), the drying is carried out in vacuum at 60-70 ℃ for 24-30 hours.
10. The Ce-Bi according to any one of claims 1 to 32WO6The electrocatalyst is used for nitrate reduction.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103611527A (en) * 2013-09-12 2014-03-05 陕西科技大学 Visible-light response Ce doped Bi2WO6 microcrystal, preparation method and application thereof
CN112090423A (en) * 2020-09-27 2020-12-18 湖北科技学院 Enhancement of Bi based on electron beam radiation2WO6Method for photocatalytic performance
CN112958135A (en) * 2021-03-02 2021-06-15 陕西科技大学 Cerium-doped and cerium-nitrogen-codoped bismuth tungstate photocatalytic material and preparation method thereof
CN113368858A (en) * 2020-03-08 2021-09-10 天津大学 Cobaltosic oxide-nickel oxide double-layer mesoporous nanotube composite material and preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103611527A (en) * 2013-09-12 2014-03-05 陕西科技大学 Visible-light response Ce doped Bi2WO6 microcrystal, preparation method and application thereof
CN113368858A (en) * 2020-03-08 2021-09-10 天津大学 Cobaltosic oxide-nickel oxide double-layer mesoporous nanotube composite material and preparation method and application thereof
CN112090423A (en) * 2020-09-27 2020-12-18 湖北科技学院 Enhancement of Bi based on electron beam radiation2WO6Method for photocatalytic performance
CN112958135A (en) * 2021-03-02 2021-06-15 陕西科技大学 Cerium-doped and cerium-nitrogen-codoped bismuth tungstate photocatalytic material and preparation method thereof

Non-Patent Citations (2)

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Title
XUETAO YANG等: ""Defect-Induced Ce-Doped Bi2WO6 for Efficient Electrocatalytic N2 Reduction"", 《APPL.MATER.INTERFACES》 *
王春英等: "稀土Ce~(3+)掺杂Bi_2WO_6光催化降解罗丹明B的研究", 《中国环境科学》 *

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