CN115216789A - Titanium mesh in-situ growing iron modified TiO for nitrate electroreduction 2 Nano belt - Google Patents

Titanium mesh in-situ growing iron modified TiO for nitrate electroreduction 2 Nano belt Download PDF

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CN115216789A
CN115216789A CN202210964629.2A CN202210964629A CN115216789A CN 115216789 A CN115216789 A CN 115216789A CN 202210964629 A CN202210964629 A CN 202210964629A CN 115216789 A CN115216789 A CN 115216789A
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titanium mesh
nitrate
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CN115216789B (en
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王焱
陈海军
冯哲圣
张梦梦
黄梦林
王雅芳
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University of Electronic Science and Technology of China
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Abstract

The invention belongs to the technical field of electrocatalysis, and relates to a titanium mesh in-situ grown iron modified TiO for nitrate electroreduction 2 A nanoribbon. The main scheme includes that a three-dimensional conductive substrate titanium mesh is placed into a sodium hydroxide solution for hydrothermal reaction to form Na 2 Ti 2 O 5 ·H 2 O nanobelts; soaking the obtained reaction product in dilute hydrochloric acid, adding Na + Is replaced by H + Form H 2 Ti 2 O 5 ·H 2 O nanobelts, and then cleaning and drying; dissolving a certain amount of ferric trichloride in deionized water, adding concentrated hydrochloric acid to obtain a mixed solution containing ferric salt, and placing a reaction product obtained after drying into the mixed solution to perform hydrothermal reaction to obtain a precursor iron-modified H 2 Ti 2 O 5 ·H 2 O nanobelts; cooling to room temperature, washing with deionized water and vacuum drying the precursor; calcining the dried precursor at high temperature under the protection of inert atmosphere to obtain the in-situ grown iron modified TiO on the titanium mesh 2 A nanoribbon.

Description

Titanium mesh in-situ growing iron modified TiO for nitrate electroreduction 2 Nano belt
Technical Field
The invention belongs to the technical field of electrocatalysis, and relates to a titanium mesh in-situ grown iron modified TiO for nitrate electroreduction 2 A nanoribbon.
Background
Ammonia plays an important role in fertilizer synthesis and is also a potential next-generation energy carrier. Currently, ammonia is produced predominantly by the Haber-Bosch process as N 2 And H 2 Is used as raw material and synthesized under high temperature and high pressure. This process of high energy consumption and large greenhouse gas emissions has prompted researchers to find economical and environmentally friendly alternatives. The electrochemical synthesis of ammonia is of great interest because of its low energy consumption and zero pollution. In recent years, electrocatalytic nitrogen reduction (NRR) is a widely studied strategy for ammonia synthesis. However, the ultra-high dissociation energy, inert N of the stable N ≡ N bond 2 Weak chemisorption on catalysts and nonpolar N 2 The ultra-low water solubility of (a) results in poor NRR efficiency. Nitrate is not only a common nitrogen source in nature but also widely present in industrial waste water and domestic waste water. In addition, the enrichment of nitrate has been in progress for a century, causing serious environmental problems such as eutrophication and global acidification. And N 2 In contrast, since the dissociation energy (204 kJ/mol) of N = O bond is about 4.6 times lower than that of N ≡ N bond (941 kJ/mol), it has high water solubility and higher activity. Thus, compared to NRR, nitrate reduction reaction (NO) 3 - RR) has greater potential as an alternative to the Haber-Bosch process, while addressing environmental concerns.
The reduction of nitrate to ammonia is a complex 9 protons and 8 electrons (NO) 3 - +9H + +8e - →NH 3 +3H 2 O) transfer reactions involving a number of pathways and intermediates (NO) 2 - 、N 2 H 4 、N 2 Etc.), which implies a fuzzy mechanism and several reduction by-products. Hydrogen evolution is also an unavoidable competing reaction in aqueous systems. Thus, NO 3 - RR requires a highly efficient catalyst with high selectivity for NH production 3 。
Disclosure of Invention
The invention aims to provide a titanium mesh in-situ grown iron modified TiO for nitrate electroreduction 2 The nanobelt and the titanium mesh are three-dimensional conductive substrates with excellent conductivity, and the prepared iron-modified TiO 2 The nanobelt has a large specific surface area and more catalytic active sites, can improve the conversion efficiency and the cycle stability of reducing nitrate into ammonia, and has wide application prospect in the field of electrocatalysis; the preparation method has the advantages of simple process, low production cost, safety, reliability and the like.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
in-situ growing iron modified TiO on titanium mesh for nitrate electroreduction 2 A nanoribbon comprising the steps of:
step (1), putting the three-dimensional conductive substrate titanium mesh into a sodium hydroxide solution for hydrothermal reaction to form Na 2 Ti 2 O 5 ·H 2 O nanobelts;
step (2), soaking the reaction product obtained in the step (1) in dilute hydrochloric acid, and adding Na + Is replaced by H + Form H 2 Ti 2 O 5 ·H 2 O nanobelts, and then cleaning and drying;
step (3) dissolving a certain amount of ferric trichloride in deionized water, adding concentrated hydrochloric acid to obtain a mixed solution containing ferric salt, putting a reaction product obtained after drying in step (2) into the mixed solution for hydrothermal reaction to obtain a precursor iron modified H 2 Ti 2 O 5 ·H 2 O nanobelts;
cooling to room temperature, washing with deionized water and vacuum drying the precursor;
step (5) calcining the precursor dried in the step (4) at high temperature under the protection of inert atmosphere to obtain in-situ grown iron modified TiO on the titanium mesh 2 A nanoribbon.
In the step (1), the three-dimensional conductive substrate titanium mesh and NaOH solution are hydrothermally reacted to form Na 2 Ti 2 O 5 ·H 2 The O nanobelts are soaked with dilute hydrochloric acid to remove Na + Is replaced by H + Form H 2 Ti 2 O 5 ·H 2 O nanobelts; h is to be 2 Ti 2 O 5 ·H 2 Putting the O nanobelt into a ferric trichloride mixed solution for hydrothermal reaction to obtain a precursor iron modified H 2 Ti 2 O 5 ·H 2 O-nanobelts, fe modification can generate lattice defects and more catalytically active sites in the precursor, and the final high-temperature calcination is carried out by evaporating H 2 Modification of TiO by conversion of O into Fe 2 A nanoribbon. The catalyst exhibits excellent catalytic efficiency and cycle stability. The preparation method provided by the invention has the advantages of simple process, low production cost, safety, reliability and the like.
Preferably, the concentration of the sodium hydroxide solution in the step (1) is 3-6 mol/L, the temperature of the hydrothermal reaction is 120-200 ℃, and the time is 8-24 h.
Preferably, the concentration of the dilute hydrochloric acid in the step (2) is 0.1-2 mol/L, and the soaking time is 0.5-1.5 h.
Preferably, the dosage proportion of the ferric trichloride, the deionized water and the concentrated hydrochloric acid in the step (3) is 5-15 mg; 20-40 mL; 0.01-0.1 mL, the temperature of the hydrothermal reaction is 60-120 ℃, and the time is 6-18 h.
Preferably, the vacuum drying temperature in the step (4) is 60 ℃, and the drying time is 12h.
Preferably, the inert atmosphere in the step (5) is argon or nitrogen, the high-temperature calcination temperature is 300-600 ℃, and the time is 1-3 h.
Compared with the prior art, the invention has the following beneficial effects:
1. firstly prepares the in-situ growth iron modified TiO on the titanium mesh 2 The nanobelt, a titanium mesh, is a three-dimensional conductive substrate having excellent conductivity and the dispersion and size of Fe particles can be controlled by the content of iron salt.
2. The preparation method has the advantages of simple process, easy operation, low production cost, safety, reliability and the like, and can realize large-scale application.
3. The nanobelts uniformly grow on the three-dimensional conductive titanium net and have large specific surface area, and active sites are increased by Fe modification, so that nitrate can be effectively catalyzed and reduced into ammonia and stable cycle performance can be maintained.
Drawings
FIG. 1 shows iron-modified TiO prepared in example 1 and comparative example 1 2 And TiO 2 2 Electrocatalyst X-ray diffraction (XRD) pattern;
FIG. 2 shows TiO prepared in comparative example 1 2 Scanning Electron Microscope (SEM) images of the electrocatalyst;
FIG. 3 is the iron-modified TiO prepared in example 1 2 Scanning Electron Microscope (SEM) images of the electrocatalyst;
FIG. 4 shows the Fe-modified TiO prepared in example 1 2 An electrocatalyst SEM image and a corresponding energy dispersive X-ray (EDX) elemental distribution plot;
FIG. 5 shows the Fe-modified TiO prepared in example 1 2 A catalytic performance diagram of the electrocatalyst under different voltage conditions;
FIG. 6 shows iron-modified TiO prepared in example 1 2 And (4) an electrocatalyst cycling performance diagram.
Detailed Description
Hereinafter, a detailed description will be given of embodiments of the present invention. While the invention will be described and illustrated in connection with certain specific embodiments thereof, it should be understood that the invention is not limited to those embodiments. Rather, modifications and equivalents of the invention are intended to be included within the scope of the claims.
Furthermore, in the following detailed description, numerous specific details are set forth in order to provide a better understanding of the invention. It will be understood by those skilled in the art that the present invention may be practiced without these specific details.
Titanium mesh in-situ growing iron modified TiO for nitrate electroreduction 2 The nanobelt comprises the following operation steps:
step (1), putting the three-dimensional conductive substrate titanium mesh into a sodium hydroxide solution for hydrothermal reaction to form Na 2 Ti 2 O 5 ·H 2 And the concentration of the sodium hydroxide solution is 3-6 mol/L, the temperature of the hydrothermal reaction is 120-200 ℃, and the time is 8-24 h.
Step (2), soaking the reaction product obtained in the step (1) in dilute hydrochloric acid, and adding Na + Is replaced by H + Form H 2 Ti 2 O 5 ·H 2 And (3) cleaning and drying the O nanobelts, wherein in the step (2), the concentration of the dilute hydrochloric acid is 0.1-2 mol/L, and the soaking time is 0.5-1.5 h.
Step (3), dissolving a certain amount of ferric trichloride in deionized water, adding concentrated hydrochloric acid to obtain a mixed solution containing ferric salt, and placing a reaction product obtained after drying in step (2) into the mixed solution for hydrothermal reaction to obtain a precursor iron-modified H 2 Ti 2 O 5 ·H 2 An O nanobelt, wherein in the step (3), the dosage proportion of ferric trichloride, deionized water and concentrated hydrochloric acid is 5-15 mg; 20-40 mL; 0.01-0.1 mL, the temperature of the hydrothermal reaction is 60-120 ℃, and the time is 6-18 h.
And (4) cooling to room temperature, washing with deionized water, and drying the precursor in vacuum at 60 ℃ for 12h in the step (4).
Step (5) calcining the precursor dried in the step (4) at high temperature under the protection of inert atmosphere to obtain in-situ grown iron modified TiO on the titanium mesh 2 The nanobelt, wherein the inert atmosphere is argon or nitrogen, the high-temperature calcination temperature is 300-600 ℃, and the time is 1-3 h.
Example 1:
titanium in-situ in-net generation for nitrate electroreductionLong iron modified TiO 2 The preparation method of the nanobelt comprises the following steps:
(1) Putting the titanium mesh into 5mol/L sodium hydroxide solution for hydrothermal reaction at 180 ℃ for 24 hours;
(2) Soaking the reaction product obtained in the step (1) in lmol/L diluted hydrochloric acid for 1 hour, and cleaning and drying after soaking;
(3) Dissolving 10mg of ferric trichloride in 30mL of deionized water, adding 0.05mL of concentrated hydrochloric acid, putting a reaction product obtained after drying in the step (2) into the mixed solution, and carrying out hydrothermal reaction at 90 ℃ for 12 hours;
(4) Cooling to room temperature, washing with deionized water, and vacuum drying at 60 deg.C for 12h to obtain precursor;
(5) Calcining the precursor dried in the step (4) at the high temperature of 500 ℃ for 2h in the argon atmosphere to obtain the in-situ grown iron modified TiO on the titanium mesh 2 A nanoribbon.
Example 2:
titanium mesh in-situ growing iron modified TiO for nitrate electroreduction 2 The preparation method of the nanobelt comprises the following steps:
(1) Putting the titanium mesh into 2mol/L sodium hydroxide solution for hydrothermal reaction at 180 ℃ for 24h;
(2) Soaking the reaction product obtained in the step (1) in 1mol/L diluted hydrochloric acid for 0.5h, and cleaning and drying after soaking;
(3) Dissolving 5mg of ferric trichloride in 30mL of deionized water, adding 0.05mL of concentrated hydrochloric acid, putting a reaction product obtained after drying in the step (2) into the mixed solution, and carrying out hydrothermal reaction at 90 ℃ for 6 hours;
(4) Cooling to room temperature, washing with deionized water, and vacuum drying at 60 deg.C for 12h to obtain precursor;
(5) Calcining the precursor dried in the step (4) at the high temperature of 500 ℃ for 2h in the argon atmosphere to obtain the in-situ grown iron modified TiO on the titanium mesh 2 A nanoribbon.
This example has a slight effect on the morphology of the product, mainly in that the Fe particles are dispersed much less than in example 1.
Example 3:
titanium mesh in-situ growing iron for nitrate electroreductionModified TiO 2 The preparation method of the nanobelt comprises the following steps:
(1) Putting the titanium mesh into 5mol/L sodium hydroxide solution for hydrothermal reaction at 180 ℃ for 24 hours;
(2) Soaking the reaction product obtained in the step (1) in 1mol/L diluted hydrochloric acid for 0.5h, and cleaning and drying after soaking;
(3) Dissolving 10mg of ferric trichloride in 30mL of deionized water, adding 0.05mL of concentrated hydrochloric acid, putting a reaction product obtained after drying in the step (2) into the mixed solution, and carrying out hydrothermal reaction at 90 ℃ for 12 hours;
(4) Cooling to room temperature, washing with deionized water, and vacuum drying at 60 deg.C for 12h to obtain precursor;
(5) Calcining the precursor dried in the step (4) at the high temperature of 350 ℃ for 2h in the argon atmosphere to obtain the in-situ grown iron modified TiO on the titanium mesh 2 A nanoribbon.
This example had no effect on the morphology of the product, and had a slight effect on the crystallinity of the product, with the XRD peak of the product prepared at this stage being less intense than that of example 1.
Example 4:
titanium mesh in-situ growing iron modified TiO for nitrate electroreduction 2 The preparation method of the nanobelt comprises the following steps:
(1) Putting the titanium mesh into 5mol/L sodium hydroxide solution for hydrothermal reaction at 180 ℃ for 24 hours;
(2) Soaking the reaction product obtained in the step (1) in 1mol/L diluted HCl solution for 1h, and cleaning and drying after soaking;
(3) Dissolving 5mg of ferric trichloride in 30mL of deionized water, adding 0.05mL of concentrated hydrochloric acid, putting a reaction product obtained after drying in the step (2) into the mixed solution, and carrying out hydrothermal reaction at 90 ℃ for 12 hours;
(4) Cooling to room temperature, washing with deionized water, and vacuum drying at 60 deg.C for 12h to obtain precursor;
(5) Calcining the precursor dried in the step (4) at the high temperature of 350 ℃ for 2h in the nitrogen atmosphere to obtain the in-situ grown iron modified TiO on the titanium mesh 2 A nanoribbon.
This example has a slight effect on morphology, mainly as Fe particles are dispersed much less than example 1, and has a slight effect on the crystallinity of the product, the XRD peak of the product prepared at this step is less intense than that of example 1.
Comparative example 1
TiO grown in situ on titanium mesh 2 The preparation method of the nanobelt comprises the following steps:
(1) Putting the titanium mesh into 5mol/L sodium hydroxide solution for hydrothermal reaction at 180 ℃ for 24 hours;
(2) Soaking the reaction product obtained in the step (1) in 1mol/L diluted hydrochloric acid for 1 hour, and cleaning and drying after soaking;
(3) Calcining the precursor dried in the step (2) at the high temperature of 500 ℃ for 2h in the air atmosphere to obtain TiO grown in situ on the titanium mesh 2 A nanoribbon.
The electrocatalytic test method is as follows:
the test adopts a three-electrode system, a titanium mesh is clamped by an electrode clamp to be used as a working electrode, a mercury/mercury oxide electrode is used as a reference electrode, a platinum sheet is used as a counter electrode, a mixed solution of 0.1mol/L sodium hydroxide and 0.1mol/L sodium nitrate is used as an electrolyte, and an electrochemical workstation is used for carrying out the catalytic performance test.
The ammonia concentration in the experiment was determined quantitatively by means of a UV spectrophotometer. The ammonia yield was calculated by the following equation:
V NH3 ＝c(NH 3 )×V/(t×A)
the faradaic efficiency of ammonia was calculated using the following equation:
FE＝8F×c(NH 3 )×V/(17×Q)×100％
wherein c (NH) 3 ) Is the measured ammonia concentration (. Mu.g/mL), V is the volume of electrolyte (mL), t is the electrolysis time (h), A is the geometric area of the working electrode (cm) 2 ) F is the Faraday constant (96485C/mol) and Q is the total charge passing through the electrode.
Analysis of results
FIG. 1 shows iron-modified TiO prepared in example 1 and comparative example 1 2 And TiO 2 2 The X-ray diffraction (XRD) pattern of the electrocatalyst can be seen, and the main peaks and anatase TiO of the two samples can be seen 2 And (4) matching well.
FIG. 2 shows TiO prepared in comparative example 1 2 Scanning Electron Microscope (SEM) image of the electrocatalyst from which the TiO can be seen 2 The appearance of (a) is a nano-belt array and the surface of the nano-belt is smoother, and the iron modified TiO of comparative example 1 and example 1 2 The shapes of the two are obviously different by comparison, which shows that more catalytic active sites can be provided by iron modification.
FIG. 3 shows the Fe-modified TiO prepared in example 1 2 Scanning Electron Microscope (SEM) image of the electrocatalyst, from which it can be seen that TiO was modified after Fe modification 2 The surface of the nano-belt is rougher and Fe nano-particles are uniformly dispersed in the whole TiO 2 Surface of nanoribbons, this is in contrast to TiO in FIG. 2 2 The shape of the nanobelt is obviously different, which indicates that Fe modification can be performed on TiO 2 The surface of the nanobelt generates more catalytic active sites, which is beneficial to electrocatalytic nitrate reduction activity.
FIG. 4 shows the Fe-modified TiO prepared in example 1 2 SEM image of the electrocatalyst and corresponding energy dispersive X-ray (EDX) elemental distribution map, from which it can be seen that Ti, O and Fe elements are uniformly distributed throughout the iron-modified TiO 2 On the nanobelt.
FIG. 5 shows the iron-modified TiO compound prepared in example 1 2 The result of the catalytic performance test of the electrocatalyst under different voltage conditions shows that the Faraday efficiency is highest under-0.6V voltage and the ammonia yield is highest under-0.8V voltage.
FIG. 6 shows the Fe-modified TiO compound prepared in example 1 2 The electrocatalyst cycling performance diagram shows that when the test voltage is-0.6V, better ammonia yield and Faraday efficiency can be still maintained after 5 cycles, which indicates the excellent electrochemical stability of the catalyst.
The invention mainly prepares the iron modified TiO growing on the titanium mesh in situ 2 The catalyst prepared by the nano-belt catalyst has excellent ammonia yield and stable cycle performance, the excellent electro-catalytic performance not only solves the problem of degradation of nitrate pollutants, but also generates value-added ammonia, and important reference value is provided for the renewable utilization of energy sources in the future.
In summary, the present invention is only a preferred embodiment, and is not limited to the present invention, and any simple modification, change and equivalent changes made to the above embodiment according to the technical essence of the present invention still belong to the protection scope of the technical solution of the present invention.

Claims (6)

1. Titanium mesh in-situ growing iron modified TiO for nitrate electroreduction 2 Nanobelt characterized by comprising the following operative steps:
step (1), putting the three-dimensional conductive substrate titanium mesh into a sodium hydroxide solution for hydrothermal reaction to form Na 2 Ti 2 O 5 ·H 2 O nanobelts;
step (2), soaking the reaction product obtained in the step (1) in dilute hydrochloric acid, and adding Na + Is replaced by H + Form H 2 Ti 2 O 5 ·H 2 O nanobelts, and then cleaning and drying;
step (3), dissolving a certain amount of ferric trichloride in deionized water, adding concentrated hydrochloric acid to obtain a mixed solution containing ferric salt, and placing a reaction product obtained after drying in step (2) into the mixed solution for hydrothermal reaction to obtain a precursor iron-modified H 2 Ti 2 O 5 ·H 2 O nanobelts;
cooling to room temperature, washing with deionized water and vacuum drying the precursor;
step (5), calcining the precursor dried in the step (4) at high temperature under the protection of inert atmosphere to obtain the in-situ grown iron modified TiO on the titanium mesh 2 A nanoribbon.
2. The titanium mesh-on-site growing iron-modified TiO for nitrate electroreduction according to claim 1 2 The nanobelt is characterized in that in the step (1), the concentration of the sodium hydroxide solution is 3-6 mol/L, the temperature of the hydrothermal reaction is 120-200 ℃, and the time is 8-24 h.
3. The titanium mesh-on-site growing iron-modified TiO for nitrate electroreduction according to claim 1 2 Nanobelt characterized by the step (2)) Wherein the concentration of the dilute hydrochloric acid is 0.1-2 mol/L, and the soaking time is 0.5-1.5 h.
4. The titanium mesh-on-site growing iron-modified TiO for nitrate electroreduction according to claim 1 2 The nanobelt is characterized in that in the step (3), the dosage proportion of ferric trichloride, deionized water and concentrated hydrochloric acid is 5-15 mg; 20-40 mL; 0.01-0.1 mL, the temperature of the hydrothermal reaction is 60-120 ℃, and the time is 6-18 h.
5. The titanium mesh-on-site growing iron-modified TiO for nitrate electroreduction according to claim 1 2 The nanobelt is characterized in that in the step (4), the vacuum drying temperature is 60 ℃ and the drying time is 12 hours.
6. The in-situ growth of iron-modified TiO on titanium mesh for electroreduction of nitrate according to claim 1 2 The nanobelt is characterized in that in the step (5), the inert atmosphere is argon or nitrogen, the high-temperature calcination temperature is 300-600 ℃, and the time is 1-3 hours.
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