CN102784659A - Visible light response type photocatalytic material of tantalum nitride modified by cobalt and preparation method thereof - Google Patents

Visible light response type photocatalytic material of tantalum nitride modified by cobalt and preparation method thereof Download PDF

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Publication number
CN102784659A
CN102784659A CN201210310172XA CN201210310172A CN102784659A CN 102784659 A CN102784659 A CN 102784659A CN 201210310172X A CN201210310172X A CN 201210310172XA CN 201210310172 A CN201210310172 A CN 201210310172A CN 102784659 A CN102784659 A CN 102784659A
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preparation
precursor solution
tantalum
cobalt
paper tinsel
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丛燕青
李哲
张轶
王齐
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Zhejiang Gongshang University
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Zhejiang Gongshang University
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Abstract

The invention discloses a visible light response type photocatalytic material of tantalum nitride modified by cobalt and a preparation method thereof. The preparation method includes cleanly washing a pure tantalum foil, using the pure tantalum foil as a substrate, dropping a precursor solution A containing Ta5+ onto the substrate, air drying at the room temperature to obtain a tantalum foil loaded with Ta5+, dropping a precursor solution B containing metal cobalt ions onto the tantalum foil loaded with Ta5+, air drying at the room temperature to obtain a tantalum foil loaded with Ta5+ and the metal cobalt ions, and subjecting the tantalum foil loaded with Ta5+ and the metal cobalt ions to a constant temperature calcination in a flowing anhydrous ammonia gas atmosphere to obtain the photocatalytic material. By means of the method, the prepared photocatalytic material has the advantages that the stability of Ta3N5 is effectively improved, the self oxidation of the Ta3N5 is inhibited, the electron transfer can be facilitated, the photoproduction electron-hole pair recombination is inhibited, and the photolysis efficiency is improved.

Description

A kind of cobalt is modified visible light responsive photocatalytic material of tantalum nitride and preparation method thereof
Technical field
The present invention relates to the catalysis material technical field, be specifically related to a kind of cobalt and modify visible light responsive photocatalytic material of tantalum nitride and preparation method thereof.
Background technology
Current society, face of mankind energy shortage and environmental pollution two big severe problems.Solar energy is a kind of typical natural energy resources, utilizes the solar energy photocatalytic hydrogen production by water decomposition, has very important scientific value and great realistic significance at aspects such as alleviating energy crisis, minimizing environmental pollutions.At present, the key of solar energy photocatalytic decomposition aquatic products hydrogen is to develop and develop efficient, stable novel visible catalysis material.
Tantalum nitride (Ta 3N 5) as a kind of high visible light response type catalysis material, possessed the essential condition of photodissociation aquatic products hydrogen: its energy gap is 2.1eV, can absorbing wavelength until the visible light of 600nm; During pH=0, be reference with the standard hydrogen electrode, its conduction band potential and valence band electromotive force are respectively-0.4V and 1.7V, and the sunshine phototranstormation efficiency reaches as high as 15.9% in theory.Up to now, study the Ta that obtains 3N 5Form include Ta 3N 5Powder, Ta 3N 5Film, Ta 3N 5Nano particle and Ta 3N 5Nano-tube array etc.
Because tantalum nitride (Ta 3N 5) excellent photocatalysis performance, emerged a large amount of in recent years about tantalum nitride (Ta 3N 5) research, for example, application number is that 200410023088.5 Chinese invention patent discloses a kind of tantalum nitride powder and preparation method thereof; The tantalum powder is packed in the vacuum reaction container; Be evacuated to the high pure nitrogen that charges into purity>=99.999% behind pressure＜0.1Pa, the maintenance nitrogen pressure is 0.02～0.16MPa, is warmed up to 700 ℃～1200 ℃ and be incubated 5～12 hours simultaneously; Behind the cool to room temperature that product is broken then, sieve; Remove impurity through pickling, wash to the pH value of solution value again and dry for neutral back, nitrogen content is 6.8～7.39% in the prepared high-nitrogen tantalum nitride powder.
And for example; Application number is that 200510031585.4 Chinese invention patent discloses a kind of ultra-fine high-nitrogen tantalum nitride powder and preparation method thereof, and the nitrogen content of tantalum nitride powder is 6.8～7.40%, content of impurities＜0.0090%; Surplus is a tantalum, Fisher particle size Fsss＜1um.Its preparation method 1 is conventional vacuum reactor that the hypoxemia tantalum powder of oxygen content≤0.4% is packed into; Be warmed up to 400～750 ℃ after being evacuated to pressure≤0.1Pa; Charge into nitrogen behind the constant temperature and be warmed up to 700～1200 ℃ again, and be constant temperature under 0.02～0.16Mpa at nitrogen pressure; Its preparation method 2 for the hyperoxia tantalum powder of oxygen content＞0.4% with mix the conventional vacuum reactor of packing into for the magnesium powder of tantalum grain weight amount 2～10%; Be warmed up to 400～550 ℃ after being evacuated to pressure≤0.1Pa; Charge into high-purity argon gas behind the constant temperature and be warmed up to 700～800 ℃, extract argon gas behind the constant temperature and charge into nitrogen, be warmed up to 950～1200 ℃ again; And be constant temperature under 0.02～0.16Mpa at nitrogen pressure; Two kinds of preparation methods' product is broken behind cool to room temperature, sieve pickling impurity removal, washing oven dry.
Yet, existing Ta 3N 5When utilizing sunshine photodissociation water, there is the autoxidation problem, part Ta 3N 5Can be oxidized under the effect of photohole, activity of such catalysts and stability are reduced.Therefore,, improve semi-conductive phototranstormation efficiency of tantalum nitride and stability and be still a challenge, be badly in need of developing the new more highly active stable visible light catalyst that has though existing many research is devoted to optimize the structure and the performance of tantalum nitride.
Summary of the invention
The invention provides a kind of cobalt and modify visible light responsive photocatalytic material of tantalum nitride and preparation method thereof, effectively improve Ta 3N 5Stability, suppress himself oxidation, and can promote electronics to shift, suppress the light induced electron hole to compound, improve photolysis efficiency.
A kind of cobalt is modified the visible light responsive photocatalytic preparation methods of tantalum nitride, comprising:
Pure tantalum paper tinsel is cleaned, as substrate;
To contain Ta 5+Precursor solution A drip to said substrate, the room temperature air dried, load Ta 5+The tantalum paper tinsel;
Precursor solution B with the containing metal cobalt ions drips to said load Ta again 5+The tantalum paper tinsel on, the room temperature air dried, load Ta 5+Tantalum paper tinsel with the metallic cobalt ion;
With load Ta 5+Tantalum paper tinsel calcining at constant temperature in the anhydrous ammonia gas atmosphere that flows with the metallic cobalt ion gets said catalysis material.
Adopt cobalt to modify tantalum nitride, can effectively improve Ta 3N 5Stability, suppress himself oxidation, and can promote electronics to shift, suppress the light induced electron hole to compound, improve photodissociation water speed.Cobalt nitride can also change into the cobalt oxide with electro catalytic activity under the photohole oxidation, participate in the oxidation Decomposition of water, significantly strengthens the photoelectrocatalysis performance of catalyst.
As preferably, said precursor solution A is dripped several times, at room temperature air-dry after each the dropping, carry out dropping next time again; Said precursor solution B is dripped several times, at room temperature air-dry after each the dropping, carry out dropping next time again.
Repeatedly drip and can guarantee that precursor solution more is evenly distributed in tantalum paper tinsel surface, the catalyst thickness that assurance makes is homogeneous more, thereby helps improving catalysis material to the absorption of visible light utilization, shows more excellent photoelectric catalytically active.
As preferably, the Ta among the said precursor solution A 5+With the mol ratio of metallic cobalt ion among the precursor solution B be 5～9.5: 0.5～5.More preferably, the Ta among the said precursor solution A 5+With the mol ratio of metallic cobalt ion among the precursor solution B be 9.5/0.5,9/1,8/2,7/3,6/4 and 5/5.
Ta 5+Cause the photoelectrocatalysis performance of catalyst different with the different meetings of metallic cobalt ion mol ratio, the ratio of cobalt is low excessively, can't effectively suppress Ta 3N 5The autoxidation of catalyst, and the ratio of cobalt is too high, then can be to Ta 3N 5The photocatalytic activity of catalyst produces inhibitory action.Suitable Ta/Co ratio can not only improve the catalyst self stability; And can suppress the light induced electron hole to compound, and improving photolysis efficiency, preferred Ta/Co realizes than representative and easy operating among the present invention; Help carrying out the investigation of catalyst catalytic performance, obtain optimal T a/Co ratio.
As preferably, said precursor solution A is TaCl 5Methyl alcohol or ethanolic solution, molarity is 10～30mM.
Also can adopt other tantalum salt,, compare other tantalum salt, TaCl like nitric acid tantalum, sulfuric acid tantalum 5Dissolubility best, so preferred TaCl among the present invention 5
As preferably, among the said precursor solution B, solute is Co (NO 3) 2, CoSO 4, CoCl 2, cobalt acetate or cobalt oxalate, solvent is methyl alcohol or ethanol, molarity is 10～30mM.
As preferably, the flowing velocity of said ammonia is 40～200mL/min, and more preferably 80～150mL/min most preferably is 80～100mL/min.
As preferably, the temperature of said calcining at constant temperature is 500～1000 ℃, more preferably 700～1000 ℃, most preferably is 800～850 ℃.
As preferably, the time of said calcining at constant temperature is 1～10h, and more preferably 2～8h most preferably is 2～4h.
The flowing velocity of ammonia can not be low excessively, and low excessively ammonia flow velocity causes the Ta that obtains 3N 5Have small amount of oxygen in the catalyst, the existence of small amount of oxygen element can reduce the photocatalysis performance of catalyst, and same, calcination time can not be too short, and too short calcination time also can make the Ta that makes 3N 5Catalyst is impure.Under this preferred ammonia flowing velocity, calcining heat and calcination time condition, help obtaining purer catalyst, and obtain desirable crystalline phase and degree of crystallinity.
The present invention also provides a kind of visible light responsive photocatalytic material for preparing like said preparation method, and the substrate of this catalysis material is pure tantalum paper tinsel, and active component is attached to suprabasil Ta yCo 1-yN xFilm, wherein y is 0.5～0.95, x is 0.9～1.6.
Beneficial effect of the present invention:
Adopt the cobalt modification tantalum nitride catalysis material of the present invention's preparation to have good visible light photoelectrochemical behaviour:
1. under radiation of visible light, with the Ta of the inventive method preparation yCo 1-yN xThe photoelectric current of catalysis material is with respect to Ta 3N 512 times have been improved.
2. the Ta for preparing with the present invention yCo 1-yN xThe stability of catalysis material obviously is superior to Ta 3N 5, explain that the modification of cobalt can effectively suppress Ta 3N 5Autoxidation.
The present invention adopts a stain legal system to be equipped with cobalt and modifies the tantalum nitride catalysis material, and technology is simple, with low cost, the Ta that makes yCo 1-yN xPhotochemical catalyst shows high visible light response property and photoelectric catalytically active under solar light irradiation, can be used for fields such as photodissociation aquatic products hydrogen, photoelectric catalysis degrading environmental contaminants, photoelectrocatalysis is synthetic.
Description of drawings
Fig. 1 a is Ta 3N 5And Ta 0.9Co 0.1N 1.5The linear scan volt-ampere curve of film under the ultraviolet-visible irradiation.
Fig. 1 b is Ta 3N 5And Ta 0.9Co 0.1N 1.5The linear scan volt-ampere curve of film under radiation of visible light.
Fig. 2 is Ta 0.6Co 0.4N 1.1The GIXRD figure of film.
Fig. 3 a and Fig. 3 b are Ta 0.6Co 0.4N 1.1The SEM figure of film.
Fig. 4 a is same Ta 3N 5The linear scan volt-ampere curve of 3 scannings of repetition under the ultraviolet-visible irradiation (stability relatively).
The same Ta of Fig. 4 b 0.8Co 0.2N 1.4The linear scan volt-ampere curve of film 3 scannings of repetition under the ultraviolet-visible irradiation (stability relatively).
Fig. 5 a～Fig. 5 d is Ta 0.6Co 0.4N 1.1The XPS spectrum figure of film behind the ultraviolet-visible pre-irradiation.
Fig. 6 a is the Ta of different Ta/Co ratios yCo 1-yN xThe linear scan volt-ampere curve of film under the ultraviolet-visible irradiation.
Fig. 6 b is the Ta of different Ta/Co ratios yCo 1-yN xThe linear scan volt-ampere curve of film under radiation of visible light.
Fig. 7 is Ta 3N 5And Ta yCo 1-yN xThe electricity conversion comparison diagram of film.
Fig. 8 is Ta yCo 1-yN xFilm separation of charge under the ultraviolet-visible irradiation shifts sketch map.
The specific embodiment
The raw materials used commercially available prod that is in following examples.
Embodiment 1
Pure tantalum paper tinsel (2cm*2cm) is used acetone, absolute ethyl alcohol and deionized water ultrasonic cleaning successively; With TaCl 5Be dissolved in the methyl alcohol, being made into concentration is the precursor solution A of 10mM; With Co (NO 3) 2Be dissolved in the methyl alcohol, being made into concentration is the precursor solution B of 10mM.Draw 30 μ L precursor solution A and drip to the tantalum paper tinsel, at room temperature air-dry, repeat 9 times after, draw 30 μ L precursor solution B and drip to the tantalum paper tinsel, at room temperature air-dry.The sample that drips after the stain is put into tube furnace, and under 850 ℃, flow velocity is that cycle annealing is handled 2h in the anhydrous ammonia gas atmosphere of 80mL/min, obtains Ta 0.9Co 0.1N 1.5Film.
Fig. 1 a is Ta 3N 5And Ta 0.9Co 0.1N 1.5The linear scan volt-ampere curve of film under the ultraviolet-visible irradiation; Fig. 1 b is Ta 3N 5And Ta 0.9Co 0.1N 1.5The linear scan volt-ampere curve of film under radiation of visible light can be known by Fig. 1 a and 1b, with respect to Ta 3N 5, Ta 0.9Co 0.1N 1.5The photoelectric current of film has improved 5 times and 12 times respectively under ultraviolet-visible and radiation of visible light, the modification of visible cobalt has improved Ta greatly 3N 5Photoelectric catalytically active.
Embodiment 2
Pure tantalum paper tinsel (2cm*2cm) is used acetone, absolute ethyl alcohol and deionized water ultrasonic cleaning successively; With TaCl 5Be dissolved in the methyl alcohol, being made into concentration is the precursor solution A of 10mM; With Co (NO 3) 2Be dissolved in the methyl alcohol, being made into concentration is the precursor solution B of 10mM.Draw 30 μ L precursor solution A and drip to the tantalum paper tinsel, at room temperature air-dry, repeat 6 times after, draw 30 μ L precursor solution B and drip to the tantalum paper tinsel, repeat 4 times after, at room temperature air-dry.The sample that drips after the stain is put into tube furnace, and under 850 ℃, flow velocity is that cycle annealing is handled 2h in the anhydrous ammonia gas atmosphere of 100mL/min, obtains Ta 0.6Co 0.4N 1.1Film.
Fig. 2 is Ta 0.6Co 0.4N 1.1The GIXRD figure of film can be known that by Fig. 2 the main component that cobalt is modified the tantalum nitride catalysis material is Ta 3N 5And Co 5.47N, owing to adopt the tantalum paper tinsel as substrate, ammonia also can react with the substrate of tantalum paper tinsel after infiltrating and dripping the stain sample, so also contains a small amount of TaN in the sample 0.43Middle phase.Fig. 3 a and Fig. 3 b are Ta 0.6Co 0.4N 1.1The SEM figure of film can see that sample is more even, is vesicular texture.
Embodiment 3
Pure tantalum paper tinsel (2cm*2cm) is used acetone, absolute ethyl alcohol and deionized water ultrasonic cleaning successively; With TaCl 5Be dissolved in the methyl alcohol, being made into concentration is the precursor solution A of 10mM; With Co (NO 3) 2Be dissolved in the methyl alcohol, being made into concentration is the precursor solution B of 10mM.Draw 30 μ L precursor solution A and drip to the tantalum paper tinsel, at room temperature air-dry, repeat 8 times after, draw 30 μ L precursor solution B and drip to the tantalum paper tinsel, repeat 2 times after, at room temperature air-dry.The sample that drips after the stain is put into tube furnace, and under 800 ℃, flow velocity is that cycle annealing is handled 4h in the anhydrous ammonia gas atmosphere of 100mL/min, obtains Ta 0.8Co 0.2N 1.4Film.
Fig. 4 a is same Ta 3N 5The linear scan volt-ampere curve of 3 scannings of repetition under the ultraviolet-visible irradiation; The same Ta of Fig. 4 b 0.8Co 0.2N 1.4The linear scan volt-ampere curve of film 3 scannings of repetition under the ultraviolet-visible irradiation.Along with the increase of scanning times, Ta 3N 5The photoelectric current of film reduces gradually, and Ta 0.8Co 0.2N 1.4The photoelectric current of film is almost constant, and the interpolation of visible Co has improved Ta 3N 5The stability of film.Fig. 5 a～Fig. 5 d is Ta 0.6Co 0.4N 1.1XPS spectrum figure changed not quite before and after XPS (X-ray photoelectron spectroscopic analysis) spectrogram of film behind the ultraviolet-visible pre-irradiation, illumination were penetrated, and proved that also the stability of cobalt modification tantalum nitride membrane is better.
Fig. 6 a is the Ta of different Ta/Co ratios yCo 1-yN xThe linear scan volt-ampere curve of film under the ultraviolet-visible irradiation; Fig. 6 b is the Ta of different Ta/Co ratios yCo 1-yN xThe linear scan volt-ampere curve of film under radiation of visible light.When illumination was opened, Ta/Co was than more little, and the peak point current that moment occurs is big more; But the amplitude of current attenuation is also big more; The doping that Co is described is very crucial, and The addition of C o helps improving electricity conversion, but excessive Co also possibly become right complex centre, light induced electron hole.
Fig. 7 is Ta 3N 5And Ta yCo 1-yN xThe electricity conversion comparison diagram of film can know that by figure the modification of Co has significantly improved Ta 3N 5Electricity conversion.
Fig. 8 is Ta yCo 1-yN xFilm separation of charge under the ultraviolet-visible irradiation shifts sketch map.Be modified at Ta 3N 5On metallic cobalt in course of reaction, exist with nitride and two kinds of forms of oxide respectively, play eelctro-catalyst, anti-autoxidation inhibitor and electron hole pair composite inhibitor triple role.

Claims (10)

1. the visible light responsive photocatalytic preparation methods that cobalt is modified tantalum nitride is characterized in that, comprising:
Pure tantalum paper tinsel is cleaned, as substrate;
To contain Ta 5+Precursor solution A drip to said substrate, the room temperature air dried, load Ta 5+The tantalum paper tinsel;
Precursor solution B with the containing metal cobalt ions drips to said load Ta again 5+The tantalum paper tinsel on, the room temperature air dried, load Ta 5+Tantalum paper tinsel with the metallic cobalt ion;
With load Ta 5+Tantalum paper tinsel calcining at constant temperature in the anhydrous ammonia gas atmosphere that flows with the metallic cobalt ion gets said catalysis material.
2. preparation method according to claim 1 is characterized in that, said precursor solution A is dripped several times, and is at room temperature air-dry after each the dropping, carries out dropping next time again.
3. preparation method according to claim 1 is characterized in that, said precursor solution B is dripped several times, and is at room temperature air-dry after each the dropping, carries out dropping next time again.
4. preparation method according to claim 1 is characterized in that, the Ta among the said precursor solution A 5+With the mol ratio of metallic cobalt ion among the precursor solution B be 5～9.5: 0.5～5.
5. preparation method according to claim 1 is characterized in that, said precursor solution A is TaCl 5Methyl alcohol or ethanolic solution, molarity is 10～30mM.
6. preparation method according to claim 1 is characterized in that, among the said precursor solution B, solute is Co (NO 3) 2, CoSO 4, CoCl 2, cobalt acetate or cobalt oxalate, solvent is methyl alcohol or ethanol, molarity is 10～30mM.
7. preparation method according to claim 1 is characterized in that, the flowing velocity of said ammonia is 40～200mL/min.
8. preparation method according to claim 1 is characterized in that, the temperature of said calcining at constant temperature is 500～1000 ℃.
9. preparation method according to claim 1 is characterized in that, the time of said calcining at constant temperature is 1～10h.
10. visible light responsive photocatalytic material for preparing like the said preparation method of the arbitrary claim of claim 1～9.
CN201210310172XA 2012-08-29 2012-08-29 Visible light response type photocatalytic material of tantalum nitride modified by cobalt and preparation method thereof Pending CN102784659A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108525692A (en) * 2018-02-12 2018-09-14 山东大学 A kind of preparation method of the photocatalytic system with high photocatalysis efficiency and stability
CN108640092A (en) * 2018-04-18 2018-10-12 南京大学 The method that a kind of one step nitriding of oxygenatedchemicals auxiliary prepares metal nitride film
CN111871446A (en) * 2020-08-14 2020-11-03 大连工业大学 Preparation method of biomass-based carbon @ tantalum nitride composite photocatalytic material and application of composite photocatalytic material in photocatalytic degradation of methylene blue

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CN1919458A (en) * 2006-08-29 2007-02-28 中国科学院上海硅酸盐研究所 Method for preparing tantalum nitride oxide assembly mesoporous molecular sieve

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CN1919458A (en) * 2006-08-29 2007-02-28 中国科学院上海硅酸盐研究所 Method for preparing tantalum nitride oxide assembly mesoporous molecular sieve

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YANQING CONG等: "Tantalum Cobalt Nitride Photocatalysts for Water Oxidation under Visible Light", 《CHEMISTRY OF MATERIALS》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108525692A (en) * 2018-02-12 2018-09-14 山东大学 A kind of preparation method of the photocatalytic system with high photocatalysis efficiency and stability
CN108640092A (en) * 2018-04-18 2018-10-12 南京大学 The method that a kind of one step nitriding of oxygenatedchemicals auxiliary prepares metal nitride film
CN111871446A (en) * 2020-08-14 2020-11-03 大连工业大学 Preparation method of biomass-based carbon @ tantalum nitride composite photocatalytic material and application of composite photocatalytic material in photocatalytic degradation of methylene blue

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Application publication date: 20121121