CN109865524A - A kind of carbon support transition metal phosphide produces hydrogen elctro-catalyst and preparation method thereof - Google Patents
A kind of carbon support transition metal phosphide produces hydrogen elctro-catalyst and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to carbon support transition metal phosphides to produce hydrogen elctro-catalyst and preparation method thereof.Metal front in carbon is supported using the preparation of transition metal-catalyzed carbon material growth in situ, then phosphating metal forerunner obtains carbon support transition metal phosphide and produces hydrogen elctro-catalyst.In electrochemistry hydrogen production reaction, carbon support iron phosphide (FeP/Fe@NC) being prepared is 10 and 100mA/cm in current density2When, it is only necessary to overpotential 49 and 130mV；The catalyst has excellent stability simultaneously, in 10mA/cm2Current density under stablize 90 hours or more non-inactivations.The preparation method is simple and easy to do, and required raw material is cheap and easy to get, can guarantee combination strong between catalyst-carbon carrier and excellent catalyst dispersity, so that catalyst has good electric conductivity and electron transport property.
Description
Technical field
The present invention relates to a kind of catalyst and preparation method thereof, specially in electrocatalytic decomposition water and hydrogen sulfide hydrogen production process
A kind of carbon support transition metal phosphide produce hydrogen elctro-catalyst and preparation method thereof.
Background technique
A kind of clean energy resource of the Hydrogen Energy as high-energy density can be made by electrocatalytic decomposition water and hydrogen sulfide.Its
In, the best elctro-catalyst of performance for hydrogen production reaction is the noble metals such as Pt, however its low reserves and high price limit it
Large-scale use, therefore much researchs are dedicated to developing cheap base metal and produce hydrogen elctro-catalyst.Metal phosphide by
In cheap and high activity feature, extensive research and concern are received, they are formed to carbon support metal in conjunction with carbon material
Phosphide can further promote its catalytic performance.The method for being used to prepare carbon support metallic catalyst developed at present is main
It is the group by way of the ex situs such as dipping, hydro-thermal, physical mixed by phosphide or other catalyst and their presoma
Dress is on the carbon material.As reported in the literature FeP (ACS Appl.Mater.Interfaces 2014,6,20579-20584,
Chem.Commun.2014,50,11554-11557.),MoWP(Energy Environ.Sci.2016,9,1468-1475.),
CoP (Angew.Chem.Int.Ed.2014,53,6710-6714.), and MoS2(J.Am.Chem.Soc.2011,133,
7296-7299.).Carbon made from these methods supports the combination between its carbon material of metal phosphide and catalyst weaker, charge
Transmission and stability are relatively poor, and furthermore these preparation process are more complex, and higher cost, industrial Applicability is lower, prepare potentiality
Also small.Based on this, the present invention by reasonably design and modulation, propose using cheap transition metal iron, cobalt, nickel, copper, molybdenum,
The source metal of catalyst and synthesis phosphide that tungsten etc. is grown as carbon material, by being simply heat-treated the side with direct phosphating
Formula is prepared the support transition metal phosphide of the carbon with strong combination and produces hydrogen elctro-catalyst, is catalyzed in acid system
Excellent catalytic activity and stability are shown when producing hydrogen reaction.
Summary of the invention
The object of the present invention is to provide a kind of carbon support transition metal phosphides to produce hydrogen elctro-catalyst and preparation method.
To achieve the above object, the technical solution adopted by the present invention are as follows:
It is using the carbon material containing transition metal as conductive base that a kind of carbon support transition metal phosphide, which produces hydrogen elctro-catalyst,
Bottom, the transition metal phosphide obtained after transition metal some or all of in direct phosphating carbon material are catalytic active species
Carbon supports transition metal phosphide to produce hydrogen elctro-catalyst；
Transition metal is one or more of Fe, Co, Ni, Cu, Mo, W.
Carbon support transition metal phosphide produce hydrogen elctro-catalyst the preparation method is as follows:
(1) transition metal-type compound, carbon compound are weighed, mixed-powder is mixed to get, mixed-powder is put into pipe
It in formula furnace, is roasted in argon atmosphere, Temperature fall obtains carbon support metal precursor；
(2) after supporting metal precursor and phosphorus source to mix in obtained carbon, the phosphorating treatment in argon atmosphere drops naturally
Drying is washed after warming to room temperature, and is obtained carbon support transition metal phosphide and is produced hydrogen elctro-catalyst.
Preferably, the transition metal-type compound closes iron (II) acid ferrous iron using ferrocene, ferric citrate, six cyanogen
Phthalocyanine-like compound, the acetylacetone,2,4-pentanedione of the respective metals such as ammonium, ammonium heptamolybdate, ammonium phosphomolybdate, Yi Jitie, cobalt, nickel, copper, molybdenum, tungsten
One or more of salt, citrate, acetate, chlorate, nitrate, sulfate, phosphate, preferably lemon
Hydrochlorate and acetate.
Preferably, the carbon compound using cdicynanmide, melamine, urea, glucose, ethylenediamine tetra-acetic acid,
One or more of polystyrene, thiophene, imidazoles, hexachloro-benzene, toluene, benzene, biomass material, preferably dicyan ammonium and three
Poly cyanamid.
Preferably, transition metal-type compound and carbon compound are dissolved into mixing, water-bath with the mass ratio of 1:1~1:20
Mixed-powder, preferably 1:4-1:10 are obtained after being evaporated.
Preferably, mixed-powder is warming up to 400 DEG C~1200 with the heating rate of 2~15 DEG C/min in argon atmosphere
DEG C, and 1h~10h is kept, it is naturally cooling to room temperature.
Preferably, preparing phosphorus source used in metal phosphide is sodium hypophosphite, red phosphorus, organic phosphine, sodium dihydrogen phosphate, phosphorus
Acid dihydride ammonium, preferably red phosphorus and sodium hypophosphite
Preferably, carbon support metal precursor and phosphorus source are uniformly mixed with metal with the atomic ratio of phosphorus for 1:1~1:10, excellent
Select 1:3-1:7.
Preferably, support the mixed-powder of metal precursor and phosphorus source in argon gas with the heating of 2~15 DEG C/min in carbon
Rate is warming up to 300 DEG C~800 DEG C, and keeps 1h~10h, is naturally cooling to room temperature.
Compared with prior art, the present invention has the advantage that
Carbon support transition metal phosphide of the present invention produces hydrogen elctro-catalyst, wherein the carbon material containing transition metal
The conductive substrates and dispersible carrier of catalyst are served not only as, also the presoma as synthesis metal phosphide, is provided needed for phosphatization
Source metal, the catalyst particle size being prepared is uniform, and dispersion degree is high, large specific surface area, good conductivity, has excellent charge
Transmission characteristic and stability.Wherein carbon support iron phosphide (FeP/Fe@NC) is in the H of 0.5M2SO4When catalysis produces hydrogen reaction in solution,
It is 10 and 100mA/cm in current density2When, overpotential is down to 49 and 130mV；The catalyst has excellent stability simultaneously,
In 10mA/cm2Current density under stablize 90 hours or more non-inactivations.
Catalyst of the present invention has excellent catalytic properties when being used for electro-catalysis hydrogen manufacturing, and preparation method
Simple and easy to do, required raw material is cheap and easy to get, has certain industrial Applicability.
In preparation method of the present invention, the height that is prepared in a manner of the growth of transition metal-catalyzed carbon compound
Electric conductivity, high surface area, high stability carbon material be the excellent conductive substrates of transition metal phosphide catalyst and dispersion carry
Body.
In addition, the carbon prepared by the present invention supports in metal precursor, strong gold is formd between metal and carbon material
Category-carbon material combination.Further, it is mutual to form strong interface later between metal phosphide and carbon material for phosphatization
Effect, this help to obtain the elctro-catalyst of good electric conductivity, dispersibility and excellent electron transport property.
Preparation method of the present invention can effectively solve the phosphatization present in high temperature phosphorization and catalytic reaction process
The problems such as object is reunited, sintering, while the strong interface interaction formed between transition metal phosphide and carbon material can be effective
The physical and chemical stability that ground improves elctro-catalyst obtains excellent catalytic performance to improve its electrochemical stability.
Detailed description of the invention
Fig. 1 (a), 1 (b), 1 (c), 1 (d) are the XRD diagram that sample is made in embodiment 1-4.
Fig. 2 (a), 2 (b), 2 (c), 2 (d) are the TEM figure that sample is made in embodiment 1-4.
Fig. 3 (a) supports iron phosphide (FeP/Fe@NC-650-8) in 0.5MH for carbon obtained in embodiment 12SO4In solution
Linear sweep voltammetry (LSV) curve, Fig. 3 (b) is that carbon obtained supports iron phosphide catalyst Fe P/Fe@NC- in embodiment 1
The stability test figure of 650-8.
Fig. 4 (a) supports phosphatization cobalt (CoP/Co@NC-680-8) in 0.5M H for carbon obtained in embodiment 32SO4In solution
Linear sweep voltammetry (LSV) curve, Fig. 4 (b) is that carbon obtained supports phosphatization Co catalysts CoP/Co@NC- in embodiment 3
The stability test figure of 680-8.
Fig. 5 (a) is carbon support nickel phosphide (Ni obtained in embodiment 42P/Ni@NC-680-8) in 0.5M H2SO4Solution
In linear sweep voltammetry (LSV) curve, Fig. 5 (b) is that carbon obtained supports catalyst of phosphatizing nickel Ni in embodiment 42P/Ni@
The stability test figure of NC-680-8.
Specific embodiment
In order to further illustrate the present invention, following embodiment is enumerated, but not thereby limiting the invention.
Embodiment 1
This example demonstrates that the preparation of carbon support iron phosphide (FeP/Fe@NC) catalyst and the control of heat treatment temperature (T)
Example:
Use ferric citrate and cdicynanmide for raw material, according to cdicynanmide: ferric citrate=8:1 mass ratio feeds intake,
In deionized water by 8.0g cdicynanmide and the dispersion of 1.0g ferric citrate, stirring is evaporated in a water bath, and grinding obtains mixed powder
End.Next mixed-powder is put into quartz ampoule, is separately heated in argon atmosphere with the heating rate of 10 DEG C/min
600,625,650,665,680 and 700 DEG C, 2h is reacted, room temperature is naturally cooling to, obtains a series of at a temperature of different heat treatment
Iron content carbon matrix precursor (Fe/Fe@NC-T-8)；
Presoma obtained and sodium hypophosphite are mixed with the ratio of Fe:P=1:5 (atomic ratio), grinding uniformly, is put into
In tube furnace in argon atmosphere phosphorating treatment, be warming up to 500 DEG C with the heating rate of 5 DEG C/min, and keep 2h, Temperature fall
To room temperature, carbon support iron phosphide (FeP/Fe@NC-T-8) is obtained after washing is dry and produces hydrogen elctro-catalyst.
The XRD diagram for producing hydrogen elctro-catalyst is shown in Fig. 1 (a).
The activity and stability test result of FeP/Fe NC-650-8 obtained in it is shown in Fig. 3, and test uses three electrode bodies
System: the glass-carbon electrode for having modified catalyst is working electrode；Pt piece is to electrode；Saturated calomel electrode is reference electrode.Test
What is used sweeps speed as 50mV/s.
It is analyzed in conjunction with XRD, XPS and HRTEM, it was demonstrated that catalyst obtained is by metal Fe, metal phosphide FeP and nitrogenous carbon
Material NC composition.
Embodiment 2
This example demonstrates that the control of the reactant ratio (X) of carbon support iron phosphide (FeP/Fe@NC) catalyst preparation is real
Example:
Use ferric citrate and cdicynanmide for raw material, the ingredient proportion of the two is adjusted to cdicynanmide: ferric citrate=
4:1,6:1,8:1,10:1 (mass ratio).The inventory of fixed cdicynanmide is 8.0g, and the ferric citrate of corrresponding quality is added, it
Afterwards in deionized water by mixture dispersion, stirring is evaporated in a water bath, and mixed-powder is obtained after grinding.Next by mixed powder
End is put into quartz ampoule, is warming up to 650 DEG C in argon atmosphere with the heating rate of 10 DEG C/min, is naturally cooling to room temperature, obtains
To a series of iron content carbon matrix precursor (Fe/Fe@NC-650-X) of differential responses object ratios；
Presoma obtained and sodium hypophosphite are mixed with the ratio of Fe:P=1:5 (atomic ratio), grinding uniformly, is put into
In tube furnace in argon atmosphere phosphorating treatment, be warming up to 500 DEG C with the heating rate of 5 DEG C/min, and keep 2h, Temperature fall
To room temperature, carbon support iron phosphide (FeP/Fe@NC-650-X) is obtained after washing is dry and produces hydrogen elctro-catalyst.
The XRD diagram for producing hydrogen elctro-catalyst is shown in Fig. 1 (b).
Embodiment 3
This example demonstrates that the preparation of carbon support phosphatization cobalt (CoP/Co@NC) catalyst and the control of heat treatment temperature (T)
Example:
Use cobalt acetate and cdicynanmide for raw material, according to cdicynanmide: cobalt acetate=8:1 mass ratio feeds intake, by 8.0g bis-
In deionized water, stirring is evaporated in a water bath, and grinding obtains mixed-powder for cyanamide and the dispersion of 1.0g cobalt acetate.Next it will mix
It closes powder to be put into quartz ampoule, is warming up to 650,680,700 DEG C respectively in argon atmosphere with the heating rate of 10 DEG C/min, from
It so is cooled to room temperature, obtains carbon matrix precursor containing cobalt (Co/Co@NC-T-8)；
Presoma obtained and sodium hypophosphite are mixed with the ratio of Co:P=1:5 (atomic ratio), grinding uniformly, is put into
In tube furnace in argon atmosphere phosphorating treatment, be warming up to 500 DEG C with the heating rate of 5 DEG C/min, and keep 2h, Temperature fall
To room temperature, carbon support phosphatization cobalt (CoP/Co@NC-T-8) is obtained after washing is dry and produces hydrogen elctro-catalyst.
The XRD diagram for producing hydrogen elctro-catalyst is shown in Fig. 1 (c).
The activity and stability test result of CoP/Co NC-680-8 obtained in it is shown in Fig. 4.
Embodiment 4
This example demonstrates that carbon supports nickel phosphide (Ni2P/Ni@NC) preparation of catalyst and the control of heat treatment temperature (T)
Example:
Use nickel acetate and cdicynanmide for raw material, according to cdicynanmide: nickel acetate=8:1 mass ratio feeds intake, by 8.0g bis-
In deionized water, stirring is evaporated in a water bath, and grinding obtains mixed-powder for cyanamide and the dispersion of 1.0g nickel acetate.Next it will mix
It closes powder to be put into quartz ampoule, is warming up to 650,680,700 DEG C respectively in argon atmosphere with the heating rate of 10 DEG C/min, from
It so is cooled to room temperature, obtains nickeliferous carbon matrix precursor (Ni/Ni@NC-T-8)；
Presoma obtained and sodium hypophosphite are mixed with the ratio of Ni:P=1:5 (atomic ratio), grinding uniformly, is put into
In tube furnace in argon atmosphere phosphorating treatment, be warming up to 500 DEG C with the heating rate of 5 DEG C/min, and keep 2h, Temperature fall
To room temperature, carbon support nickel phosphide (Ni is obtained after washing is dry2P/Ni@NC) produce hydrogen elctro-catalyst.
The XRD diagram for producing hydrogen elctro-catalyst is shown in Fig. 1 (d).
Ni obtained in it2The activity and stability test result of P/Ni@NC-680-8 is shown in Fig. 5.
Embodiment 5
This example demonstrates that carbon support transition metal phosphide (by taking carbon supports iron phosphide FeP/Fe@NC as an example) catalyst system
The control example of the ratio of standby metal and phosphorus source:
Use ferric citrate and cdicynanmide for raw material, according to cdicynanmide: ferric citrate=8:1 mass ratio feeds intake,
In deionized water by 8.0g cdicynanmide and the dispersion of 1.0g ferric citrate, stirring is evaporated in a water bath, and grinding obtains mixed powder
End.Next mixed-powder is put into quartz ampoule, is warming up to 650 DEG C in argon atmosphere with the heating rate of 10 DEG C/min,
It is naturally cooling to room temperature, obtains iron content carbon matrix precursor (Fe/Fe@NC-650-8)；
The ratio of presoma obtained and sodium hypophosphite is adjusted to Fe:P=1:5,1:4,1:3,1:2,1:1 (atom
Than), it is ground uniformly after the two is mixed, mixed-powder is put into tube furnace the phosphorating treatment in argon atmosphere later, with 5
DEG C/heating rate of min is warming up to 500 DEG C, and keeps 2h, it is naturally cooling to room temperature, obtains a series of phosphatizations after washing is dry
Carbon support iron phosphide (FeP/Fe@NC) afterwards produces hydrogen elctro-catalyst.
Embodiment 6
This example demonstrates that carbon support transition metal phosphide (by taking carbon supports iron phosphide FeP/Fe@NC as an example) catalyst system
The control example of standby phosphatization temperature:
Iron content carbon matrix precursor (Fe/Fe@NC-650-8) is prepared according to embodiment 5；
Presoma obtained and sodium hypophosphite are mixed according to the ratio of Fe:P=1:5 (atomic ratio), grinding uniformly, will
Mixed-powder is put into tube furnace in argon atmosphere with the heating rate of 5 DEG C/min respectively at 300,400,500,600 DEG C
Phosphorating treatment, and 2h is kept, it is naturally cooling to room temperature, a series of carbon support phosphorus at a temperature of different phosphatizations is obtained after washing is dry
Change iron (FeP/Fe@NC) and produces hydrogen elctro-catalyst.
Skilled addressee readily understands that in the item for the thought for not departing from material and method disclosed in description above
The present invention can be combined or be changed under part, it is believed that this change is included within the scope of the invention.Therefore, specifically above
The special embodiment of description is merely illustrative, and is not limited the scope of the invention, by accessory claim and its it is any and
Whole equivalent ways provide complete scope of the invention.
Claims (9)
1. a kind of carbon support transition metal phosphide produces hydrogen elctro-catalyst, it is characterised in that:
Catalyst is the transition some or all of in direct phosphating carbon material using the carbon material containing transition metal as conductive substrates
The transition metal phosphide obtained after metal is that the carbon of catalytic active species supports transition metal phosphide to produce hydrogen elctro-catalyst；
Transition metal is one or more of Fe, Co, Ni, Cu, Mo, W.
2. a kind of carbon support transition metal phosphide described in claim 1 produces the preparation method of hydrogen elctro-catalyst, feature exists
In: it prepares and includes the following steps,
(1) transition metal-type compound, carbon compound are weighed, mixed-powder is mixed to get, mixed-powder is put into tube furnace
In, it is roasted in argon atmosphere, Temperature fall obtains carbon support metal precursor；
(2) after supporting metal precursor and phosphorus source to mix in obtained carbon, the phosphorating treatment in argon atmosphere is naturally cooling to
Drying is washed after room temperature, is obtained carbon support transition metal phosphide and is produced hydrogen elctro-catalyst.
3. carbon support transition metal phosphide according to claim 2 produces the preparation method of hydrogen elctro-catalyst, feature exists
In:
The transition metal-type compound be ferrocene, ferric citrate, six cyanogen close iron (II) sour ferrous ammonium, ammonium heptamolybdate,
Ammonium phosphomolybdate, Yi Jitie, cobalt, nickel, copper, molybdenum, phthalocyanine-like compound, acetylacetonate, citrate, second corresponding to tungsten metal
One or more of hydrochlorate, chlorate, nitrate, sulfate or phosphate, optimization citric acid salt, acetate.
4. carbon support transition metal phosphide according to claim 2 produces the preparation method of hydrogen elctro-catalyst, feature exists
In:
The carbon compound be cdicynanmide, melamine, urea, glucose, ethylenediamine tetra-acetic acid, polystyrene, thiophene,
One or more of imidazoles, hexachloro-benzene, toluene, benzene or biomass material, preferably dicyan ammonium, melamine.
5. carbon support transition metal phosphide according to claim 2 produces the preparation method of hydrogen elctro-catalyst, feature exists
In:
Transition metal-type compound and carbon compound are dissolved into mixing with the mass ratio of 1:1~1:20, obtained after water bath method
Mixed-powder, preferably 1:4-1:10.
6. carbon support transition metal phosphide according to claim 2 produces the preparation method of hydrogen elctro-catalyst, feature exists
In:
Mixed-powder is warming up to 400 DEG C~1200 DEG C with the heating rate of 2~15 DEG C/min in argon atmosphere, and keeps 1h
~10h, is naturally cooling to room temperature.
7. carbon support transition metal phosphide according to claim 2 produces the preparation method of hydrogen elctro-catalyst, feature exists
In:
Preparing phosphorus source used in metal phosphide is in sodium hypophosphite, red phosphorus, organic phosphine, sodium dihydrogen phosphate or ammonium dihydrogen phosphate
One or more, preferably red phosphorus, sodium hypophosphite.
8. according to right want 2 described in carbon support transition metal phosphide produce hydrogen elctro-catalyst preparation method, it is characterised in that:
Carbon support metal precursor and phosphorus source are uniformly mixed with metal with the atomic ratio of phosphorus for 1:1~1:10, preferably 1:3-
1:7。
9. carbon support transition metal phosphide according to claim 2 produces the preparation method of hydrogen elctro-catalyst, feature exists
In:
The mixed-powder of metal precursor and phosphorus source is supported to be warming up in argon gas with the heating rate of 2~15 DEG C/min in carbon
300 DEG C~800 DEG C, and 1h~10h is kept, it is naturally cooling to room temperature.
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