CN116651444A - IrO (Infrared radiation) device 2 /TiO 2 Composite catalyst, preparation method and application thereof - Google Patents

IrO (Infrared radiation) device 2 /TiO 2 Composite catalyst, preparation method and application thereof Download PDF

Info

Publication number
CN116651444A
CN116651444A CN202310872587.4A CN202310872587A CN116651444A CN 116651444 A CN116651444 A CN 116651444A CN 202310872587 A CN202310872587 A CN 202310872587A CN 116651444 A CN116651444 A CN 116651444A
Authority
CN
China
Prior art keywords
tio
iro
composite catalyst
preparation
carrier
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202310872587.4A
Other languages
Chinese (zh)
Inventor
杨辉
杨晨璐
王国樑
程庆庆
乐舟莹
李军
徐建峰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Advanced Research Institute of CAS
Original Assignee
Shanghai Advanced Research Institute of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Advanced Research Institute of CAS filed Critical Shanghai Advanced Research Institute of CAS
Priority to CN202310872587.4A priority Critical patent/CN116651444A/en
Publication of CN116651444A publication Critical patent/CN116651444A/en
Pending legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/468—Iridium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • 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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • 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
    • C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Electrochemistry (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

The invention provides an IrO 2 /TiO 2 A composite catalyst, a preparation method and application thereof, comprising: s1, tiO 2 Dispersing the carrier in an alkali solution to obtain a carrier solution; s2, transferring the carrier solution to a reaction kettle for hydrothermal reaction, cooling and centrifuging to obtain a solid product; s3, adding the solid product into an acid solution, heating and stirring, centrifuging, washing and drying to obtain H 2 Ti 6 O 13 A precursor; s4, HTO frontGrinding and mixing the precursor and nitrate, dispersing in ethanol, and dispersing liquid; s5, adding an iridium source into the dispersion liquid, heating and stirring, and performing rotary evaporation and vacuum drying to obtain solid powder; s6, calcining the solid powder in air to obtain IrO 2 /TiO 2 A composite catalyst. The invention is characterized in IrO 2 Incorporating OH-rich functional groups in TiO 2 A carrier through OH functional groups and IrO 2 Strong interaction between them without sacrificing IrO 2 The catalytic stability is improved and the intrinsic catalytic activity is improved.

Description

IrO (Infrared radiation) device 2 /TiO 2 Composite catalyst, preparation method and application thereof
Technical Field
The invention belongs to the technical field of hydrogen production by water electrolysis, and particularly relates to IrO 2 /TiO 2 A composite catalyst, a preparation method and application thereof.
Background
With the rapid development of low-carbon emission economy and renewable energy sources, hydrogen energy is widely focused as an ideal energy carrier and an efficient energy storage technology, and the Proton Exchange Membrane (PEM) water electrolysis hydrogen production is a key point of research on a green hydrogen production technology and is the most potential hydrogen production technology due to the advantages of cleanliness, no pollution, high current density, high electrolysis efficiency, high hydrogen purity and the like. In PEM water electrolysis hydrogen production, high performance catalysts are limited to noble metals, so cost reduction is critical to the implementation of PEM water electrolysis hydrogen production for scale applications. At present, iridium-based and ruthenium-based catalysts are mainly used in acidic electrolyzed water, but the ruthenium-based catalysts are extremely easy to dissolve under acidic and high-potential conditions, so that the catalyst is deactivated, and the activity of the iridium-based catalysts is low, so that the improvement of the intrinsic activity of the iridium-based catalysts is an important and hot spot of research at the present stage.
One effective way to increase the activity of iridium-based catalysts is to introduce a support, which is selected to have high conductivity, high specific surface area and good durability. Transition metal oxides, nitrides and carbides are considered to be potential carriers, whereas carbon carriers widely used in fuel cell catalysts are highly susceptible to oxidation due to their strong acid and high potentialAnd corrosion causes catalyst deactivation. The carriers currently studied in relatively large numbers are: nb doped titanium dioxide, niobium oxide (ITO), tin oxide (ATO); straser et al use Sb-doped SnO 2 (ATO) is used as a carrier of Ir nano dendrites, and the obtained composite catalyst shows OER activity of 70A/gIr under 280mV overpotential. Chen et al prepared Nb 0.05 Ti 0.95 O 2 As IrO 2 Carrier, mass active site 471A/gIrO at 1.6V 2 Superior to unsupported IrO 2 (198A/gIrO 2 ). In addition to metal oxides, metal carbides (e.g., tiC, taC, siC, WC), metal nitrides (e.g., tiN) have also been reported as support materials for OER. However, while increasing activity, metal utilization, etc., no loss of stability is currently a major challenge.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, an object of the present invention is to provide IrO 2 /TiO 2 The composite catalyst, the preparation method and the application thereof are used for solving the problems that the iridium-based catalyst in the prior art cannot improve the intrinsic catalytic activity and the metal utilization rate and does not lose the stability.
To achieve the above and other related objects, the present invention provides an IrO 2 /TiO 2 A method for preparing a composite catalyst, the method comprising the steps of:
s1, tiO 2 Dispersing the carrier in an alkali solution to obtain a carrier solution;
s2, transferring the carrier solution into a reaction kettle for hydrothermal reaction, naturally cooling to room temperature, and centrifugally separating out solids to obtain a solid product;
s3, adding the solid product into an acid solution, heating and stirring for a period of time, centrifuging, washing and drying to obtain H 2 Ti 6 O 13 A precursor;
s4, carrying out H treatment on the 2 Ti 6 O 13 Mixing the precursor with nitrate, fully grinding, and dispersing in ethanol to obtain a dispersion liquid;
s5, adding an iridium source into the dispersion liquid, stirring for a period of time under a heating condition, and performing rotary evaporation and vacuum drying to obtain solid powder;
s6, calcining the solid powder in air to obtain IrO 2 /TiO 2 A composite catalyst.
Preferably, the TiO in step S1 2 The particle size of the carrier is 25 nm-100 nm.
Preferably, the alkali solution in the step S1 comprises one or a combination of KOH and NaOH, and the concentration of the alkali solution is 0.1-10 mol/L.
Preferably, the TiO in the carrier solution obtained in step S1 2 The concentration of the carrier is 0.5-3 mg/ml.
Preferably, the temperature of the hydrothermal reaction in the step S2 is 100-200 ℃, and the time of the hydrothermal reaction is 12-72 h.
Preferably, the acid solution in step S3 is HCl, H 2 SO 4 、HNO 3 One or a combination of the above, and the concentration of the acid solution is 0.1 to 1mol/L.
Preferably, in step S3, the solid product is added to the acid solution to form a mixed solution, and the concentration of the solid product in the mixed solution is 0.5-3 mg/ml.
Preferably, the temperature of the heating and stirring in the step S3 is 50-90 ℃, and the time of the heating and stirring is 4-24 hours.
Preferably, the nitrate in step S4 is NaNO 3 Or KNO 3 One of or a combination of the above,
preferably, the nitrate and the H in step S4 2 Ti 6 O 13 The mass ratio between the precursors is 1:1 to 10:1.
preferably, the iridium source in step S5 is one or a combination of chloroiridic acid, iridium trichloride hydrate and iridium acetylacetonate.
Preferably, the heating temperature in the step S5 is 50-90 ℃, and the stirring time is 3-10 hours.
Preferably, in the step S6, the calcination is performed after the temperature is raised from room temperature to the calcination temperature, wherein the temperature raising rate is 1-5 ℃/min, the calcination temperature is 200-800 ℃, and the time of heat preservation is 0.5-3 h.
Preferably, the IrO obtained in step S6 2 /TiO 2 IrO in composite catalyst 2 The content of (2) is 15-60 wt%.
The invention also provides the IrO prepared by the preparation method 2 /TiO 2 A composite catalyst.
The invention also provides an IrO 2 /TiO 2 Use of a complex catalyst, irO 2 /TiO 2 Use of a complex catalyst as an oxygen evolution catalyst in an acidic electrolyzed water oxygen evolution reaction, wherein the IrO 2 /TiO 2 The composite catalyst is prepared by adopting the preparation method.
As described above, irO of the present invention 2 /TiO 2 The composite catalyst, the preparation method and the application thereof have the following beneficial effects:
the present invention employs a modified Adam melting process to effect IrO 2 In TiO 2 The carrier has continuous electron conductivity, overcomes the defect of TiO 2 Factors that are bad in carrier conductivity, in IrO 2 Incorporating OH-rich functional groups in TiO 2 A carrier through OH functional groups and IrO 2 Strong interaction between them without sacrificing IrO 2 The catalytic stability is improved and the intrinsic catalytic activity is improved, and finally the IrO with uniform dispersion and particle diameter of only about 1nm is obtained 2 /TiO 2 A composite catalyst; and the catalyst was at 10mA cm -2 Is 278mV at a current density of 10mA cm -2 Can stabilize for at least 312 hours; irO prepared 2 /TiO 2 The composite catalyst still keeps high activity and high stability on the membrane electrode, and simultaneously has high metal utilization rate of 2A/cm 2 The cell pressure at 80 ℃ is only 1.787V, at 1A/cm 2 The operation can be stably performed for at least 350 hours.
Drawings
FIG. 1 shows IrO of the present invention 2 /TiO 2 Process flow for a method for producing a composite catalystA flowchart.
FIG. 2a shows IrO prepared in example 1 of the present invention 2 /TiO 2 HRTEM diagram of the composite catalyst.
FIG. 2b shows IrO prepared in example 1 of the present invention 2 /TiO 2 Particle size distribution of the composite catalyst.
FIG. 3a shows IrO prepared in examples 1 and 2 of the present invention 2 /TiO 2 XPS O1s spectrum of the composite catalyst.
FIG. 3b shows IrO prepared in examples 1 and 2 of the present invention 2 /TiO 2 XPS Ir4f spectrum of the composite catalyst.
FIG. 4 shows IrO prepared in examples 1 and 2 of the present invention 2 /TiO 2 XRD pattern of the composite catalyst.
FIG. 5 shows IrO prepared in example 1 and example 2 of the present invention 2 /TiO 2 Composite catalyst, and commercial IrO 2 Catalyst, commercialized IrO 2 /TiO 2 (IrO 2 /TiO 2 -Heraeus) Linear Sweep Voltammetry (LSV) profile of the catalyst.
FIG. 6 shows IrO prepared in example 1 of the present invention 2 /TiO 2 Composite catalyst at 10mA cm -2 The following electrochemical life test chart.
Fig. 7 shows polarization graphs of the membrane electrodes prepared in examples 3, 4, and 5 of the present invention.
Fig. 8 shows a stability test chart of the membrane electrode prepared in embodiment 3 of the present invention.
Detailed Description
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention.
The invention provides an IrO 2 /TiO 2 The preparation method of the composite catalyst comprises the following steps:
s1, tiO 2 Dispersing the carrier in an alkali solution to obtain a carrier solution;
s2, transferring the carrier solution into a reaction kettle for hydrothermal reaction, naturally cooling to room temperature, and centrifugally separating out solids to obtain a solid product;
s3, adding the solid product into an acid solution, heating and stirring for a period of time, centrifuging, washing and drying to obtain H 2 Ti 6 O 13 A precursor;
s4, carrying out H obtained in the step S3 2 Ti 6 O 13 Mixing the precursor with nitrate, fully grinding, and dispersing in ethanol to obtain a dispersion liquid;
s5, adding an iridium source into the dispersion liquid, stirring for a period of time under a heating condition, and performing rotary evaporation and vacuum drying to obtain solid powder;
s6, calcining the solid powder in air to obtain IrO 2 /TiO 2 A composite catalyst.
In particular, tiO 2 Dispersing the carrier in alkali solution to form carrier solution, and performing hydrothermal reaction on the carrier solution to form titanate solid product to obtain H 2 Ti 6 O 13 Precursor (HTO precursor), step S3, adding the solid product into acid solution for H + Exchange, on the one hand, to neutralize the OH functional groups adsorbed on the surface of the solid product, which are not completely reacted, and on the other hand, to exchange the metal ions in the titanate solid product; the nitrate is added in the step S4 to decompose the nitrate at high temperature to generate oxygen, and the purpose of mixing the HTO precursor and the nitrate is to oxidize the iridium source in the step S5 more fully, and the iridium source is uniformly adsorbed on the mixture of the HTO precursor and the nitrate by stirring after the iridium source is added in the step S5. As an example, tiO in step S1 2 The particle size of the carrier is 25 nm-100 nm.
In particular, tiO 2 The particle size of the support may include values in any of the ranges 25nm, 50nm, 75nm, 100nm, etc.
As an example, the alkali solution in step S1 includes one or a combination of KOH and NaOH, and the concentration of the alkali solution is 0.1 to 10mol/L.
Specifically, the concentration of the alkali solution in step S1 may include values in any range of 0.1mol/L, 0.5mol/L, 1mol/L, 3mol/L, 5mol/L, 7mol/L, 9mol/L, 10mol/L, etc., and may be specifically adjusted according to the actual use.
As an example, tiO in the support solution obtained in step S1 2 The concentration of the carrier is 0.5-3 mg/ml.
Specifically, tiO in the carrier solution obtained in step S1 2 The concentration of the carrier may include values in any range of 0.5mg/ml, 1mg/ml, 1.5mg/ml, 2mg/ml, 2.5mg/ml, 3mg/ml, etc., and may be specifically adjusted according to the actual use.
As an example, the temperature of the hydrothermal reaction in step S2 is 100 to 200 ℃, and the time of the hydrothermal reaction is 12 to 72 hours.
Specifically, the temperature of the hydrothermal reaction in step S2 may include values in any range of 100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃, 200 ℃ and the like, and may be specifically adjusted according to the actual situation; the time of the hydrothermal reaction may include values in any range of 12h, 18h, 24h, 36h, 48h, 60h, 72h, etc., and may be specifically adjusted according to the actual situation.
As an example, the acid solution in step S3 is HCl, H 2 SO 4 、HNO 3 One or a combination of the above, and the concentration of the acid solution is 0.1 to 1mol/L.
Specifically, the concentration of the acid solution in step S3 may include values in any range of 0.1mol/L, 0.3mol/L, 0.5mol/L, 0.7mol/L, 0.9mol/L, 1mol/L, etc., and may be specifically adjusted according to the actual use.
As an example, the solid product in step S3 is added to the acid solution to form a mixed solution, and the concentration of the solid product in the mixed solution is 0.5 to 3mg/ml.
Specifically, in step S3, the solid product is added into an acid solution to carry out H + Exchange, one partyThe surface is used for neutralizing the OH functional groups which are adsorbed on the surface of the solid product and are not completely reacted, and on the one hand, the surface is used for exchanging metal ions in the titanate solid product; wherein, the solid product is added into the acid solution to form a mixed solution, and the concentration of the solid product in the mixed solution can comprise values in any range of 0.5mg/ml, 1mg/ml, 1.5mg/ml, 2mg/ml, 2.5mg/ml, 3mg/ml and the like, and can be specifically adjusted according to the actual practice.
As an example, the temperature of heating and stirring in the step S3 is 50-90 ℃, and the time of heating and stirring is 4-24 hours.
Specifically, the purpose of heating and stirring is to accelerate H + The exchange rate, the temperature of heating and stirring in the step S3 can comprise values in any range of 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ and the like, and the values can be specifically adjusted according to actual conditions; the heating and stirring time can comprise any range of values of 4h, 8h, 12h, 16h, 20h, 24h and the like, and can be specifically adjusted according to actual conditions.
As an example, the nitrate in step S4 is NaNO 3 Or KNO 3 One or a combination of the above.
By way of example, nitrate with H 2 Ti 6 O 13 The mass ratio between the precursors is 1:1 to 10:1.
specifically, nitrate and H 2 Ti 6 O 13 The mass ratio between the precursors may include 1: 1. 2: 1. 4: 1. 6: 1. 8: 1. 10:1, etc., and may be specifically adjusted according to the actual situation.
As an example, the iridium source in step S5 is chloroiridic acid (H 2 IrCl 6 ·xH 2 O,) iridium trichloride hydrate (IrCl) 3 ·xH 2 O), iridium acetylacetonate (Ir (acac) 3 ) One or a combination of the above.
Preferably, the chloroiridic acid is liquid and has a specific molecular formula of H 2 IrCl 6 ·6H 2 O, wherein the content of iridium is 35wt%; the iridium trichloride hydrate and the iridium acetylacetonate are solid powder, and the content of the iridium trichloride hydrate and the iridium acetylacetonate is more than or equal to 99 percent.
As an example, the heating temperature in the step S5 is 50-90 ℃, and the stirring time is 3-10 h.
Specifically, the heating temperature in step S5 may include values in any range of 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, etc., and may be specifically adjusted according to the actual situation; the stirring time can comprise values in any range of 3h, 5h, 7h, 9h, 10h, etc., and can be specifically adjusted according to the actual situation.
As an example, the calcination in step S6 is performed by heating from room temperature to calcination temperature, wherein the heating rate is 1-5 ℃/min, the calcination temperature is 200-800 ℃, and the time of heat preservation is 0.5-3 h.
Specifically, the calcining temperature can influence the crystallinity of the prepared catalyst, the higher the calcining temperature is, the higher the crystallinity of the prepared catalyst is, but when the temperature is too high, the particle size of the prepared catalyst is increased, the corresponding active area is reduced, and the reaction is incomplete when the calcining temperature is too low, so that on the basis of other various influencing factors, the heating rate can be obtained by a large amount of creative labor, and the heating rate can comprise values in any range of 1 ℃/min, 2 ℃/min, 3 ℃/min, 4 ℃/min, 5 ℃/min and the like, and can be specifically adjusted according to the actual conditions; the calcination temperature can comprise values in any range of 200 ℃, 400 ℃, 600 ℃, 800 ℃ and the like, and can be specifically adjusted according to actual conditions; the time of the heat preservation can comprise values in any range of 0.5h, 1h, 2h, 2.5h, 3h and the like, and the time can be specifically adjusted according to actual practice.
Preferably, the calcination temperature is in any range of 350 to 450 ℃ (e.g., 350 ℃, 370 ℃, 390 ℃, 410 ℃, 430 ℃, 450 ℃, etc.).
As an example, irO obtained in step S6 2 /TiO 2 IrO in composite catalyst 2 The content of (2) is 15-60 wt%.
Specifically, irO obtained in step S6 2 /TiO 2 IrO in composite catalyst 2 The content of (c) may include values in any range of 15wt%, 20wt%, 30wt%, 40wt%, 50wt%, 55wt%, 60wt%, etc., and may be specifically adjusted according to the actual use.
The invention also provides an IrO 2 /TiO 2 Composite materialA catalyst comprising IrO as described above 2 /TiO 2 The preparation method of the composite catalyst is used for preparing the catalyst.
In particular, the present invention overcomes the problem of TiO by using a modified Adam melting process 2 Factors that are bad in carrier conductivity, in IrO 2 Incorporating OH-rich functional groups in TiO 2 A carrier through OH functional groups and IrO 2 Strong interaction between them without sacrificing IrO 2 The catalytic stability is improved and the intrinsic catalytic activity is improved, so that the IrO with uniformly dispersed particle size of 0.8 nm-1.5 nm (such as values in any range of 0.8nm, 1.0nm, 1.2nm, 1.4nm, 1.5nm and the like) is finally obtained 2 /TiO 2 A composite catalyst; wherein, commercialized IrO 2 The catalyst is prepared by adopting an Adam melting method, and the precursor chloroiridium acid and sodium nitrate are fully mixed and sintered to obtain the high-purity nanoscale iridium oxide catalyst.
The invention also provides an IrO 2 /TiO 2 Application of composite catalyst and IrO 2 /TiO 2 Application of composite catalyst as oxygen evolution catalyst in acidic electrolyzed water oxygen evolution reaction, wherein IrO 2 /TiO 2 The composite catalyst is prepared by adopting the preparation method.
For a better understanding of IrO in the present invention 2 /TiO 2 The IrO in the present invention is described below with reference to specific examples 2 /TiO 2 The composite catalyst, the method of preparation and the use thereof are described in the description, it being noted that these examples are merely illustrative and do not limit the invention in any way.
Commercial IrO used in the examples below 2 The catalyst is purchased from Hangzhou City, innovative energy company, commercial IrO 2 /TiO 2 (IrO 2 /TiO 2 -Heraeus) brand is Heraeus.
Example 1
The present embodiment provides an IrO 2 /TiO 2 The preparation method of the composite catalyst comprises the following steps:
s1, weighing 0.5g of TiO 2 Dispersing the carrier in 50mL of KOH solution with the concentration of 10mol/L, and stirring for 30min at normal temperature to obtain a carrier solution; wherein, tiO 2 The particle size of the carrier is 25nm;
s2, transferring the carrier solution in the step S1 into a reaction kettle with the volume of 50mL, performing hydrothermal reaction at 180 ℃ for 72h, and centrifuging to separate out solids after the carrier solution is naturally cooled to room temperature to obtain a solid product;
s3, adding the solid product obtained in the step S2 into 100mL of 0.5mol/L HCl solution, stirring for 8 hours at 85 ℃, centrifuging, washing with deionized water to pH 7, and then drying in vacuum at 60 ℃ to obtain H 2 Ti 6 O 13 A precursor;
s4, weighing 71mg of H obtained in the step S3 2 Ti 6 O 13 Mixing the precursor with 5g of sodium nitrate, fully grinding, and dispersing the ground mixture in 70mL of ethanol to obtain a dispersion liquid;
s5, adding 200uL of chloroiridic acid (the iridium content is 35 wt%) into the dispersion liquid, stirring for 8 hours at 70 ℃, then rotationally steaming out ethanol at 60 ℃, then vacuum drying at 60 ℃, and grinding to obtain solid powder;
s6, placing the solid powder in an air atmosphere of a tube furnace, heating to 400 ℃ at a heating rate of 2 ℃/min, preserving heat for 1h, cooling, washing with deionized water to remove redundant sodium nitrate, and vacuum drying at 60 ℃ to obtain IrO 2 IrO content of 45wt% 2 /TiO 2 A composite catalyst.
Example 2
The present embodiment provides an IrO 2 /TiO 2 The preparation method of the composite catalyst is different from that of example 1 in that: in the step S6, the temperature is increased to 400 ℃ at the heating rate of 2 ℃/min and the temperature is kept for 2 hours; other steps and methods are the same as those in embodiment 1, and will not be described here.
Performance test results:
referring to FIGS. 2a and 2b, irO prepared in example 1, respectively 2 /TiO 2 HRTEM and particle size distribution of the composite catalyst, as can be seen from the figure, example 1 successfully produced uniformly distributed ultra-small IrO 2 /TiO 2 The particle size of the composite catalyst is about 1 nm.
Referring to FIGS. 3a and 3b, irO prepared in example 1 and example 2, respectively 2 /TiO 2 The O1s XPS spectrum and the Ir4f XPS spectrum of the composite catalyst show that the surface of the catalysts prepared in example 1 and example 2 has high content of OH functional groups.
Referring to FIG. 4, irO prepared in example 1 and example 2 2 /TiO 2 XRD pattern of composite catalyst, irO calculated according to Shelle's formula 2 The particle size of (2) is 1-2 nm.
Evaluation of electrochemical Properties
IrO prepared in example 1 and example 2 above was used 2 /TiO 2 Composite catalyst and no TiO 2 Commercialization of vectors IrO 2 Catalyst and commercialized IrO 2 /TiO 2 (IrO 2 /TiO 2 -Heraeus) is applied to an acidic electrolyzed water oxygen evolution reaction for electrochemical performance evaluation, and the specific method comprises the following steps:
a1, mixing 4.3mg of a catalyst, 10 mu L of 5% perfluorosulfonic acid (Nafion) solution, 750 mu L of isopropyl alcohol and 250 mu L of ultrapure water, and performing ultrasonic dispersion for 1h to prepare an electrochemical test ink (ink) solution;
a2, a glassy carbon electrode head with the diameter of 5mm (GC, area of 0.196cm is selected 2 ) Dropping 15 mu L of ink solution on the GC which is polished in advance, naturally airing to prepare a test electrode, wherein the Ir loading amount is 150 mu g cm -2 ；
A3, carrying out electrolytic water oxygen evolution performance test on the test electrode, specifically taking 0.5. 0.5M H 2 SO 4 Placing the solution in a five-port electrolytic cell, and introducing N 2 Half an hour, the solution was saturated and Cyclic Voltammetry (CV) and Linear Sweep Voltammetry (LSV) tests were performed; wherein the scanning speed in CV test is 50mVs -1 Scanning until CV curves coincide, wherein the voltage range is 0.7-1.5V/RHE; during linear scan testScanning speed is 5mVs -1 Scanning range is 1.2-1.7V/RHE; then at a current density of 10mA cm -2 Electrochemical life testing was performed as follows.
Test results referring to FIGS. 5 and 6, it can be seen from FIG. 5 that IrO prepared in example 1 2 /TiO 2 Composite catalyst at 10mA cm -2 Is 278mV over IrO 2 Catalyst (29 mV) and commercial IrO 2 /TiO 2 -Heraeus (84 mV); as can be seen from FIG. 6, irO prepared in example 1 2 /TiO 2 The composite catalyst has excellent stability, and has no obvious attenuation after 312 hours of constant current.
Example 3
The embodiment provides a preparation method of an electrolytic water film electrode with low noble metal loading, which comprises the following steps:
b1, irO prepared in example 1 was taken 2 /TiO 2 20mg of composite catalyst, which is prepared from water, isopropanol and catalyst according to a mass ratio of 15:15:1, adding water and isopropanol in proportion, then adding 20% Nafion film solution, carrying out ultrasonic treatment for 1h to obtain anode catalyst ink, and spraying the anode catalyst ink on the surface of a proton exchange film (Nafion 115);
20mg of Pt/C catalyst (the content of Pt is 60 wt%) is taken, and the mass ratio of water to isopropanol to the Pt/C catalyst is 15:15:1, adding water and isopropanol in a proportion of 1, then adding a 20% Nafion film solution, wherein the mass of Nafion resin is 20% of that of the Pt/C catalyst, obtaining cathode catalyst ink after ultrasonic treatment for 1h, spraying the cathode catalyst ink on the other side of the proton exchange film (Nafion 115), and finally obtaining the low noble metal loading electrolytic water film electrode (marked as IrO) 2 /TiO 2 -0.3mg Ir /cm 2 )。
The catalyst loading in the membrane electrode prepared in this example was measured using a weight measurement, and the Ir loading in the membrane electrode was determined to be 0.3mg/cm 2 。
Example 4
The present embodiment provides a method for producing a membrane electrode, which is different from that of embodiment 3 in that: the catalyst used in step B1 was commercial IrO 2 Catalyst (IrO) 2 -com) at an Ir loading of 2mg/cm 2 Preparation of a Membrane electrode (denoted IrO) 2 -commercial-2mg Ir /cm 2 ) Other steps and methods are the same as those in embodiment 1, and will not be described here.
Example 5
The present embodiment provides a method for preparing a membrane electrode, which is different from embodiment 3 in that: the catalyst used in step B1 was commercial IrO 2 Catalyst (IrO) 2 -a com-munic) according to an Ir loading of 0.3mg/cm 2 Preparation of a Membrane electrode (denoted IrO) 2 -commercial-0.3mg Ir /cm 2 ) Other steps and methods are the same as those in embodiment 1, and will not be described here.
The membrane electrode (IrO) prepared in examples 3, 4, 5 was prepared 2 /TiO 2 -0.3mg Ir /cm 2 、IrO 2 -commercial-2mg Ir /cm 2 、IrO 2 -commercial-0.3mg Ir /cm 2 ) The method is applied to the water electrolysis catalytic reaction of the proton exchange membrane, each membrane electrode is respectively put into a small-sized electrolytic water clamp, deionized pure water at 80 ℃ is fused into the anode, the whole system is in the environment of 80 ℃, and the current density of the electrolytic water is set to be 0-2A/cm 2 The test was performed to obtain the polarization curves of the electrolyzed water of each membrane electrode, and referring to FIG. 7, it can be seen from FIG. 7 that IrO 2 /TiO 2 -0.3mg Ir /cm 2 Is far higher than IrO with the same Ir loading 2 -commercial-0.3mg Ir /cm 2 In case the Ir loading is reduced many times, irO 2 /TiO 2 -0.3mg Ir /cm 2 Performance of (1) and IrO 2 -commercial-2mg Ir /cm 2 Is equivalent to the membrane electrode IrO prepared in example 3 2 /TiO 2 -0.3mg Ir /cm 2 At 2A/cm 2 The cell tank pressure is only 1.787V at 80 ℃; indicating the IrO prepared in example 1 2 /TiO 2 The membrane electrode prepared by the composite catalyst can effectively promote the benefits of the electrolyzed water catalystUtilization, enhancement of the reactivity, i.e. IrO prepared in example 1 2 /TiO 2 The composite catalyst has high catalytic activity and high metal utilization rate.
The membrane electrode (IrO) prepared in example 3 was subjected to 2 /TiO 2 -0.3mg Ir /cm 2 ) The method is applied to the water electrolysis catalytic reaction of the proton exchange membrane, membrane electrodes are respectively placed in a small-sized electrolytic water clamp, stability test is carried out at 80 ℃, during the test, ultra-pure water is introduced into an anode, and the current density is set to be 1A/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The results of the stability test are shown in FIG. 8, and as can be seen from FIG. 8, irO 2 /TiO 2 -0.3mg Ir /cm 2 At 1A/cm 2 The operation can be stably performed for at least 350 hours.
In summary, the present invention overcomes the problem of TiO using a modified Adam melting process 2 Factors that are bad in carrier conductivity, in IrO 2 Incorporating OH-rich functional groups in TiO 2 A carrier through OH functional groups and IrO 2 Strong interaction between them without sacrificing IrO 2 The catalytic stability is improved and the intrinsic catalytic activity is improved, and finally the IrO with uniform dispersion and particle diameter of only about 1nm is obtained 2 /TiO 2 A composite catalyst; and the catalyst was at 10mA cm -2 Is 278mV at a current density of 10mA cm -2 Can stabilize for at least 312 hours; irO prepared 2 /TiO 2 The composite catalyst still keeps high activity and high stability on the membrane electrode, and simultaneously has high metal utilization rate of 2A/cm 2 The cell pressure at 80 ℃ is only 1.787V, at 1A/cm 2 The operation can be stably performed for at least 350 hours. Therefore, the invention effectively overcomes various defects in the prior art and has high industrial utilization value.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.

Claims (10)

1. IrO (Infrared radiation) device 2 /TiO 2 The preparation method of the composite catalyst is characterized by comprising the following steps:
s1, tiO 2 Dispersing the carrier in an alkali solution to obtain a carrier solution;
s2, transferring the carrier solution into a reaction kettle for hydrothermal reaction, naturally cooling to room temperature, and centrifugally separating out solids to obtain a solid product;
s3, adding the solid product into an acid solution, heating and stirring for a period of time, centrifuging, washing and drying to obtain H 2 Ti 6 O 13 A precursor;
s4, carrying out H treatment on the 2 Ti 6 O 13 Mixing the precursor with nitrate, fully grinding, and dispersing in ethanol to obtain a dispersion liquid;
s5, adding an iridium source into the dispersion liquid, stirring for a period of time under a heating condition, and performing rotary evaporation and vacuum drying to obtain solid powder;
s6, calcining the solid powder in air to obtain IrO 2 /TiO 2 A composite catalyst.
2. IrO according to claim 1 2 /TiO 2 The preparation method of the composite catalyst is characterized by comprising the following steps: step S1 includes one or a combination of the following conditions:
the TiO 2 The particle size of the carrier is 25 nm-100 nm;
the alkali solution comprises one or a combination of KOH and NaOH, and the concentration of the alkali solution is 0.1-10 mol/L;
the TiO in the carrier solution obtained 2 The concentration of the carrier is 0.5-3 mg/ml.
3. IrO according to claim 1 2 /TiO 2 Preparation of composite catalystThe preparation method is characterized in that: the temperature of the hydrothermal reaction in the step S2 is 100-200 ℃, and the time of the hydrothermal reaction is 12-72 h.
4. IrO according to claim 1 2 /TiO 2 The preparation method of the composite catalyst is characterized by comprising the following steps: step S3 includes one or a combination of the following conditions:
the acid solution is HCl, H 2 SO 4 、HNO 3 One or a combination of the above, and the concentration of the acid solution is 0.1 to 1mol/L;
the solid product is added into an acid solution to form a mixed solution, and the concentration of the solid product in the mixed solution is 0.5-3 mg/ml;
the temperature of the heating and stirring is 50-90 ℃, and the time of the heating and stirring is 4-24 hours.
5. IrO according to claim 1 2 /TiO 2 The preparation method of the composite catalyst is characterized by comprising the following steps: step S4 includes one or a combination of the following conditions:
the nitrate is NaNO 3 Or KNO 3 One or a combination of the above;
the nitrate and the H 2 Ti 6 O 13 The mass ratio between the precursors is 1:1 to 10:1.
6. IrO according to claim 1 2 /TiO 2 The preparation method of the composite catalyst is characterized by comprising the following steps: step S5 includes one or a combination of the following conditions:
the iridium source is one or a combination of chloroiridic acid, iridium trichloride hydrate and iridium acetylacetonate;
the heating temperature is 50-90 ℃, and the stirring time is 3-10 h.
7. IrO according to claim 1 2 /TiO 2 The preparation method of the composite catalyst is characterized by comprising the following steps: the calcination in the step S6 is to heat from room temperature toAnd (3) carrying out heat preservation after the calcination temperature, wherein the heating rate is 1-5 ℃/min, the calcination temperature is 200-800 ℃, and the heat preservation time is 0.5-3 h.
8. IrO according to claim 1 2 /TiO 2 The preparation method of the composite catalyst is characterized by comprising the following steps: the IrO obtained in step S6 2 /TiO 2 IrO in composite catalyst 2 The content of (2) is 15-60 wt%.
9. IrO prepared by the preparation method according to any one of claims 1 to 8 2 /TiO 2 A composite catalyst.
10. IrO (Infrared radiation) device 2 /TiO 2 The application of the composite catalyst is characterized in that: the IrO 2 /TiO 2 Use of a complex catalyst as an oxygen evolution catalyst in an acidic electrolyzed water oxygen evolution reaction, wherein the IrO 2 /TiO 2 The composite catalyst is prepared by the preparation method of any one of claims 1 to 8.
CN202310872587.4A 2023-07-17 2023-07-17 IrO (Infrared radiation) device 2 /TiO 2 Composite catalyst, preparation method and application thereof Pending CN116651444A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310872587.4A CN116651444A (en) 2023-07-17 2023-07-17 IrO (Infrared radiation) device 2 /TiO 2 Composite catalyst, preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310872587.4A CN116651444A (en) 2023-07-17 2023-07-17 IrO (Infrared radiation) device 2 /TiO 2 Composite catalyst, preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN116651444A true CN116651444A (en) 2023-08-29

Family

ID=87724324

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310872587.4A Pending CN116651444A (en) 2023-07-17 2023-07-17 IrO (Infrared radiation) device 2 /TiO 2 Composite catalyst, preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN116651444A (en)

Similar Documents

Publication Publication Date Title
Amini et al. Metal and metal oxide electrocatalysts for redox flow batteries
KR102569084B1 (en) An electrocatalyst composition comprising a noble metal oxide supported on tin oxide
Tang et al. NiSe nanowire film supported on nickel foam: an efficient and stable 3D bifunctional electrode for full water splitting
JP5199575B2 (en) Noble metal oxide catalysts for water electrolysis
CN110252335B (en) Carbon-coated nickel-ruthenium nano material and preparation method and application thereof
CN111545250B (en) Ruthenium catalyst with efficient electrocatalytic full-hydrolytic performance and application thereof
Cheng et al. Preparation of Ir0. 4Ru0. 6MoxOy for oxygen evolution by modified Adams’ fusion method
CN101733095B (en) Catalyst for water electrolysis and preparation and application thereof
CN109701545B (en) Electro-catalytic material loaded with vanadium-cobalt alloy nanoparticles and preparation method thereof
CN111266110B (en) Anode catalyst for water electrolysis hydrogen production by using transition metal doped titanium oxide as carrier and preparation method thereof
US20140322631A1 (en) Precious metal oxide catalyst for water electrolysis
CN110479329A (en) A kind of preparation and application of phosphorus doping cobaltous telluride nano material
Wang et al. Elaborately tailored NiCo 2 O 4 for highly efficient overall water splitting and urea electrolysis
CN113437314A (en) Nitrogen-doped carbon-supported low-content ruthenium and Co2Three-function electrocatalyst of P nano particle and preparation method and application thereof
CN111085195A (en) Metal alloy catalyst and preparation method thereof
Zhang et al. Amorphous mixed Ir–Mn oxide catalysts for the oxygen evolution reaction in PEM water electrolysis for H2 production
JP2010227843A (en) Method for producing electrode catalyst, and electrode catalyst
CN109012673B (en) Preparation method and application of oxygen evolution catalyst
CN116651444A (en) IrO (Infrared radiation) device 2 /TiO 2 Composite catalyst, preparation method and application thereof
CN113430555B (en) Iridium oxide-platinum composite nano catalyst, preparation method and application thereof
CN115196697A (en) Transition metal doped ruthenium oxide nano material, preparation method and application thereof
CN114232022A (en) Carbon-supported iridium molybdenum tungsten intermetallic compound and preparation method and application thereof
CN110055555B (en) Oxygen evolution reaction catalyst and preparation method and application thereof
CN115786974B (en) Catalyst for water electrolysis and preparation method thereof
CN115094475B (en) Electrode material with high-performance oxygen evolution catalytic activity and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination