WO2016082262A1 - 一种分级多孔材料及其制备方法 - Google Patents

一种分级多孔材料及其制备方法 Download PDF

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WO2016082262A1
WO2016082262A1 PCT/CN2014/094286 CN2014094286W WO2016082262A1 WO 2016082262 A1 WO2016082262 A1 WO 2016082262A1 CN 2014094286 W CN2014094286 W CN 2014094286W WO 2016082262 A1 WO2016082262 A1 WO 2016082262A1
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Prior art keywords
metal
porous material
silver
electrode
oxide
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PCT/CN2014/094286
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English (en)
French (fr)
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孙公权
袁丽只
姜鲁华
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中国科学院大连化学物理研究所
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Priority claimed from CN201410698615.6A external-priority patent/CN105702966B/zh
Priority claimed from CN201410697301.4A external-priority patent/CN105689733B/zh
Priority claimed from CN201410697812.6A external-priority patent/CN105696048A/zh
Priority claimed from CN201410706344.4A external-priority patent/CN105688909B/zh
Priority claimed from CN201410697811.1A external-priority patent/CN105688950A/zh
Application filed by 中国科学院大连化学物理研究所 filed Critical 中国科学院大连化学物理研究所
Priority to US14/900,440 priority Critical patent/US10052613B2/en
Priority to EP14894183.4A priority patent/EP3231512B1/en
Publication of WO2016082262A1 publication Critical patent/WO2016082262A1/zh

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Definitions

  • the invention belongs to the field of nano materials, and in particular relates to a graded porous material and a preparation method thereof.
  • Nanoporous materials are a new class of nanostructured materials developed in recent years. Due to their large specific surface area, small density, flexible structure and good permeability, porous materials are widely used in separation, catalysis and transmission. Sense, medicine, electrodes, machinery and other fields.
  • the Adzic team found that a single layer of Cu atoms was formed on the surface of noble metal particles by Cu-UPD, and then replaced with Pt 2+ to obtain a Pt single-layer catalyst.
  • the highly dispersed Pt greatly improved the ORR specific mass activity of the catalyst.
  • the core generally uses precious metals such as Pd and Au and alloys thereof, and the cost is high.
  • precious metals such as Pt, Pd and Au
  • Ag has more reserves and lower price, but it has less research.
  • Porous silver has shown good application prospects in the field of catalysis due to its large surface area and favorable mass transfer. Because silver is not resistant to acid corrosion, its application in acidic environments is limited. Precious metals such as Pt and Pd are used as shell materials. The preparation of a porous core-shell structure using porous silver as a core material allows its application in an acidic environment, but research in this area has not been reported.
  • the /Mn 3 O 4 /C electrocatalyst reduced the difference between Pt/C and overpotential to 31mV, indicating that the combination of silver and some oxides such as manganese and cobalt can improve its ORR activity.
  • Linic et al. (Nature Chem. 6 (2014) 828) proved that AgCo forming alloy can improve ORR activity by quantum chemical calculation, and prepared AgCo electrocatalyst with alloy on the surface, which has a higher ORR activity than silver, but its ORR There is still a certain gap between the activity and the Pt/C catalyst.
  • the present invention addresses a problem existing in the prior art and invents a porous material and a method of preparing the same.
  • a hierarchical porous material formed by first-order pore aggregates formed by aggregation of nanoparticles, secondary pore aggregates formed by re-aggregation of primary pore aggregates, and secondary pore aggregates connected to each other;
  • the primary pore aggregate has a first-order pore, the primary pore has a pore diameter of 5 to 500 nm; the secondary pore aggregate has a secondary pore, and the secondary pore has a pore diameter of 1-5 ⁇ m.
  • the nanoparticles have a diameter of 20 to 300 nm, and the size of the first-order pore aggregates is 0.5 to 5 ⁇ m.
  • the graded porous material is a metal, and the metal is one or two or more of silver, copper, zinc, iron, aluminum, magnesium, and lead.
  • the graded porous material is a noble metal coated non-precious metal, the noble metal is one of platinum, palladium, gold and rhodium; the non-precious metal is one or two of silver, copper, zinc, iron, aluminum, magnesium and lead.
  • the above alloy; the precious metal in the porous material has a mass content of 1% to 99%.
  • the graded porous material is a metal/metal oxide composite.
  • the metal is one or more of silver, copper, zinc, iron, aluminum, magnesium, lead; the metal oxide is manganese oxide, iron oxide, cobalt oxide, nickel oxide, copper oxide, zinc oxide
  • One or more of the metal oxides have a mass content of 1% to 99% in the porous material.
  • the graded porous material is a metal/corresponding metal salt precipitated composite material; the metal is one or more alloys of silver, copper, zinc, iron, aluminum, magnesium, lead; metal salt precipitates correspond to silver and copper Zinc, iron, aluminum, magnesium and lead are respectively silver chloride, copper carbonate, zinc sulfide, iron phosphate, aluminum phosphate, magnesium phosphate, lead sulfide, and the metal salt has a mass content of 1% to 99% in the porous material.
  • the method for preparing the graded porous material comprises the following steps,
  • the step (2) is a complete reduction or an incomplete reduction; the complete reduction produces a graded porous metal material; and the incomplete reduction produces a composite material of a graded porous metal/corresponding metal salt precipitate.
  • the method for preparing the graded porous material, when the graded porous material is a noble metal-coated non-precious metal further comprises placing the surface of the metal material after the reduction treatment directly or after depositing the intermediate metal element in the precious metal salt solution for the displacement reaction, or A step of sputtering a precious metal on the surface of the metal material after the reduction treatment.
  • the method for preparing the graded porous material, when the graded porous material is a metal/metal oxide composite material further comprises the step of electrodepositing the metal oxide surface on the surface of the metal material after the reduction treatment.
  • the electrolyte in the step (1) contains an anion having a molar concentration of >1 mM, and the anion is one or two of PO 4 3- , S 2 - , CO 3 2- , Cl - , Br - , I - More specifically, the electrolyte contains a cation having a molar concentration of more than 1 mM, and the cation is one or more of Na + , K + , and H + .
  • the method for preparing the classified porous material, the reducing method in the step (2) is one or more of electrochemical reduction, photoreduction, electron beam reduction, radiation reduction, and laser reduction.
  • the specific process of oxidizing the metal material in the electrolyte by electrochemical method is to use the metal material as a working electrode, and one of platinum, graphite rod, silver and gold
  • the counter electrode, silver/silver chloride, mercury/mercury oxide or saturated calomel is used as a reference electrode for electrochemical oxidation treatment in the electrolyte.
  • the intermediate metal element is one or two of Cu and Pb;
  • the precious metal salt solution is chloroplatinic acid, chloroauric acid, chloropalladic acid, chloroantimonic acid, One or more of platinum chloride, palladium chloride, rhodium chloride, platinum nitrate, and palladium nitrate;
  • the concentration of the noble metal salt is 1 mM to 1 M, and the displacement reaction time is 10 s to 2 h.
  • the intermediate metal element deposited on the graded porous metal surface is an underpotential deposition method or a sputtering method.
  • the method for preparing the graded porous material the electrodeposition deposition method of the metal oxide is specifically manganese nitrate, iron nitrate, cobalt nitrate, nickel nitrate, copper nitrate, zinc nitrate, manganese acetate, iron acetate, cobalt acetate, nickel acetate,
  • One or more of copper acetate and zinc acetate are electrolytes, and one of platinum, graphite rod, silver, gold, etc. is used as a counter electrode, and silver/silver chloride, mercury/mercury oxide or saturated calomel is used.
  • One of them is a reference electrode, and one or more of manganese oxide, iron oxide, cobalt oxide, nickel oxide, copper oxide, and zinc oxide are electrodeposited on the surface of the graded porous silver.
  • the method for preparing the graded porous material, the electrodeposition method is one or more of cyclic voltammetry, linear voltammetry, pulse voltammetry, potentiostatic method, and galvanostatic method.
  • the graded porous material of the present invention has the advantages of large surface area, high utilization rate of precious metals, and the like, and is beneficial to its mass transfer reaction as an oxidizing catalyst and other special fields.
  • the preparation method of the graded porous material of the invention has the advantages of being green, environmentally friendly, simple, easy to implement, low in production cost, and controllable in the pore size and porosity distribution of the graded porous material in the preparation process. When it is used as a oxidogen electrocatalyst or a photocatalyst, its catalytic activity is greatly improved.
  • Example 1 is a SEM electron micrograph of graded porous silver prepared according to Example 1.
  • Example 2 is an oxygen reduction performance curve of Comparative Example 1-3 and the classified porous silver prepared according to Example 1 as an oxygen reduction reaction electrocatalyst.
  • Example 3 is an oxygen reduction activity curve of a platinum-coated silver graded porous material of Comparative Example 1 and Example 2.
  • FIG 2 and Comparative Example 4 Preparation Example 3 MnO X / Ag grade oxygen reduction activity curve of the porous material.
  • Example 5 is a SEM electron micrograph of a porous Ag/AgI graded porous material prepared according to Example 4.
  • Comparative Example 1 Commercial 20% Pt/C (Johnson Matthey, USA) catalyst.
  • Comparative Example 2 Ag rotating disk electrode (round, diameter 5 mm) (Tianjin Aida Hengyi Technology Development Co., Ltd.).
  • Comparative Example 3 Pt rotating disk electrode (circular, diameter 5 mm) (Tianjin Aida Hengyi Technology Development Co., Ltd.).
  • Example 1 A solution containing 0.005 M NaCl and 0.1 M NaOH was set and used as an electrolyte, a silver block electrode having a diameter of 5 mm was used as a working electrode, a platinum plate was a counter electrode, and a mercury/mercury oxide electrode was a reference electrode. After electrochemical treatment for 2 h at 1.0 V (vs. reversible hydrogen electrode) and electrochemical reduction at 0.15 V (relative to the reversible hydrogen electrode) for 5 min in a 0.1 M NaOH electrolyte, graded porous silver was obtained.
  • Example 2 A solution containing 0.005 M NaCl and 0.1 M NaOH was set and used as an electrolyte, a silver block electrode having a diameter of 5 mm was used as a working electrode, a platinum plate was a counter electrode, and a mercury/mercury oxide electrode was a reference electrode. Porous silver was obtained by electrochemical treatment at 1.0 V (relative to the reversible hydrogen electrode) for 2 h and then electrochemical reduction at 0.15 V (relative to the reversible hydrogen electrode) for 5 min in a 0.1 M NaOH electrolyte. The obtained classified porous silver was immersed in an electrolytic solution containing 50 mM of chloroplatinic acid for 10 minutes. A platinum-coated silver graded porous material was obtained after washing.
  • Example 3 A solution containing 0.005 M NaCl and 0.1 M NaOH was set and used as an electrolyte, a silver block electrode having a diameter of 5 mm was used as a working electrode, a platinum plate was a counter electrode, and a mercury/mercury oxide electrode was a reference electrode. Porous silver was obtained by electrochemical treatment at 1.0 V (relative to the reversible hydrogen electrode) for 2 h and then electrochemical reduction at 0.15 V (relative to the reversible hydrogen electrode) for 5 min in a 0.1 M NaOH electrolyte.
  • a solution containing 50 mM manganese nitrate was prepared and used as an electrolyte, porous silver was used as a working electrode, a platinum plate was used as a counter electrode, and a silver/silver chloride electrode was used as a reference electrode for electrochemical deposition to obtain a MnO X /Ag graded porous material. sample.
  • Example 4 A solution containing 0.005 M NaI and 0.1 M NaOH was placed and used as an electrolyte, a silver block electrode having a diameter of 5 mm was used as a working electrode, a platinum plate was a counter electrode, and a mercury/mercury oxide electrode was a reference electrode.
  • the Ag/AgI graded porous material was obtained by electrochemically treating at 1.0 V (relative to the reversible hydrogen electrode) for 8 hours and then electrochemically reducing it at 0.1 V (relative to the reversible hydrogen electrode) for 11 s in a 0.1 M NaOH electrolyte.
  • Example 5 A solution containing 0.001 mM NaCl was prepared and used as an electrolyte, with a silver plate as a working electrode, a graphite rod as a counter electrode, and a silver/silver chloride electrode as a reference electrode at 1.5 V (relative to a reversible hydrogen) The electrode was subjected to electrochemical treatment for 100 hours and then irradiated for 1 hour under strong light of 200,000 lux to obtain graded porous silver.
  • Example 6 A solution containing 0.1 M HCl was used as an electrolyte, an Ag sheet was used as a working electrode, a Pt sheet was used as a counter electrode, and a saturated calomel electrode was a reference electrode, which was electrochemically treated at 2.0 V for 1 hour. A 1W laser was irradiated for 1 hour to obtain a graded porous silver.
  • Example 7 Dissolving a solution containing 2M NaBr and 0.1M HBr as an electrolyte, using a silver rod as a work As the electrode, the silver plate is the counter electrode, and the saturated calomel electrode is the reference electrode. After electrochemical treatment for 1 s at 5.0 V, the target X-ray is irradiated for 1 hour to obtain the graded porous silver.
  • Example 8 A solution of saturated NaBr was prepared and used as an electrolyte, sintered silver powder as a working electrode, a gold piece as a counter electrode, and a silver/silver chloride electrode as a reference electrode, which was electrochemically treated at 10.0 V for 60 s. The electron gun bundle was bombarded for 40 min to obtain graded porous silver.
  • Example 9 A solution containing 0.001 mM NaI was set up as an electrolyte with a silver plate as the working electrode, a graphite rod as the counter electrode, and a silver/silver chloride electrode as the reference electrode at 0.5 V (relative to the reversible hydrogen) The electrode was subjected to electrochemical treatment for 100 hours and then heated at 400 ° C for 10 hours to obtain a graded porous silver.
  • Example 10 A solution containing 2M NaI and 0.1M HI was prepared and used as an electrolyte, a silver rod was used as a working electrode, a silver plate was used as a counter electrode, and a saturated calomel electrode was a reference electrode, which was electrochemically treated at 5.0 V. After 60 s, aluminum target X-ray irradiation was carried out for 1 hour to obtain graded porous silver.
  • Example 11 A solution containing 0.1 M cetyltrimethylammonium chloride and 0.1 M NaOH was used as an electrolyte, a silver plate was used as a working electrode, a graphite rod was a counter electrode, and a silver/silver chloride electrode was used.
  • graded porous silver was obtained by electrochemical treatment at 1.5 V (relative to the reversible hydrogen electrode) for 1 h and then under strong light of 300,000 lux for 20 min.
  • Example 12 A solution containing 0.5 M 1,3-dimethylimidazolium bromide and 0.1 M NaOH was used as an electrolyte, a silver rod was used as a working electrode, a silver plate was used as a counter electrode, and a saturated calomel electrode was used as a reference.
  • the specific electrode was electrochemically treated at 2.0 V (relative to the reversible hydrogen electrode) for 5 hours, and then subjected to aluminum target X-ray irradiation for 2 hours to obtain graded porous silver.
  • Example 13 A solution containing 2 M NaCl and 0.1 M HCl was set up as an electrolyte, a silver rod was used as a working electrode, a silver plate was used as a counter electrode, and a saturated calomel electrode was a reference electrode, which was electrochemically treated at 5.0 V. After 360 s, copper target X-ray irradiation was carried out for 1 hour to obtain graded porous silver. The obtained porous silver was immersed in an electrolytic solution containing 50 mM of chloropalladium acid for 10 minutes. After washing, a graded porous material of palladium-coated silver is obtained.
  • Example 14 A solution of saturated NaCl was prepared and used as an electrolyte, sintered silver powder as a working electrode, a gold piece as a counter electrode, and a silver/silver chloride electrode as a reference electrode, which was electrochemically treated at 10.0 V for 1 s.
  • the electron gun bundle was bombarded for 20 min to obtain graded porous silver.
  • the obtained porous silver was deposited under an underpotential of 390 mV (relative to the reversible hydrogen electrode) in a solution of 50 mM copper nitrate and 50 mM nitric acid for 5 min, and further immersed in an electrolytic solution containing 50 mM of chloroauric acid for 10 min. After washing, a graded porous material of gold-coated silver is obtained.
  • Example 15 A solution containing 0.1 M HCl was used as an electrolyte, an Ag sheet was used as a working electrode, a Pt sheet was a counter electrode, and a saturated calomel electrode was a reference electrode, which was electrochemically treated at 2.0 V for 1 hour. A 1W laser was irradiated for 1 hour to obtain a graded porous silver. The obtained porous silver was immersed in an electrolytic solution containing 50 mM of chlorodecanoic acid for 10 minutes. After washing, a graded porous material coated with silver is obtained.
  • Example 16 A solution containing 0.005 M NaBr and 0.1 M NaOH was set and used as an electrolyte, a silver block electrode having a diameter of 5 mm was used as a working electrode, a platinum plate was a counter electrode, and a mercury/mercury oxide electrode was a reference electrode. After electrochemical treatment at 1.0 V (relative to the reversible hydrogen electrode) for 20 h and electrochemical reduction at 0.3 V (relative to the reversible hydrogen electrode) for 10 min in a 0.1 M NaOH electrolyte, graded porous silver was obtained. The obtained porous silver was immersed in an electrolytic solution containing 50 mM of chloroplatinic acid for 10 minutes. A platinum-coated silver graded porous material was obtained after washing.
  • Example 17 A solution of saturated NaBr was prepared and used as an electrolyte, sintered silver powder as a working electrode, a gold piece as a counter electrode, and a silver/silver chloride electrode as a reference electrode, which was electrochemically treated at 10.0 V for 60 s.
  • the electron gun bundle was bombarded for 40 min to obtain graded porous silver.
  • the obtained porous silver was immersed in an electrolytic solution containing 50 mM of palladium chloride and 50 mM of nitric acid for 10 minutes. After washing, a graded porous material of palladium-coated silver is obtained.
  • Example 18 A solution containing 0.1 M HBr was used as an electrolyte, an Ag sheet was used as a working electrode, a Pt sheet was used as a counter electrode, and a saturated calomel electrode was a reference electrode, which was electrochemically treated at 2.0 V for 1 hour.
  • a 2W laser was irradiated for 3 hours to obtain a graded porous silver.
  • the obtained porous silver was deposited under an underpotential of -210 mV (relative to the reversible hydrogen electrode) in a solution of 50 mM lead nitrate and 50 mM nitric acid for 5 min, and then in an electrolyte containing 50 mM of chloroplatinic acid. Dip for 10 min.
  • a platinum-coated silver graded porous material was obtained after washing.
  • Example 19 A solution containing 0.001 mM NaI was placed and used as an electrolyte with a silver plate as the working electrode, a graphite rod as the counter electrode, and a silver/silver chloride electrode as the reference electrode at 0.5 V (relative to the reversible hydrogen) The electrode was subjected to electrochemical treatment for 100 hours and then heated at 400 ° C for 10 hours to obtain a graded porous silver. The obtained classified porous silver was immersed in an electrolytic solution containing 50 mM of platinum chloride and 50 mM of nitric acid for 10 minutes. A platinum-coated silver graded porous material was obtained after washing.
  • Example 20 A solution containing 0.001 mM NaCl was prepared and used as an electrolyte with a silver plate as a working electrode, a graphite rod as a counter electrode, and a silver/silver chloride electrode as a reference electrode at 1.5 V (relative to a reversible hydrogen) The electrode was subjected to electrochemical treatment for 100 hours and then irradiated for 1 hour under strong light of 200,000 lux to obtain porous silver.
  • a solution containing 50 mM copper nitrate was prepared and used as an electrolyte, porous silver was used as a working electrode, a platinum plate was used as a counter electrode, and a silver/silver chloride electrode was used as a reference electrode for electrochemical deposition to obtain a CuO X /Ag graded porous material. .
  • Example 21 A solution of saturated NaCl was prepared and used as an electrolyte, sintered silver powder as a working electrode, a gold piece as a counter electrode, and a silver/silver chloride electrode as a reference electrode, which was electrochemically treated at 10.0 V for 1 s. The electron gun bundle was bombarded for 20 min to obtain porous silver. A solution containing 50 mM cobalt nitrate was prepared and used as an electrolyte, porous silver was used as a working electrode, a platinum plate was used as a counter electrode, and a silver/silver chloride electrode was used as a reference electrode for electrochemical deposition to obtain a CoO X /Ag graded porous material. .
  • Example 22 A solution containing 0.001 mM NaBr was prepared and used as an electrolyte with a silver plate as the working electrode, a graphite rod as the counter electrode, and a silver/silver chloride electrode as the reference electrode at 1.5 V (relative to the reversible hydrogen) Porous silver was obtained by electrochemically treating the electrode for 100 hours and then irradiating it under strong light of 500,000 lux for 5 minutes.
  • a solution containing 50 mM zinc nitrate was prepared and used as an electrolyte, porous silver was used as a working electrode, a platinum plate was used as a counter electrode, and a silver/silver chloride electrode was used as a reference electrode for electrochemical deposition to obtain a ZnO X /Ag graded porous material. .
  • Example 23 A solution containing 2 M NaCl and 0.1 M HCl was set up as an electrolyte, a silver rod was used as a working electrode, a silver plate was used as a counter electrode, and a saturated calomel electrode was used as a reference electrode, and electrochemically treated at 5.0 V. After 360 s, copper target X-ray irradiation was carried out for 1 hour to obtain porous silver.
  • a solution containing 50 mM iron acetate was prepared and used as an electrolyte, porous silver was used as a working electrode, a platinum plate was used as a counter electrode, and a silver/silver chloride electrode was used as a reference electrode for electrochemical deposition to obtain a FeO X /Ag graded porous material. .
  • Example 24 A solution containing 0.1 M HCl was used as an electrolyte, an Ag sheet was used as a working electrode, a Pt sheet was a counter electrode, and a saturated calomel electrode was a reference electrode, which was electrochemically treated at 2.0 V for 1 hour. Porous silver was obtained by laser irradiation of 1 W for 1 h. A solution containing 50 mM nickel acetate was prepared and used as an electrolyte, porous silver was used as a working electrode, a platinum plate was used as a counter electrode, and a silver/silver chloride electrode was used as a reference electrode for electrochemical deposition to obtain a NiO X /Ag graded porous material. .
  • Example 25 A solution containing 2 M NaCl and 0.1 M HCl was set up as an electrolyte, a silver rod was used as a working electrode, a silver plate was used as a counter electrode, and a saturated calomel electrode was a reference electrode, which was electrochemically treated at 5.0 V. After 360 s, copper target X-ray irradiation for 5 s was performed to obtain Ag/AgCl graded porous material.
  • Example 26 A solution containing 0.001 mM NaBr was prepared and used as an electrolyte with a silver plate as the working electrode, a graphite rod as the counter electrode, and a silver/silver chloride electrode as the reference electrode at 1.5 V (relative to the reversible hydrogen) The electrode was subjected to electrochemical treatment for 100 h and then irradiated for 20 s under strong light of 500 lux to obtain Ag/AgBr graded porous material.
  • Example 27 A solution containing 2 M NaI and 0.1 M HI was set up as an electrolyte, a silver rod was used as a working electrode, a silver plate was used as a counter electrode, and a saturated calomel electrode was a reference electrode, which was electrochemically treated at 5.0 V. After 60 s, the aluminum target X-ray was irradiated for 20 s to obtain Ag/AgI graded porous material.
  • Example 28 A solution of saturated NaI was prepared and used as an electrolyte, sintered silver powder as a working electrode, a gold piece as a counter electrode, and a silver/silver chloride electrode as a reference electrode, which was electrochemically treated at 10.0 V for 10 s. The electron gun bundle was bombarded for 20 s to obtain Ag/AgI graded porous material.
  • Example 29 A solution containing 0.1 M Na 3 PO 4 was prepared and used as an electrolyte, a magnesium sheet was used as a working electrode, a platinum sheet was a counter electrode, and a mercury/mercury oxide electrode was a reference electrode, first at 2.5 V (relatively Electrochemical oxidation treatment was carried out under a reversible hydrogen electrode for 2 h, followed by electrochemical reduction for 200 s at -1.5 V (relative to the reversible hydrogen electrode) to obtain porous magnesium.
  • Example 30 A solution containing 0.3 M Na 3 PO 4 was prepared and used as an electrolyte, an aluminum foil was used as a working electrode, a platinum plate was a counter electrode, and a saturated calomel electrode was a reference electrode, first at 2.0 V (relative to reversible) Electrochemical oxidation treatment was carried out for 1 h under a hydrogen electrode, followed by electrochemical reduction for 150 s at -1.0 V (relative to a reversible hydrogen electrode) to obtain porous aluminum.
  • Example 31 A solution containing 0.4 M Na 2 S was prepared and used as an electrolyte zinc plate as a working electrode, a platinum plate as a counter electrode, and a mercury/mercury oxide electrode as a reference electrode, first at 1.8 V (relative to reversible) Electrochemical oxidation treatment was carried out for 30 min under a hydrogen electrode, followed by electrochemical reduction for 100 s at -1.3 V (relative to a reversible hydrogen electrode) to obtain porous zinc.
  • Example 32 A solution containing 0.5 M Na 3 PO 4 was prepared and used as an electrolyte, an iron piece was used as a working electrode, a platinum plate was a counter electrode, and a silver/silver chloride electrode was first at 2.6 V (relative to a reversible hydrogen) The electrode was subjected to electrochemical oxidation treatment for 1.5 h, and then electrochemical reduction was carried out for 300 s at -1.2 V (relative to the reversible hydrogen electrode) to obtain porous iron.
  • Example 33 Preparing a solution containing 0.6 M Na 2 S and using it as an electrolyte, a lead plate as a working electrode, a platinum plate as a counter electrode, and a mercury/mercury oxide electrode as a reference electrode, first at 2.0 V (relative to 2.0 V) Electrochemical oxidation treatment was carried out for 2.5 h under a reversible hydrogen electrode, followed by electrochemical reduction for 500 s at -0.9 V (relative to the reversible hydrogen electrode) to obtain porous lead.
  • Example 34 A solution containing 0.7 M Na 2 CO 3 was prepared and used as an electrolyte, a copper plate was used as a working electrode, a platinum plate was a counter electrode, and a mercury/mercury oxide electrode was a reference electrode, first at 1.5 V (relatively Electrolytic oxidation treatment was carried out for 4 h under a reversible hydrogen electrode, followed by electrochemical reduction for 1000 s at -1.4 V (relative to the reversible hydrogen electrode) to obtain porous copper.
  • Example 1 is a SEM electron micrograph of a graded porous silver obtained according to Example 1.
  • the obtained porous silver has a multi-stage pore structure. It can be seen from the analysis that the primary pores are formed by the voids left by the aggregation of the silver nanoparticles, and the secondary pores are again formed by the primary pore silver aggregates. Formed by the voids left during the gathering.
  • the primary pore has a pore diameter of 5 to 500 nm, and the secondary pore has a pore diameter of 1-5 ⁇ m.
  • Example 2 is an oxygen reduction performance curve of Comparative Example 1-3 and the classified porous silver prepared according to Example 1 as an oxygen reduction reaction electrocatalyst.
  • the prepared graded porous silver has an optimum oxygen reduction property due to its large specific surface area and pore structure favorable for mass transfer.
  • Example 3 is an oxygen reduction activity curve of samples prepared in Comparative Example 1 and Example 2. It can be seen from the figure that the platinum-coated silver graded porous material serves as an oxygen reduction catalyst due to the specific surface area activity close to that of the commercial carbon supported platinum catalyst.
  • Example 4 is an oxygen reduction activity curve of samples prepared in Comparative Example 2 and Example 3. As shown in the figure, the oxidogen catalytic activity of the polycrystalline silver electrode deposited after the deposition of manganese oxide is greatly improved.
  • Example 5 is a SEM electron micrograph of an Ag/AgI composite prepared according to Example 4; the graded porous Ag/AgI is composed of silver iodide nanoparticles covered by silver nanoparticles; as shown, the diameter of the silver nanoparticles is 10-90 nm.
  • the silver iodide nanoparticles have a side length of 0.1 to 0.5 ⁇ m.

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Abstract

一种分级多孔材料及其制备方法。一种分级多孔材料，由纳米粒子聚集形成的一级孔聚集体再次聚集形成的二级孔聚集体相互连接而形成；所述一级孔聚集体上具有一级孔，一级孔的孔径为 5-500 nm；所述二级孔聚集体上具有二级孔，二级孔的孔径为 1-5um。所述分级多孔材料具有表面积大、活性成分利用率高等优点，有助于其作为氧化原催化剂及其它特殊领域应用时的传质反应和催化反应。分级多孔材料的制备方法具有绿色环保、简便、易于实施、生产成本低；以及制备过程中分级多孔材料的孔径及孔隙率分布可控等优点。

Description

一种分级多孔材料及其制备方法 技术领域
本发明属于纳米材料领域，具体的说涉及一种分级多孔材料及其制备方法。
背景技术
纳米多孔材料是近年来发展起来的一类新型纳米结构材料，由于它具有比表面积大、密度小、结构灵活可调、渗透性好等特点，使得多孔材料被广泛地应用于分离、催化、传感、医药、电极、机械等领域。
制备多孔金属的一种常用方法是脱合金法和模板法。马正青等(CN101391304A)利用脱合金法得到了高比表面积的多孔银粉，其步骤是：采用氩气保护熔炼金属镁，待镁完全熔融后加入金属银，二者混合后浇铸，将冷却后的浇铸品机械破碎、球磨、分级；用混合酸腐蚀达到粒径要求的银-镁合金粉，再经过洗涤、过滤、干燥等后处理即可得到多孔银粉。但由于原材料制备所需要的冶金熔炼过程需要在较高的温度才可以完成，并且需要惰性气体保护，所以对设备要求较高。同时，在接下来的电化学溶解过程中，也需要不断调整和优化参数，并且通常采用硝酸、硫酸等强腐蚀性溶液作为腐蚀电解液，所以脱合金方法在应用过程中对操作人员与环境都存在危害。Jin R H和Yuan JJ(Journal of Materials Chemistry 15(2005)4513)以聚乙亚胺为模板制得大孔的银粉。模板法，工艺相对复杂，成本高，难以实现工业化生产，同时采用上述方法制备的银的孔隙结构单一，且难以控制。
Adzic研究组发现通过Cu-UPD在贵金属粒子表面形成单层Cu原子，再与Pt2+进行置换得到Pt单层催化剂，高度分散的Pt使得该类催化剂的ORR比质量活性大大提高。然而其内核一般采用Pd、Au等贵金属及其合金，成本较高。Ag相对与Pt、Pd、Au等贵金属而言，具有储量多，价格低得优势，然而对其研究较少。多孔银由于其表面积大，有利于传质等优点在催化领域显示出了良好的应用前景，由于银不耐酸腐蚀，限制了其在酸性环境中的应用，以Pt、Pd等贵金属为壳材料，以多孔银为核材料制备多孔核壳结构的催化剂可以使其在酸性环境中的应用，但此方面的研究还未见报道。
由于银在碱性介质中具有较高活性和稳定性以及优异的抗甲醇渗透能力等优势，引起了研究人员的广泛关注。在碱性燃料电池领域已有商品Ag/C电催化剂，但其氧还原(ORR)过电位比Pt/C高100～150mV(J.Electrochem.Soc.152(2005)D117)。文献(Electrochem.Commun.31(2013)108)将Ag与Co3O4复合提高了其ORR活性；唐等人(Appl.Catal.B:Environ.104(2011)337)采用一步法制备的Ag/Mn3O4/C电催化剂将其与Pt/C过电位差距缩小到了31mV，说明银与一些锰、钴等氧化物复合能够提高其ORR活性。Linic等人(Nature Chem.6(2014)828)通过量子化学计算证明AgCo形成合金能提高ORR活性，并且制备了表面是合金的AgCo电催化剂，较银的ORR活性有较大提高，但其ORR活性与Pt/C催化剂相比仍有一定的差距。
发明内容
本发明针对现有技术中存在的问题，发明了一种多孔材料及其制备方法。
为实现上述发明内容，本发明采用以下技术方案来实现：
一种分级多孔材料，所述分级多孔材料由纳米粒子聚集形成的一级孔聚集体、一级孔聚集体再次聚集形成的二级孔聚集体、二级孔聚集体相互连接而形成；所述一级孔聚集体上具有一级孔，一级孔的孔径为5-500nm；所述二级孔聚集体上具有二级孔，二级孔的孔径为1-5μm。
所述纳米粒子的直径为20-300nm，一级孔聚集体的大小为0.5-5μm。
所述分级多孔材料为金属，金属为银、铜、锌、铁、铝、镁、铅中的一种或两种以上的合金。
所述分级多孔材料为贵金属包覆的非贵金属，贵金属为铂、钯、金、铱中的一种；非贵金属为银、铜、锌、铁、铝、镁、铅中的一种或两种以上的合金；贵金属于多孔材料中的质量含量1％-99％。
所述分级多孔材料为金属/金属氧化物复合材料。；金属为银、铜、锌、铁、铝、镁、铅中的一种或两种以上的合金；金属氧化物为氧化锰、氧化铁、氧化钴、氧化镍、氧化铜、氧化锌中的一种或两种以上，金属氧化物于多孔材料中的质量含量1％-99％。
所述分级多孔材料为金属/相应的金属盐沉淀复合材料；金属为银、铜、锌、铁、铝、镁、铅中的一种或两种以上的合金；金属盐沉淀相应于银、铜、锌、铁、铝、镁、铅分别为氯化银、碳酸铜、硫化锌、磷酸铁、磷酸铝、磷酸镁、硫化铅，金属盐于多孔材料中的质量含量1％-99％。
所述分级多孔材料的制备方法，包括以下步骤，
(1)采用电化学方法于电解液中对金属材料进行氧化处理；
(2)对步骤(1)所得处理后的金属材料进行还原。
所述步骤(2)为完全还原或不完全还原；所述完全还原制得的为分级多孔金属材料；所述不完全还原制得的为分级多孔的金属/相应的金属盐沉淀的复合材料。
所述分级多孔材料的制备方法，当分级多孔材料为贵金属包覆的非贵金属时，还包括将还原处理后的金属材料表面直接或沉积中间金属元素后置于贵金属盐溶液中进行置换反应，或者在还原处理后的金属材料表面溅射贵金属的步骤。
所述分级多孔材料的制备方法，当分级多孔材料为金属/金属氧化物复合材料时，还包括将将还原处理后的金属材料表面电沉积金属氧化物的步骤。
步骤(1)中所述电解液中含有摩尔浓度＞1mM的阴离子，所述阴离子为PO4 3-、S2-、CO3 2-，Cl-、Br-、I-中的一种或两种以上，所述电解液中同时含有摩尔浓度大于1mM的阳离子，所述阳离子为Na+、K+、H+中的一种或者两种以上。
所述分级多孔材料的制备方法，步骤(2)所述还原方法为电化学还原、光照还原、电子束还原、辐射还原、激光还原中的一种或两种以上。
所述分级多孔材料的制备方法，采用电化学方法于电解液中对金属材料进行氧化处理的具体过程为以所述金属材料为工作电极，以铂、石墨棒、银、金中的一种为对电极，银/氯化银、汞/氧化汞或饱和甘汞为参比电极，于电解液中进行电化学氧化处理。
当分级多孔材料为贵金属包覆的非贵金属时，所述中间金属元素为Cu、Pb中的一种或两种；贵金属盐溶液为氯铂酸、氯金酸、氯钯酸、氯铱酸、氯化铂、氯化钯、氯化铱、硝酸铂、硝酸钯中的一种或两种以上；所述贵金属盐的浓度为1mM～1M，所述置换反应时间为10s～2h。
所述多孔材料的制备方法，所述分级多孔金属表面沉积中间金属元素为欠电位沉积法或者溅射法。
所述分级多孔材料的制备方法，金属氧化物的电沉积沉积方法具体为以硝酸锰、硝酸铁、硝酸钴、硝酸镍、硝酸铜、硝酸锌、醋酸锰、醋酸铁、醋酸钴、醋酸镍、醋酸铜、醋酸锌中的一种或两种以上为电解液，以铂、石墨棒、银、金等中的一种为对电极，以银/氯化银、汞/氧化汞或饱和甘汞中的一种为参比电极，在分级多孔银表面电沉积氧化锰、氧化铁、氧化钴、氧化镍、氧化铜、氧化锌中的一种或两种以上。
所述分级多孔材料的制备方法，电沉积方法为循环伏安法、线性伏安法、脉冲伏安法、恒电位法、恒电流法中的一种或两种以上。
与现有技术相比，本发明所述分级多孔材料具有表面积大、贵金属利用率高等优点，有助于其作为氧化原催化剂及其它特殊领域应用时的传质反应。本发明所述分级多孔材料的制备方法具有绿色环保、简便、易于实施、生产成本低；以及制备过程中分级多孔材料的孔径及孔隙率分布可控等优点。将其用作氧化原电催化剂或光催化剂时，其催化活性大幅提高。
附图说明
图1为根据实实施例1制备的分级多孔银的SEM电镜图片；
图2为比较例1-3和根据实实施例1制备的分级多孔银作为氧还原反应电催化剂时的氧还原性能曲线。
图3为比较例1和实施例2制备铂包覆银的分级多孔材料的氧还原活性曲线。
图4为比较例2和实施例3制备MnOX/Ag分级多孔材料的氧还原活性曲线。
图5为根据实施例4制备的多孔Ag/AgI分级多孔材料的SEM电镜图片。
具体实施方式
下面结合实施例对本发明做详细的描述。当然本发明并不仅限于这些具体的实施例。
比较例1：商品20％Pt/C(Johnson Matthey，USA)催化剂。
比较例2：Ag旋转盘电极(圆形，直径为5mm)(天津艾达恒晟科技发展有限公司)。
比较例3：Pt旋转盘电极(圆形，直径为5mm)(天津艾达恒晟科技发展有限公司)。
实施例1：配置含0.005M NaCl和0.1M NaOH的溶液并将其作为电解液，直径为5mm的银块状电极作为工作电极，铂片为对电极，汞/氧化汞电极为参比电极，在1.0V(相对于可逆氢电极)下电化学处理2h后再在0.1M NaOH电解液中在0.15V(相对于可逆氢电极)下进行电化学还原5min得到分级多孔银。
实施例2：配置含0.005M NaCl和0.1M NaOH的溶液并将其作为电解液，直径为5mm的银块状电极作为工作电极，铂片为对电极，汞/氧化汞电极为参比电极，在1.0V(相对于可逆氢电极)下电化学处理2h后再在0.1M NaOH电解液中在0.15V(相对于可逆氢电极)下进行电化学还原5min得到多孔银。将得到的分级多孔银在含有50mM的氯铂酸的电解液中浸渍10min。清洗之后得到铂包覆银的分级多孔材料。
实施例3：配置含0.005M NaCl和0.1M NaOH的溶液并将其作为电解液，直径为5mm的银块状电极作为工作电极，铂片为对电极，汞/氧化汞电极为参比电极，在1.0V(相对于可逆氢电极)下电化学处理2h后再在0.1M NaOH电解液中在0.15V(相对于可逆氢电极)下进行电化学还原5min得到多孔银。配制含50mM硝酸锰的溶液并将其作为电解液，多孔银作为工作电极，铂片为对电极，银/氯化银电极为参比电极，进行电化学沉积，得到MnOX/Ag分级多孔材料样品。
实施例4：配置含0.005M NaI和0.1M NaOH的溶液并将其作为电解液，直径为5mm的银块状电极作为工作电极，铂片为对电极，汞/氧化汞电极为参比电极，在1.0V(相对于可逆氢电极)下电化学处理8h后再在0.1M NaOH电解液中在0.5V(相对于可逆氢电极)下进行电化学还原11s得到Ag/AgI分级多孔材料。
实施例5：配置含0.001mM NaCl的溶液并将其作为电解液，以银片作为工作电极，石墨棒为对电极，银/氯化银电极为参比电极，在1.5V(相对于可逆氢电极)下电化学处理100h后再在20万勒克斯的强光照下照射1h得到分级多孔银。
实施例6：配置含0.1M HCl的溶液并将其作为电解液，Ag片作为工作电极，Pt片为对电极，饱和甘汞电极为参比电极，在2.0V下电化学处理1h后再进行1W的激光照射1h得到分级多孔银。
实施例7：配置含2M NaBr和0.1M HBr的溶液并将其作为电解液，以银棒作为工 作电极，银片为对电极，饱和甘汞电极为参比电极，在5.0V下电化学处理1s后再进行镁靶X射线照射1h得到分级多孔银。
实施例8：配置饱和NaBr的溶液并将其作为电解液，烧结银粉作为工作电极，金片为对电极，银/氯化银电极为参比电极，在10.0V下电化学处理60s后再用电子枪束轰击40min得到分级多孔银。
实施例9：配置含0.001mM NaI的溶液并将其作为电解液，以银片作为工作电极，石墨棒为对电极，银/氯化银电极为参比电极，在0.5V(相对于可逆氢电极)下电化学处理100h后再进行400℃加热10h还原得到分级多孔银。
实施例10：配置含2M NaI和0.1M HI的溶液并将其作为电解液，以银棒作为工作电极，银片为对电极，饱和甘汞电极为参比电极，在5.0V下电化学处理60s后再进行铝靶X射线照射1h得到分级多孔银。
实施例11：配置含0.1M十六烷基三甲基氯化铵和0.1M NaOH的溶液并将其作为电解液，以银片作为工作电极，石墨棒为对电极，银/氯化银电极为参比电极，在1.5V(相对于可逆氢电极)下电化学处理1h后再在30万勒克斯的强光照下照射20min得到分级多孔银。
实施例12：配置含0.5M 1,3-二甲基咪唑溴盐和0.1M NaOH的溶液并将其作为电解液，以银棒作为工作电极，银片为对电极，饱和甘汞电极为参比电极，在2.0V(相对于可逆氢电极)下电化学处理5h后，再进行铝靶X射线照射2h得到分级多孔银。
实施例13：配置含2M NaCl和0.1M HCl的溶液并将其作为电解液，以银棒作为工作电极，银片为对电极，饱和甘汞电极为参比电极，在5.0V下电化学处理360s后再进行铜靶X射线照射1h得到分级多孔银。将得到的多孔银在含有50mM的氯钯酸的电解液中浸渍10min。清洗之后得到钯包覆银的分级多孔材料。
实施例14：配置饱和NaCl的溶液并将其作为电解液，烧结银粉作为工作电极，金片为对电极，银/氯化银电极为参比电极，在10.0V下电化学处理1s后再用电子枪束轰击20min得到分级多孔银。将得到的多孔银在50mM硝酸铜和50mM硝酸的溶液中390mV(相对于可逆氢电极)欠电位沉积5min，再在含有50mM的氯金酸的电解液中浸渍10min。清洗之后得到金包覆银的分级多孔材料。
实施例15：配置含0.1M HCl的溶液并将其作为电解液，Ag片作为工作电极，Pt片为对电极，饱和甘汞电极为参比电极，在2.0V下电化学处理1h后再进行1W的激光照射1h得到分级多孔银。将得到的多孔银在含有50mM的氯铱酸的电解液中浸渍10min。清洗之后得到铱包覆银的分级多孔材料。
实施例16：配置含0.005M NaBr和0.1M NaOH的溶液并将其作为电解液，直径为5mm的银块状电极作为工作电极，铂片为对电极，汞/氧化汞电极为参比电极，在1.0V(相对于可逆氢电极)下电化学处理20h后再在0.1M NaOH电解液中在0.3V(相对于可逆氢电极)下进行电化学还原10min得到分级多孔银。将得到的多孔银在含有50mM的氯铂酸的电解液中浸渍10min。清洗之后得到铂包覆银的分级多孔材料。
实施例17：配置饱和NaBr的溶液并将其作为电解液，烧结银粉作为工作电极，金片为对电极，银/氯化银电极为参比电极，在10.0V下电化学处理60s后再用电子枪束轰击40min得到分级多孔银。将得到的多孔银在含有50mM的氯化钯和50mM的硝酸的电解液中浸渍10min。清洗之后得到钯包覆银的分级多孔材料。
实施例18：配置含0.1M HBr的溶液并将其作为电解液，Ag片作为工作电极，Pt片为对电极，饱和甘汞电极为参比电极，在2.0V下电化学处理1h后再进行2W的激光照射3h得到分级多孔银。将得到的多孔银在50mM硝酸铅和50mM硝酸的溶液中-210mV(相对于可逆氢电极)欠电位沉积5min，再在含有50mM的氯铂酸的电解液中 浸渍10min。清洗之后得到铂包覆银的分级多孔材料。
实施例19：配置含0.001mM NaI的溶液并将其作为电解液，以银片作为工作电极，石墨棒为对电极，银/氯化银电极为参比电极，在0.5V(相对于可逆氢电极)下电化学处理100h后再进行400℃加热10h还原得到分级多孔银。将得到的分级多孔银在含有50mM的氯化铂和50mM的硝酸的电解液中浸渍10min。清洗之后得到铂包覆银的分级多孔材料。
实施例20：配置含0.001mM NaCl的溶液并将其作为电解液，以银片作为工作电极，石墨棒为对电极，银/氯化银电极为参比电极，在1.5V(相对于可逆氢电极)下电化学处理100h后再在20万勒克斯的强光照下照射1h得到多孔银。配制含50mM硝酸铜的溶液并将其作为电解液，多孔银作为工作电极，铂片为对电极，银/氯化银电极为参比电极，进行电化学沉积，得到CuOX/Ag分级多孔材料。
实施例21：配置饱和NaCl的溶液并将其作为电解液，烧结银粉作为工作电极，金片为对电极，银/氯化银电极为参比电极，在10.0V下电化学处理1s后再用电子枪束轰击20min得到多孔银。配制含50mM硝酸钴的溶液并将其作为电解液，多孔银作为工作电极，铂片为对电极，银/氯化银电极为参比电极，进行电化学沉积，得到CoOX/Ag分级多孔材料。
实施例22：配置含0.001mM NaBr的溶液并将其作为电解液，以银片作为工作电极，石墨棒为对电极，银/氯化银电极为参比电极，在1.5V(相对于可逆氢电极)下电化学处理100h后再在50万勒克斯的强光照下照射5min得到多孔银。配制含50mM硝酸锌的溶液并将其作为电解液，多孔银作为工作电极，铂片为对电极，银/氯化银电极为参比电极，进行电化学沉积，得到ZnOX/Ag分级多孔材料。
实施例23：配置含2M NaCl和0.1M HCl的溶液并将其作为电解液，以银棒作为工作电极，银片为对电极，饱和甘汞电极为参比电极，在5.0V下电化学处理360s后再进行铜靶X射线照射1h得到多孔银。配制含50mM醋酸铁的溶液并将其作为电解液，多孔银作为工作电极，铂片为对电极，银/氯化银电极为参比电极，进行电化学沉积，得到FeOX/Ag分级多孔材料。
实施例24：配置含0.1M HCl的溶液并将其作为电解液，Ag片作为工作电极，Pt片为对电极，饱和甘汞电极为参比电极，在2.0V下电化学处理1h后再进行1W的激光照射1h得到多孔银。配制含50mM醋酸镍的溶液并将其作为电解液，多孔银作为工作电极，铂片为对电极，银/氯化银电极为参比电极，进行电化学沉积，得到NiOX/Ag分级多孔材料。
实施例25：配置含2M NaCl和0.1M HCl的溶液并将其作为电解液，以银棒作为工作电极，银片为对电极，饱和甘汞电极为参比电极，在5.0V下电化学处理360s后再进行铜靶X射线照射5s得到Ag/AgCl分级多孔材料。
实施例26：配置含0.001mM NaBr的溶液并将其作为电解液，以银片作为工作电极，石墨棒为对电极，银/氯化银电极为参比电极，在1.5V(相对于可逆氢电极)下电化学处理100h后再在50万勒克斯的强光照下照射20s得到Ag/AgBr分级多孔材料。
实施例27：配置含2M NaI和0.1M HI的溶液并将其作为电解液，以银棒作为工作电极，银片为对电极，饱和甘汞电极为参比电极，在5.0V下电化学处理60s后再进行铝靶X射线照射20s得到Ag/AgI分级多孔材料。
实施例28：配置饱和NaI的溶液并将其作为电解液，烧结银粉作为工作电极，金片为对电极，银/氯化银电极为参比电极，在10.0V下电化学处理10s后再用电子枪束轰击20s得到Ag/AgI分级多孔材料。
实施例29：配制含0.1M的Na3PO4的溶液并将其作为电解液，镁片作为工作电极， 铂片为对电极，汞/氧化汞电极为参比电极，先在2.5V(相对于可逆氢电极)下进行电化学氧化处理2h，之后再-1.5V(相对于可逆氢电极)下进行电化学还原200s得到多孔镁。
实施例30：配制含0.3M的Na3PO4的溶液并将其作为电解液，铝箔作为工作电极，铂片为对电极，饱和甘汞电极为参比电极，先在2.0V(相对于可逆氢电极)下进行电化学氧化处理1h，之后再-1.0V(相对于可逆氢电极)下进行电化学还原150s得到多孔铝。
实施例31：配制含0.4M的Na2S的溶液并将其作为电解液锌板作为工作电极，铂片为对电极，汞/氧化汞电极为参比电极，先在1.8V(相对于可逆氢电极)下进行电化学氧化处理30min，之后再-1.3V(相对于可逆氢电极)下进行电化学还原100s得到多孔锌。
实施例32：配制含0.5M的Na3PO4的溶液并将其作为电解液，铁片作为工作电极，铂片为对电极，银/氯化银电极，先在2.6V(相对于可逆氢电极)下进行电化学氧化处理1.5h，之后再-1.2V(相对于可逆氢电极)下进行电化学还原300s得到多孔铁。
实施例33：配制含0.6M的Na2S的溶液并将其作为电解液，铅板作为工作电极，铂片为对电极，汞/氧化汞电极为参比电极，先在2.0V(相对于可逆氢电极)下进行电化学氧化处理2.5h，之后再-0.9V(相对于可逆氢电极)下进行电化学还原500s得到多孔铅。
实施例34：配制含0.7M的Na2CO3的溶液并将其作为电解液，铜片作为工作电极，铂片为对电极，汞/氧化汞电极为参比电极，先在1.5V(相对于可逆氢电极)下进行电化学氧化处理4h，之后再-1.4V(相对于可逆氢电极)下进行电化学还原1000s得到多孔铜。
图1为根据实施例1得到的分级多孔银的SEM电镜照片。从图中可以看出，所得到的多孔银具有多级孔结构，分析可知，一级孔是由银纳米粒子聚集留下的空隙形成的，而二级孔是由一级孔银聚集体再次聚集时留下的空隙而形成的。由图可知，一级孔的孔径在5-500nm，二级孔的孔径在1-5μm之间。
图2为比较例1-3和根据实实施例1制备的分级多孔银作为氧还原反应电催化剂时的氧还原性能曲线。由图可知，所制备的分级多孔银由于其大的比表面积及有利于传质的孔结构而具有最优的氧还原性能。
图3为比较例1和实施例2制备样品的氧还原活性曲线。由图中可以看出铂包覆银的分级多孔材料作为氧还原催化剂由于和商品碳载铂催化剂接近的比表面积活性。
图4为比较例2和实施例3制备样品的氧还原活性曲线。如图所示，沉积氧化锰后的样品较为沉积是的多晶银电极的氧化原催化活性有了很大程度的提高。
图5为根据实施例4制备的Ag/AgI复合材料的SEM电镜图片；分级多孔Ag/AgI由银纳米粒子覆盖的碘化银纳米粒子堆积构成；如图所示银纳米粒子的直径在10-90nm，碘化银纳米粒子的边长尺寸为0.1-0.5μm。

Claims (16)

  1. 一种分级多孔材料，其特征在于：所述分级多孔材料由纳米粒子聚集形成的一级孔聚集体、一级孔聚集体再次聚集形成的二级孔聚集体、二级孔聚集体相互连接而形成；所述一级孔聚集体上具有一级孔，一级孔的孔径为5-500nm；所述二级孔聚集体上具有二级孔，二级孔的孔径为1-5μm。
  2. 如权利要求1所述分级多孔材料，其特征在于：所述纳米粒子的直径为20-300nm，一级孔聚集体的大小为0.5-5μm。
  3. 如权利要求1所述分级多孔材料，其特征在于：所述分级多孔材料为金属，金属为银、铜、锌、铁、铝、镁、铅中的一种或两种以上的合金。
  4. 如权利要求1所述分级多孔材料，其特征在于：所述分级多孔材料为贵金属包覆的非贵金属，贵金属为铂、钯、金、铱中的一种；非贵金属为银、铜、锌、铁、铝、镁、铅中的一种或两种以上的合金；贵金属于多孔材料中的质量含量1％-99％。
  5. 如权利要求1所述分级多孔材料，其特征在于：所述分级多孔材料为金属/金属氧化物复合材料；金属为银、铜、锌、铁、铝、镁、铅中的一种或两种以上的合金；金属氧化物为氧化锰、氧化铁、氧化钴、氧化镍、氧化铜、氧化锌中的一种或两种以上，金属氧化物于多孔材料中的质量含量1％-99％。
  6. 如权利要求1所述分级多孔材料，其特征在于：所述分级多孔材料为金属/相应的金属盐沉淀复合材料；金属为银、铜、锌、铁、铝、镁、铅中的一种或两种以上的合金；金属盐沉淀相应于银、铜、锌、铁、铝、镁、铅分别为氯化银、碳酸铜、硫化锌、磷酸铁、磷酸铝、磷酸镁、硫化铅，金属盐于多孔材料中的质量含量1％-99％。
  7. 一种权利要求1-6任一所述分级多孔材料的制备方法，其特征在于：包括以下步骤，
    (1)采用电化学方法于电解液中对金属材料进行氧化处理；所述电解液含有能与所述金属材料对应的阳离子形成沉淀的阴离子，且不含有能与所述金属材料发生置换反应的金属阳离子；
    (2)对步骤(1)所得处理后的金属材料进行还原。
  8. 如权利要求7所述分级多孔材料的制备方法，其特征在于：所述步骤(2)为完全还原或不完全还原；所述完全还原制得的为分级多孔金属材料；所述不完全还原制得的为分级多孔的金属/相应的金属盐沉淀的复合材料。
  9. 如权利要求7所述分级多孔材料的制备方法，其特征在于：
    当分级多孔材料为贵金属包覆的非贵金属时，还包括将还原处理后的金属材料表面直接或者表面沉积中间金属元素后置于贵金属盐溶液中进行置换反应，或者在还原处理后的金属材料表面物理溅射贵金属的步骤；
    当分级多孔材料为金属/金属氧化物复合材料时，还包括将还原处理后的金属材料表面电沉积金属氧化物的步骤。
  10. 如权利要求7所述分级多孔材料的制备方法，其特征在于：步骤(1)中所述电解液中含有摩尔浓度大于1mM的阴离子，所述阴离子为PO4 3-、S2-、CO3 2-，Cl-、Br-、I-中的一种或两种以上，所述电解液中同时含有摩尔浓度大于1mM的阳离子，所述阳离子为Na+、K+、H+中的一种或者两种以上。
  11. 如权利要求7所述分级多孔材料的制备方法，其特征在于：步骤(2)所述还原方法为电化学还原、光照还原、电子束还原、辐射还原、激光还原中的一种或两种以上。
  12. 如权利要求7所述分级多孔材料的制备方法，其特征在于：所述采用电化学方法于电解液中对金属材料进行氧化处理的具体过程为以所述金属材料为工作电极，以 铂、石墨棒、银、金中的一种为对电极，银/氯化银、汞/氧化汞或饱和甘汞中的一种为参比电极，于电解液中进行电化学氧化处理；电解液为含Cl-、Br-、I-中的一种或两种以上卤素离子的溶液。
  13. 如权利要求9所述分级多孔材料的制备方法，其特征在于：当分级多孔材料为贵金属包覆的非贵金属时，所述中间金属元素为Cu、Pb中的一种或两种；贵金属盐溶液为氯铂酸、氯金酸、氯钯酸、氯铱酸、氯化铂、氯化钯、氯化铱、硝酸铂、硝酸钯中的一种或两种以上；所述贵金属盐的浓度为1mM～1M，所述置换反应时间为10s～2h。
  14. 如权利要求13所述多孔材料的制备方法，其特征在于：所述分级多孔金属表面沉积中间金属元素的具体方法为欠电位沉积法或者物理溅射法。
  15. 如权利要求9所述分级多孔材料的制备方法，其特征在于：所述金属氧化物的电沉积沉积方法具体为以硝酸锰、硝酸铁、硝酸钴、硝酸镍、硝酸铜、硝酸锌、醋酸锰、醋酸铁、醋酸钴、醋酸镍、醋酸铜、醋酸锌中的一种或两种以上为电解液，以铂、石墨棒、银、金中的一种为对电极，以银/氯化银、汞/氧化汞或饱和甘汞中的一种为参比电极，在分级多孔银表面电沉积氧化锰、氧化铁、氧化钴、氧化镍、氧化铜、氧化锌中的一种或两种以上。
  16. 如权利要求15所述分级多孔材料的制备方法，其特征在于：所述电沉积方法为循环伏安法、线性伏安法、脉冲伏安法、恒电位法、恒电流法中的一种或两种以上。
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Families Citing this family (2)

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Publication number Priority date Publication date Assignee Title
US10052613B2 (en) * 2014-11-27 2018-08-21 Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences Hierarchical porous material and the preparation method thereof
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4977038A (en) * 1989-04-14 1990-12-11 Karl Sieradzki Micro- and nano-porous metallic structures
CN1603033A (zh) * 2004-09-06 2005-04-06 长沙市维优金属材料有限公司 采用电化学纯化－松化工艺制备高性能金属镍粉的方法
CN101391304A (zh) 2008-11-07 2009-03-25 中南大学 高比表面积多孔银粉的制备方法
CN102181904A (zh) * 2011-05-27 2011-09-14 华南理工大学 一种钛表面活化处理的方法
CN102586786A (zh) * 2012-03-19 2012-07-18 上海交通大学医学院附属第九人民医院 一种钛表面形成分级多孔形貌的方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2724688A (en) * 1952-04-29 1955-11-22 John W Gruner Process of growing crystals of aluminum phosphate
DE10207443A1 (de) * 2002-02-22 2003-09-04 Bayer Ag Verfahren und Katalysator zur Herstellung von Alkoholen
CN102335620B (zh) * 2011-07-08 2013-07-31 华东理工大学 一种制备卤化银光催化材料的电化学方法
ES2907515T3 (es) * 2012-10-16 2022-04-25 Martin Bakker Catálisis por nanopartículas metálicas dispersas en un material de carbono jerárquicamente poroso
CN104667876B (zh) * 2013-11-29 2018-02-13 北京思达安新材料科技有限公司 系列MOF型多级孔材料IPD‑mesoMOF‑1～8及其制备方法，以及介孔大小的调节方法
US10052613B2 (en) * 2014-11-27 2018-08-21 Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences Hierarchical porous material and the preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4977038A (en) * 1989-04-14 1990-12-11 Karl Sieradzki Micro- and nano-porous metallic structures
CN1603033A (zh) * 2004-09-06 2005-04-06 长沙市维优金属材料有限公司 采用电化学纯化－松化工艺制备高性能金属镍粉的方法
CN101391304A (zh) 2008-11-07 2009-03-25 中南大学 高比表面积多孔银粉的制备方法
CN102181904A (zh) * 2011-05-27 2011-09-14 华南理工大学 一种钛表面活化处理的方法
CN102586786A (zh) * 2012-03-19 2012-07-18 上海交通大学医学院附属第九人民医院 一种钛表面形成分级多孔形貌的方法

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
APPL. CATAL. B: ENVIRON., vol. 104, 2011, pages 337
ELECTROCHEM. COMMUN., vol. 31, 2013, pages 108
J. ELECTROCHEM. SOC., vol. 152, 2005, pages D 117
JIN RH; YUAN JJ, JOUMAL OF MATERIALS CHEMISTRY, vol. 15, 2005, pages 4513
LINIC ET AL., NATURE CHEM., vol. 6, 2014, pages 828
See also references of EP3231512A4

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