Bulk synthesis of nanoporous palladium and platinum powders
View Patent ↗Disclosed is a method for providing nanoporous palladium and platinum powders. These materials were synthesized on milligram to gram scales by chemical reduction of tetrahalo-complexes with ascorbate in a concentrated aqueous surfactant at temperatures between −20° C. and 30° C. The prepared particles have diameters of approximately 50 nm, wherein each particle is perforated by pores having diameters of approximately 3 nm, as determined by electron tomography. These materials are of potential value for hydrogen and electrical charge storage applications.
1. A method for providing a finely divided palladium metal powder, comprising the steps of:
a. forming a first paste, comprising a first aqueous mixture of an ammonium or alkali metal tetrahalopalladate, a polyethylene glycol hexadecyl ether surfactant and water;
b. forming a second paste comprising an aqueous mixture of ammonium hydroxide and ascorbic acid or a salt of ascorbic acid, a polyethylene glycol hexadecyl ether surfactant, and water;
c. cooling the first and second pastes to about −20° C.;
d. kneading the first and second paste together on a surface cooled to about −20° C. to form a mixed paste;
e. warming the mixed paste to room temperature to initiate a reduction reaction to form a reacted mixed paste;
f. forming a liquid suspension of the reacted mixed paste in a quantity of a heated polar solvent;
g. separating the liquid suspension into a precipitated solid and a supernatant;
h. recovering the precipitated solid;
i. drying the precipitated solid thereby providing a quantity of finely divided powder of palladium metal.
2. The method of claim 1 , wherein the step of forming the first paste further comprises the steps of:
a. dissolving a first quantity of ammonium or alkali metal tetrahalopalladate into a first quantity of water to provide the first aqueous mixture;
b. heating the first aqueous mixture to about 80° C. to form a first solution;
c. melting a first quantity of a polyethylene glycol hexadecyl ether surfactant and adding it to the first solution to provide a second aqueous mixture;
d. mixing the second aqueous mixtures to form a first paste;
e. heating the first paste to about 80° C. to form a viscous liquid;
f. repeating steps d.) and e.) until the viscous liquid is rendered homogeneous; and
g. cooling the viscous liquid to about −20° C.
3. The method of claim 2 , wherein the halide is chloride or bromide.
4. The method of claim 1 , wherein the step of forming the second paste further comprises the steps of:
a. dissolving a first quantity of ammonium hydroxide and ascorbic acid or a salt of ascorbic acid, into a second volume of water to provide a third mixture;
b. heating the third mixture to about 80° C.;
c. melting a second quantity of a polyethylene glycol hexadecyl ether surfactant and adding it to the third mixture to form a reductant mixture;
d. mixing the reductant mixture to form a second paste;
e. heating the second paste to about 80° C. to form a viscous reducing liquid;
f. repeating steps d.) and e.) until the viscous reducing liquid is rendered homogeneous; and
g. cooling the viscous reducing liquid to about −20° C.
5. The method of claim 1 , after the step of kneading further comprises the steps of:
a. cooling the mixed paste to about −20° C. for about 24 hours; and
b. warming the mixed paste to 4° C. over about 48 hours.
6. The method of claim 1 , wherein the step of warming proceeds over a period of time sufficient to allow the reduction reaction to proceed to completion.
7. The method of claim 1 , wherein the step of forming a liquid suspension further comprises the steps of:
adding a quantity of ethanol to the mixed paste and heating ethanol/mixed paste combination to about 80° C.; and
mixing and agitating the ethanol/mixed paste combination to dissolve the mixed paste providing thereby a liquid suspension;
wherein the steps of separating the liquid suspension further comprises the steps of:
decanting the supernatant; and
resuspending the precipitated solid in water and heating the aqueous suspension to about 80° C.; and
repeating the steps of separating the liquid suspension into a precipitated solid and a supernatant, decanting the supernatant and resuspending the precipitated solid;
wherein the step of recovering the precipitated solid further comprises repeating the steps of forming and separating the liquid suspension; and
wherein the steps of drying further comprises the step of:
drying the precipitated solid under a vacuum or an inert atmosphere.
8. The method of claim 1 , wherein the step of forming a liquid suspension further comprises the steps of:
adding a quantity of a solvent solution comprising ethanol and water to the mixed paste and heating this solvent solution-mixed paste combination to about 80° C.; and
mixing and agitating the solvent solution-mixed paste combination to dissolve the mixed paste providing thereby a liquid suspension;
wherein the steps of separating further comprises the step of:
decanting the supernatant;
wherein the step of recovering further comprises repeating the steps of forming and separating the liquid suspension; and
wherein the step of drying further comprises the step of:
drying the precipitated solid under a vacuum or an inert atmosphere.
9. The method of claim 8 , wherein the solvent solution comprises 3 parts by volume ethanol to 1 part by volume water.