NZ712409B2 - A method of preparing pure precious metal nanoparticles with large fraction of (100) facets, nanoparticles obtained by this method and their use - Google Patents

Abstract

The invention provides a method of preparing pure precious metal nanoparticles of controlled sizes and having (100) facets, wherein a precursor substance contained in a reagent solution is subjected to a reduction reaction using a reducing agent contained in the reagent solution to provide nanoparticles, and the reduction reaction is stopped by rapid lowering of the reaction solution temperature. In the process of the invention, the need to use surfactants or other organic particles to stabilize the (100) facets is eliminated. cles, and the reduction reaction is stopped by rapid lowering of the reaction solution temperature. In the process of the invention, the need to use surfactants or other organic particles to stabilize the (100) facets is eliminated.

Description

A method of ing pure precious metal nanoparticles with large fraction of (100) facets, nanoparticles obtained by this method and their use The invention provides a method of preparing of pure precious metal nanoparticles with the (100) facets, nanoparticles prepared by said method and use thereof.

Methods of nanoparticle synthesis based on reduction of precious metal compounds are ly known and implemented in practice. The most popular methods, which allow to obtain nanoparticles (e.g. platinum) without any t (i.e. not supported on another material), employ chemical reduction of platinum salts or complexes in an environment ning a reducing agent, and substances controlling the size of the forming nanoparticles. For e, Pt(II) or Pt(IV) compounds are reduced with alcohols, and ethylene glycol [1-6], hydrazine [7,8] or sodium borohydride [9]. Size control is achieved by adding organic compounds (surfactants) adsorbing ly on the surface of nascent nanoparticles, such as PVP (polyvinylpyrrolidone) or other strongly adsorbing polymers [1-11].

However, the majority of synthesis methods ed nowadays do not allow to control size of the formed nanoparticles, without addition of substances strongly adsorbing on surfaces of the formed nanoparticles (surfactants). The surface of such obtained nanoparticles is contaminated with surfactants or products of their degradation, which makes possibilities of their use limited, due to the drop in catalytic activities and necessity to employ procedures for purification of the obtained nanoparticles. Numerous methods for cation were developed based on chemical or electrochemical ion of the adsorbed tant [7, 8, 10, 12]. Electrochemical purification is based on cycling of electric potential of a nanoparticle-containing electrode n the values selected to oxidize the adsorbed surfactant. Said potential is of the order of um oxide formation, or even oxygen evolution potential. The potential cycling lasts long enough to reach a constant current response of the system. However, it should be emphasized that electrochemical purification is unpractical for larger batches of the material, as the electric t of every nanoparticle with the electrode must be d. The method is usually ed for very small batches of the material deposited as a thin layer on the electrode.

The method of chemical cation s strong oxidizing agents, such as potassium ganate, potassium dichromate etc. Nanoparticles are subjected to oxidizing action of an oxidizing agent solution. Due to their oxidative properties, use of such materials requires great care, and purification of even small s of nanoparticles es ntial amounts of the oxidizing agent, which is detrimental for both persons in charge of the process, and for the environment [13].

It should be also noted that it is not certain that the purification procedure allows for complete purification of the nanoparticle surfaces from the surfactant or its decomposition products. In certain circumstances, (at least partial) purification of the surface [10, 12] can be achieved, however, the amount of the tant removed cannot be determined without additional examination. It was also shown that the methods of nanoparticle surface purification, which employ a procedure of oxidation of the adsorbed surfactant lead to formation of elemental carbon deposits on the surface. Such residues block catalyst’s surface, are practically impossible to remove and very hard to detect [14].

Moreover, the methods of purification, which employ oxidation of the adsorbed surfactant, allow for (partial) purification of the most precious metals only (such as e.g. platinum), nanoparticles of the other ones (e.g. palladium) will dissolve under such treatment.

The advantages of using tants (e.g., PVP) include the fact that their employment, due to their strong interaction with surfaces of the formed nanoparticles, results in obtaining preferential crystallographic domains at nanoparticle walls [15]. Due to stabilizing action of surfactants, it is possible to obtain rticles with the (100) facets, which are hard to obtain by other methods due to their thermodynamic instability.

However, use of chemical or electrochemical methods of purification leads to destruction of such crystallographic domains. T hus, use of surfactants , to the large extent, the possibility of employing nanoparticles with the (100) facets in catalysis.

An ative for chemical ion in the presence of a surfactant and purification of such obtained nanoparticles, are the methods which do not employ a surfactant. Such methods include, for example, cathodic corrosion or sputtering, however efficiency of such methods is too low to find a practical use. Lately it was shown that pure silver nanoparticles could be ed by the laser ablation of a metal immersed in water . Due to agglomeration of the formed particles, the method allows to obtain only colloids of nanoparticles at a low tration. In addition, the method involves very expensive infrastructure, which additionally limits its use.

The present inventors have also undertaken attempts to synthesize nanostructures without use of surfactants. discloses a process for synthesis of nanostructures in a flow system, in which a precursor substance solution undergoes reduction on using a reducing agent solution and nanoparticles are produced, wherein the reduction reaction is terminated by adding an agent neutralizing the reducing agent.

The publication by Januszewska et al. [17] discloses a process for the platinum nanoparticle synthesis by ion of platinum salts or complexes in situ with ethylene . s of the studies presented therein indicate that the method led to obtaining ultra-pure platinum nanoparticles characterized by relatively high surface organization, which was illustrated by presence of the (111) and (100) facets. r, the methods known from the prior art are still unsatisfactory. There is a need to develop an environment-friendly, simple method for the ation of nanoparticles of high surface purity and a controlled size, wherein surfactants are not employed, and consequently the purification procedure is eliminated. It would be also desirable for the method to result in obtaining pure nanoparticles with the well-organized e (e.g. characterized by the (100) facets), that would significantly increase their catalytic properties. All of the above objects are to be read disjunctively with the object of at least providing the public or ry with a useful choice.

The invention provides a method of preparing precious metal nanoparticles of controlled sizes having high e purity and (100) facets, wherein a precursor substance comprising a precious metal salt or precious metal complex, or a mixture of salts and/or complexes of various precious metals, which is contained in a reagent solution is subjected to a reduction reaction using a reducing agent contained in the reagent on to form nanoparticles, wherein the reduction reaction is conducted in the absence of a surfactant and with the initial concentration of the precursor substance in the reagent solution from 50 mM to 100 mM, and the reduction reaction is stopped after a predetermined time t, from 14 seconds to 2 hours, by rapidly lowering of the reaction solution ature at a rate higher than or equal to 0.15°C/s. A reagent on means a solution where the reduction reaction is conducted and it comprises a precursor substance and a reducing agent, and the synthesized rticles appear therein in the course of the reduction reaction. By a reaction solution, the solution is meant where the synthesized nanoparticles and optional unreacted reagents are present (i.e. the precursor substance and/or the reducing agent).

Not wishing to be bound by any theory, the t inventors noticed that a cooling rate of the reaction solution could be critical for increasing the number of nanoparticles with the (100) facets. Thus, ing to the invention, ng of the reaction solution temperature is carried out at a rate higher than or equal to 0.15°C/s. Such conditions are, for example, fulfilled when the reaction solution (e.g. t in a tube or a loop formed therefrom a mixture of a solvent, nanoparticles and optionally unreacted reagents) is placed in a bath at 0°C (e.g. a water-ice mixture), or when the on mixture present in the flow system is pumped over to the cooling zone of the flow system, wherein a tube or a loop formed therefrom is ed in the above-indicated bath.

In a further preferred embodiment of the method ing to the invention, the reduction reaction follows a rapid se of the temperature of the reagent solution prepared in advance at a room or lower temperature (i.e. „in the cold state"). For example, the reagent solution ed in advance is charged at a room or lower ature into the reaction system or the reaction zone of the flow system (e.g. to a tube or a loop formed therefrom immersed in a bath, at a temperature suitable for conducting the reduction reaction), thus resulting in increase of its temperature.

Again, not wishing to be bound by any theory, the rate the reagent solution is heated with seems also to be a key parameter for a number of the (100) facets obtained.

Thus, according to the invention, increasing the temperature of the reagent solution is carried out at a rate higher than or equal to /s.

Preferably the time t, after which the reduction reaction is stopped, is equal to 1 min., 2 min., 5 min., 15 min., 30 min. or 1 h. It should be appreciated that the time after which the reaction of the precursor substance reduction is d, includes also the step of heating the reagent on.

In a preferred embodiment, the method of the invention is carried out in a flow system, comprising interconnected tubes or loops formed therefrom, through which the reagent solution and on solution flows, said tubes or loops being located in a reaction and cooling zones of the flow system, and tube or loop lengths in the reaction zone wherein the reagent solution is charged, as well as a flow rate of the on are selected to provide a suitable time t of the reduction reaction, with the cooling zone ensuring rapid cooling of the reaction solution that flows through a tube or loop located therein.

In a system like that, a method of synthesis with a stopped flow (a d-flow type method) could also be employed. It means that, after the reagent solution is introduced into a tube or a loop formed therefrom located in the on zone, the flow of the on is stopped. T he ature of the solution increases rapidly and the reduction process leading to formation of nanoparticles takes place. After the predetermined time t, the reduction reaction is stopped by resuming the flow and passing the reaction solution into the tube or loop formed therefrom, located in a cooling zone of the system, where rapid cooling of the reaction solution takes place.

In an alternative embodiment of the method ing to the invention the reduction reaction is conducted by charging the reagent solution into a tube or a loop formed therefrom located in the reaction , and after a predetermined time t said tube or loop containing the reaction solution is transferred to a cooling system, where rapid lowering of the reaction solution temperature takes place.

In a preferred embodiment of the method according to the invention the reaction solution contained in the tube or loop formed therefrom, during the cooling step (i.e. when located in a cooling system or a cooling zone of the flow system), is subjected to ultrasonication. This prevents adhering of nanoparticles to tube walls and is particularly important in the case where the tube employed is a Teflon tube and/or in the case where neither the reduction reaction, nor the cooling is carried out with the simultaneous flow of the solutions. In the case of employing tubes made of other materials, use of the ultrasounds may not be necessary. The ultrasound treatment can be carried out by placing the cooling system in an ultrasonication bath.

The reaction zone or reaction system allows to control the temperature, in which the reduction of the precursor substance takes place. Preferably, the reaction zone or reaction system comprises a bath (e.g. a bath with ethylene , provided with a heating means) and a ature controller. This allows to maintain the temperature at which the ion on is carried out. Preferably, the reduction reaction is carried out at the temperature of from 70°C to 190°C, more preferably at about 82°C, 95°C, 109°C, 120°C, 130°C, 140°C, 147°C or 150°C. The term reaction zone or reaction system, as d herein, refers to both the element providing the suitable temperature (e.g. a bath with a temperature controller), and to such an element, in which a tube or loop formed therefrom is accommodated, wherein the reagent solution is uced into and/or passed h.

The cooling zone or cooling system allows to rapidly lower the reaction on ature, to stop the conducted reduction reaction. Most preferably, the reaction solution temperature is lowered after the time t by immersion in a water bath at the temperature of 0°C. Thus, the cooling zone or cooling system comprises a bath at suitably low temperature (e.g. a water-ice bath at 0°C). The term cooling zone or cooling , as d herein, refers to both the element providing the suitable cooling temperature, and such an element in which a tube or loop formed therefrom is accommodated, wherein the reaction solution is present into and/or passed through.

According to the present invention the reduction reaction, as well as cooling of the reaction solution, is conducted in a loop made from Teflon tube of 25 cm in length, having the outer diameter of 1/8" and the inner er of 1/16". Preferably, the diameter of the loop is 6 cm. The length of the tube is of ance only in the case of a flow synthesis method, since it determines the duration of the reduction reaction, and consequently influences the quantity of nanoparticles obtained and their sizes. Other sis system parameters, e.g. a section of the tube, influence the cooling and heating rate of the solution contained therein.

The further preferred step of the method according to the invention comprises separating the nanoparticles from the reaction solution by centrifuging. T he separated nanoparticles are preferably rinsed (e.g. with distilled water) and re-centrifuged.

Preferably, the step of rinsing with distilled water and centrifugation is carried out three times.

Preferably, in the method of the invention a precursor of a precious metal or a mixture of precursors of precious metals are employed as a precursor substance. More preferably, the metal precursor comprises a salt or complex thereof or a mixture of salts or complexes of various metals. Most preferably, a metal is selected from the group comprising platinum, palladium, silver, gold, ruthenium, osmium, iridium and rhodium. In a preferred embodiment, the precursor substance comprises a salt selected from the group sing AgNO3, , AgHSO4, Ag2SO4, AgF, AgBF4, AgPF6, CH3COOAg, AgCF3SO3, H2PtCl6, H6Cl2N2Pt, PtCl2, PtBr2, K2PtCl4, Na2[PtCl4], Li2[PtCl4], H2Pt(OH)6, Pt(NO3)2, [Pt(NH3)4]Cl2, 3)4](HCO3)2, 3)4](OAc)2, (NH4)2PtBr6, K2PtCl6, PtSO4, Pt(HSO4)2, Pt(ClO4)2, H2PdCl6, H6Cl2N2Pd, PdCl2, PdBr2, K2[PdCl4], Na2[PdCl4], Li2[PdCl4], H2Pd(OH)6, Pd(NO3)2, [Pd(NH3)4]Cl2, 3)4](HCO3)2, 3)4](OAc)2, (NH4)2PdBr6, (NH3)2PdCl6, PdSO4, Pd(HSO4)2, Pd(ClO4)2, , AuCl3, AuCl, AuF3, (CH3)2SAuCl, AuF, AuCl(SC4H8), AuBr, AuBr3, S2O3)2, HAuBr4, K[Au(CN)2], RuCl2 ((CH3)2SO)4, RuCl3, [Ru(NH3)5(N2)]Cl2, Ru(NO3)3, RuBr3, RuF3, Ru(ClO4)3, OsI, OsI2, OsBr3 , OsCl4, OsF5, OsF6, OsOF5, OsF7, IrF6, IrCl3, IrF4, IrF5, Ir(ClO4)3, K3[IrCl6], K2[IrCl6], Na3[IrCl6], Na2[IrCl6], Li3[IrCl6], Li2[IrCl6], [Ir(NH3)4Cl2]Cl, RhF3, RhF4, RhCl3, 3)5Cl]Cl2, RhCl[P(C6H5)3]3, K[Rh(CO)2Cl2], Na[Rh(CO)2Cl2] Li[Rh(CO)2Cl2], Rh2(SO4)3, Rh(HSO4)3 and Rh(ClO4)3, hydrates thereof or a mixture of salts and/or hydrates thereof. Most preferably, the precursor substance is K2PtCl4. The initial concentration of a precursor substance in the reagent solution is preferably from 1 mM to 1 M, more ably from 50 mM to 100 mM, and most preferably about 70 mM.

Using the saturated solution of the precursor substance is possible.

Preferably, the precursor nce is also a source of halides and/or pseudohalides, and chlorides in particular. The precursor substance could directly provide the reagent solution with halides and/or pseudohalides, or it could constitute a source of halides and/or pseudohalides which appear in the reaction mixture as a result of the running reaction.

The reducing agent that can be ably employed in the process of the invention is selected from the group comprising ethylene glycol, hydrazine, ic acid, sodium borohydride, sodium hypophosphite, lithium tetraethyloborohydride, methyl alcohol, 1,2- hexadecanediol, hydroxylamine and dimethylborazane DMAB. Most preferably, ethylene glycol is used as a reducing agent. The initial tration of the reducing agent in the reagent solution is from 0.5 mM to 4 M.

In a particularly preferred ment of the method according to the invention the t solution ses a solution of the precursor substance in ethylene glycol, with the precursor substance, preferably K2PtCl4, being dissolved in ethylene glycol at the t temperature (i.e. „in the cold ), and ethylene glycol plays simultaneously a role of the solvent, as well as the reducing agent.

In a preferred embodiment of the method of the invention, the reagent solution ns halides and/or pseudohalides at a relatively high concentration. The halides and/or pseudohalides are present preferably in the reaction solution at a concentration higher than mM, preferably higher than 40 mM, more preferably higher than 250 mM, and most preferably 280 mM. Alternatively, the reagent solution is the ted solution of halide and/or pseudohalide salts. In a particularly preferred embodiment, the concentration of halides in the reaction solution increases as a result of reduction (decomposition) of the precursor substance and release of the constituent halides. For example, when the precursor substance is K2PtCl4, the concentration of chlorides in the reaction on increases in the reduction process.

The s employed in the method of the invention are preferably ed from the group comprising fluorides, chlorides, bromides and iodides, the pseudohalides are selected from the group comprising cyanides, cyanates, nates and thiocyanates. Most preferably the halides and/or pseudohalides are introduced into the reagent solution in a form of m, potassium or calcium salts. Furthermore, halides and/or pseudohalides can be introduced into the reaction solution ly in a form of the precursor substance, e.g.

PtCl2 or K2PtCl4.

Not wishing to be bound by any theory, the present inventors found that high concentration of halides and/or pseudohalides could exert stabilizing effect on the (100) facets of the formed nanoparticles. In the nce example, wherein conditions of synthesis as disclosed in the ation by Januszewska et al. [17] were reproduced, the initial concentration of K2PtCl4 was about 4.5 mM, while in the method of the invention the concentration of K2PtCl4 was about 72 mM. Thus, in the method of the invention, the concentration of chlorides appearing during the course of sis was markedly higher.

Consequently, the chloride ions, which appear in the reaction mixture could influence beneficially the crystalline structure of the nascent nanoparticle surfaces.

Thus the present inventors developed an effective method of preparing of the precious metal nanoparticles, by reducing compounds of precious metals in the flow system, both by the flow , and the stopped-flow method. A e of the reducing agent and the precursor is fed to the flow system. The reaction duration is controlled by the flow rate and/or the time of the solution is t in the system after the flow is stopped, and sizes of the obtained nanoparticles depend on parameters of the process, such as the duration and ature of the reaction. In the event of employing the stopped-flow method, the amount of the nanoparticles obtained depends also on s of the tubes n the reaction is carried out. A characteristic feature of such a technical solution is a precise l of the reaction duration and a very high heating and cooling rate of the reaction mixture in the flow system and in the stopped-flow system. The high heating rate and stabilization of the end ature allows to control the nucleation process, as well as further reduction, which makes it possible to control the size of the formed nanoparticles without addition of a surfactant. The synthesis ions employed in the technical solution of the invention allow to freeze non-equilibrium states (obtaining nanoparticles with metallic glass character, alloys of non-segregated metals which segregate in normal conditions etc.). By controlling the reaction duration and the temperature, the control over size, shape of nanoparticles and crystalline properties of their surfaces was gained.

The invention provides also nanoparticles of precious metals, prepared with the method of the invention, and use of such particles as genous catalysts. The nanoparticles according to the invention are characterized by high purity (their purification is not necessary, since in the method of their preparation no surfactants are employed) and a particularly icant number of the (100) facets (as it is clear from the examples that follow, a number of that kind of facets is at average twice as large as in the case of the synthesis process disclosed in the publication by Januszewska, A. et al. [17]). Thus the nanoparticles prepared by the method of the invention, after they are isolated from the reaction solution and rinsed, could be directly employed in heterogeneous catalysis. The fact that the chemical or ochemical purification is not necessary renders the nanoparticles prepared by the method of the invention suitable for use as catalysts. er, the greater number of the (100) facets likewise es their catalytic ties.

Methods for the preparation nanoparticles in the flow-through systems are known in the art. However, the size is controlled principally by changing physicochemical properties of the reaction mixture, such as a pH value or a ition. The publication by Baumgard J. et al. discloses a process for reduction of a platinum salt with ethylene glycol in a flow system, with the use of NaOH to control the pH level and PVP to ize the size, to yield nanoparticles of the sizes of 1 do 4 nm, depending on conditions of synthesis employed [18]. It was demonstrated in ular how the ature, pH and flow rate control sizes of obtained nanoparticles. Two kinds of flow systems were employed: in the first one, nanoparticles were ed in an one-step process, in the second one, steps of nucleation and nanoparticle growth were divided into two independent steps. Regardless of the system used, the addition of surfactant (PVP) was employed.

Another research work employed the flow system, wherein a mixture of a precursor and a reducing agent were heated with microwaves. Again, in this case a mixture of starting materials ned a surfactant (the same PVP). No relationship between sizes of formed nanoparticles and a temperature of the process was demonstrated (the synthesis was conducted at the nt temperature, i.e. 160°C) and solely for the two reaction times (2.8 and 28.3 s) [19].

Preparation of nanoparticles of controlled shapes was described by Feliu et al. , however, surfactants were employed to this end.

The method of preparing of nanoparticles disclosed in the present application does not involve surfactants, and the control of shape is obtained by controlling conditions of the synthesis. The requirement of chemical or electrochemical purification of the nanoparticles obtained was eliminated thereby. r advantage of the method according to the invention is the increased presence of the (100) facets in the nanoparticles obtained, which enhances to a significant degree their catalytic properties.

The invention is rated by the drawing, n: Figure 1 shows an example of a voltammogram ed for Pt nanoparticles prepared by the method according to the invention; Figure 2 illustrates a comparison of a voltammogram recorded for the Pt rticles prepared by the method according to the invention (in the reduction reaction conducted for 1 h at 150°C) and Pt nanoparticles obtained in a reference e by the method disclosed in the publication by Januszewska A. et al. [17]; Figure 3 shows mograms ed for the Pt nanoparticles prepared by the ion reaction conducted for 1 h at 120°C, 130°C, 140°C and 150°C; Figure 4 shows a TEM micrograph of Pt nanoparticles prepared by the reduction reaction conducted for 1 h at 147°C.

EXAMPLES e 1. A method of ing of Pt rticles Reaction systems A synthesis of nanoparticles employs loops made from Teflon tubes 25 cm in length with an inner diameter of 1/8" and outer diameter of 1/16". A diameter of the loop is about 6 cm, and a volume thereof – about 1.8 cm3.

The synthesis by a flow method or a stopped-flow method employs a system comprising two connected loops: the reaction and cooling loops. The reaction loop is accommodated in an ne glycol bath and heated to a reaction temperature. The temperature of the ethylene glycol bath is controlled by a ature controller, and additionally, to provide an equal temperature in the entire bath, the content thereof is stirred with a magnetic stirrer. The cooling loop is located in an ultrasonication bath with water at 0°C. The reagent solution is forced to the reaction loop by means of a peristaltic pump and pumped as the reaction solution into the cooling loop, where it is subjected to ultra-sonication. The flow can be stopped to extend the reduction and/or cooling time.

Alternatively, a sole loop, which is initially introduced into the above-mentioned ethylene glycol bath heated to the reaction temperature, and into which the reagent solution is forced by means of a peristaltic pump, is employed. Then, after the reaction is completed, the loop is transferred to the ultrasonication bath with water at 0°C to rapidly cool the reaction solution.

In the experiments, the flow rate in the loop(s) is 0.12 cm3 s-1 (1.7 cm s-1).

Reagent solution For a synthesis of um nanoparticles, the solution of K2PtCl4 (99.9% –Alfa Aesar) in ne glycol (EG) (99.5% – Fluka) is employed. For one volume of the loop, 50 mg of the above-indicated platinum salt (corresponding to a concentration of about 30 mg/cm3 (~ 72 mM)) is used. The platinum salt solution is prepared „in the cold state" (i.e. at the room temperature).

The Pt salt tration in EG is thus much higher than in the prior art [17].

Synthesis of nanoparticles in a flow system The platinum salt solution in EG (the reagent solution) at the room temperature is forced by means of a peristaltic pump to the reaction loop maintained at the reaction temperature, and flows to the cooling loop for rapid cooling of the reaction solution (the flow rate is 12 cm3s-1). After the reaction on is pumped into the cooling loop, the flow is stopped for about 5 min. In the course of cooling, the reaction solution present in the cooling loop is subjected to ultrasonication. After cooling, the loop content is pumped over to the test tube as a sample receiver.

The synthesis of nanoparticles in the flow system is conducted by maintaining the reaction loop at various temperatures. The results shown correspond to the reduction ons carried out at 82°C, 95°C, 109°C and 147°C. No nanoparticles were ed at the flow rate of 12 cm3s-1 at 82°C and 95°C. The Pt nanoparticles produced by the flow system at 109°C and 147°C were investigated further.

Synthesis of nanoparticles by the stopped-flow method The platinum salt solution in EG (the reagent solution) at the room temperature is forced by means of a peristaltic pump to the reaction loop ined at the reaction temperature. After the entire portion of the solution is introduced into the reaction loop, the flow is stopped for a predetermined time t. After the reaction time expiry, the rapid cooling of the reaction solution was effected by pumping the solution from the reaction loop to the cooling loop or by erring the reaction loop into the cooling system (a water bath at 0°C). On cooling, the solution is ted to ultrasonication. After cooling for about 5 min. the loop content is pumped over to the test tube as a sample receiver.

The synthesis of rticles in a stopped-flow system is conducted by maintaining the reaction loop at various temperatures. The results shown correspond to the reduction reactions carried out at 82°C, 95°C, 109°C, 120°C, 130°C, 140°C, 147°C and 150°C for 1 min., 2 min., 5 min., 15 min., 30 min. and 1 h.

At 82°C no nanoparticles were obtained during the synthesis carried out for 15 min., 5 min., 2 min. and 1 min. No nanoparticles were obtained at 95°C during the synthesis conducted for 2 min. and 1 min. The Pt nanoparticles produced by this method were investigated r.

Separation of nanoparticles Centrifuging is ed to separate the nanoparticles from the post-reaction mixture. After centrifuging, the reaction solution supernatant is discarded, and the nanoparticles are rinsed three times with distilled water and separated again by centrifuging.

Example 2. Properties of the Pt nanoparticles investigated by the electrochemical method Electrochemical measurements To investigate ties of the Pt nanoparticles by the electrochemical method, the suspension of the Pt rticles ed in Example 1, is applied with an automatic measuring pipette onto an Au substrate and left to air-dry. The testing array is composed of a mercury-sulfate reference electrode (Hg/Hg2SO4/0.1M H2SO4), a gold auxiliary electrode and the nanoparticles deposited on a gold substrate, as a working electrode. The study is conducted in 0.5 M sulfuric (VI) acid as a y electrolyte. All electrodes are placed in a beaker. The system is sealed by a itting Teflon lid, and then deoxygenated by purging with argon for 35 minutes.

The gold electrode and the beaker with the Teflon lid are cleaned in the Caro acid before use.

All voltammograms are recorded at a rate of 5 mV/s. To standardize the data, a charge to reduce the oxide layer is determined for each electrode at the range of potentials from 0.5-1.1V.

Results and discussion Fig. 1 shows an exemplary voltammogram recorded for the Pt nanoparticles ed in Example 1. Peaks marked on the voltammogram are the peaks characteristic for all the ed nanoparticles. P eaks 1, 2 and 3 are connected with adsorption of en at the Pt surface. Peak 3 is a characteristic peak for adsorption at the (100) facets, peak 2 includes the contribution of adsorption at the (100) facets. The current marked as 4 is connected generally with charging of the double layer. Since that value should be independent of the kind of walls at the nanoparticle surfaces, it was used as an onal standardizing value to determine changes in peak s after deducting that value, as a baseline value, from the current value for the peak.

The appearance of the mogram confirms the fact that nanoparticles obtained in Example 1 are characterized by the high surface purity and the presence of a significant number of the (100) facets. is of values of the signals connected with hydrogen adsorption at the (100) facets and comparing them with analogous data for nanoparticles obtained by the method as described in the publication by Januszewska A. et al. [17], revealed that the number of the (100) facets in nanoparticles obtained by the method of the invention is more than two times higher.

Fig. 2 shows a comparison of a voltammogram recorded for the Pt nanoparticles ed in Example 1 by the reduction on conducted for 1 h at a temperature 150°C, and the Pt nanoparticles obtained by the method as described in the publication by Januszewska A. et al. [17].

The analysis of signals connected with hydrogen adsorption at the (100) facets for nanoparticles obtained at various atures revealed that the number of the (100) facets does not depend on a temperature the reduction reaction is conducted at (ratios of teristic signal heights to reference signal heights are practically constant).

Fig. 3 shows voltammograms ed for the Pt nanoparticles obtained by the reduction reaction carried out for 1 h at 120°C, 130°C, 140°C and 150°C. Table 1 shows a list of the peak values for voltammograms presented on Fig. 3 and compares them with the literature data [17]. Numbers represent values of t intensities in μA per cm2 of Pt nanoparticle surfaces. To calculate relative values of the current ities (the two rightmost table columns), the values of current intensities for peaks 1, 2 and 3 were corrected by a value of the capacitive current, the value of which had been subtracted from the values of peak 1, 2 and 3 currents before relative values were calculated. The value calculated in the rightmost column is of a particularly significant analytical value, since it is directly connected with a number of the (100) facets present in a sample.

Table 1: List of values of current intensities for the peaks and values of the capacitive current recorded by the voltammetric method for the Pt nanoparticles obtained in 1 h at various temperatures Pt t Current Current Capacitive current Current intensity t intensity nanoparticle intensity intensity intensity intensity value (4) value for peak 2 value for peak 3 synthesis value for value for value for[μA/cm2] to current to current temp. [°C] peak 1 peak 2 peak 3 intensity value intensity value [μA/cm2] [μA/cm2] [μA/cm2] for peak 1 ratio for peak 4 ratio 120 6.94 7.958 2.617 0.794 1.17 2.30 130 7.417 7.546 2.141 0.761 1.02 1.81 140 7.564 7.927 2.539 0.799 1.05 2.18 150 7.442 7.707 1.806 0.543 1.04 2.33 ture 7.092 7.189 1.2587 0.62478 1.01 1.01 data [17] Example 3. TEM g of the Pt nanoparticles and determining their sizes The nanoparticles obtained in Example 1 were imaged by TEM. Fig. 4 represents an illustrative TEM micrograph of the Pt nanoparticles obtained by the reduction reaction conducted for 1 h at 147°C. The shape of the nanoparticles ms further the presence of the (100) facets. The shape of the nanoparticles is determined by dominating llographic walls. On the TEM micrographs, the nanoparticles of characteristic cube shapes are e.

The TEM micrographs were used for determining an average nanoparticle size by employing the Measure IT software pack. Table 2 lists average particle size (diameter) versus a reduction time and temperature.

Table 2: List of Pt rticle sizes (nm) depending on the time and temperature of conducting the reduction reaction Reduction ature Reduction time 82°C 95°C 109°C 147°C Reaction in a flow system - - 5.32357 9 1 min - - 5.512 8.34095 2 min - - 5.1105 7.86286 min - 3.51833 BD 8.39561 min - 3.51527 5.35737 8.55111 min 5.30565 3.78313 6.3995 8.963 1 h 3.89589 4.4196 9.36355 10.98344 - means that no nanoparticles were obtained BD means no data Sizes of various numbers of nanoparticles were measured in various ces.

Nanoparticles obtained at low temperatures and short reduction times erate, making tical the measurement of sizes for more than 20 nanoparticles.

Sizes of the obtained nanoparticles depend on the duration t of the reaction and the reaction temperature. The reaction duration depends on a flow rate of the reagent solution (the Pt salt solution in EG) within the reaction loop or time when the reagent solution is present within the reaction loop following the stopping of the flow.

Reference example. Preparation of nanoparticles by the method described in the publication by Januszewska et al. [17] To 110 ml of ethylene glycol (Fluka) in a round-bottomed flask, 0.0005 mol K2PtCl4 (99.9% - Alfa Aesar) (0.2083 g) was added to provide a solution of K2PtCl4 with the concentration of about 4.56 mM.

The reduction reaction was conducted by heating the flask under reflux with concomitant agitation (using magnetic stirrer).

The flask content was heated starting at the room temperature at the rate of about °C per minute till 112°C. The reaction took place for about 5 minutes. In the course of the on the temperature increased to 123.7°C, and dropped to 119.6°C during last 2 minutes of the reaction.

The concentration of des in the post-reaction solution was about 18.25 mM.

After the reaction was completed, the flask was left to cool at the room temperature. Nanoparticles were isolated from glycol by centrifuging and rinsing (as described in Example 1).

Fig. 2 shows a voltammogram of the nanoparticles obtained by this method.

References 1. Ahmadi, T. S.; Wang, Z. L.; Green, T. C.; Henglein, A.; ElSayed, M. A., Shapecontrolled synthesis of dal platinum nanoparticles. Science 1996, 272, (5270), 1924- 1926. 2. Yamada, M.; Kon, S.; Miyake, M., Synthesis and size control of Pt nanocubes with high selectivity using the additive effect of NaI. Chem. Lett. 2005, 34, (7), 051. 3. Chen, J. Y.; Herricks, T.; Geissler, M.; Xia, Y. N., Single-crystal nanowires of um can be synthesized by controlling the reaction rate of a polyol process. J. Am.

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. Solla-Gullon, J.; Montiel, V.; Aldaz, A.; Clavilier, J., Electrochemical characterisation of platinum rticles prepared by microemulsion: how to clean them t loss of lline surface structure. J. Electroanal. Chem. 2000, 491, (1-2), 69-77. 11. Solla-Gullon, J.; Montiel, V.; Aldaz, A.; Clavilier, J., Electrochemical and electrocatalytic behaviour of platinum-palladium nanoparticle alloys. Electrochem. Comm. 2002, 4, (9), 716-721. 12. Conway, B. E.; Angerstein-Kozlowska, H.; Sharp, W. B. A.; Criddle, E. E., Ultrapurification of Water for Electrochemical and Surface Chemical Work by Catalytic stillation. Anal. Chem. 1973, 45, (8), 1331-1336. 13. Monzo, J.; Koper, M. T. M.; Rodriguez, P., Removing Polyvinylpyrrolidone from Catalytic Pt Nanoparticles without Modification of Superficial Order. Chemphyschem 2012, 13, (3), 709-715. 14. Kuhn, J. N.; Tsung, C.-K.; Huang, W.; Somorjai, G. A., Effect of organic capping layers over monodisperse platinum nanoparticles upon activity for ethylene hydrogenation and carbon monoxide oxidation. Journal of Catalysis 2009, 265, (2), 209-215.

. Beyerlein, K. R.; Solla-Gullon, J.; Herrero, E.; Garnier, E.; Pailloux, F.; Leoni, M.; Scardi, P.; Snyder, R. L.; Aldaz, A.; Feliu, J. M., Characterization of (111) surface tailored Pt nanoparticles by electrochemistry and X-ray powder diffraction. Materials Science and Engineering ctural Materials Properties Microstructure and Processing 2010, 528, (1), 83-90. 16. Pyatenko, A.; Shimokawa, K.; Yamaguchi, M.; Nishimura, O.; , M., sis of silver rticles by laser ablation in pure water. Applied Physics a- Materials Science & Processing 2004, 79, (4-6), 803-806. 17. Januszewska, A.; Dercz, G.; Piwowar J.; Jurczakowski R.; Lewera A., Outstanding catalytic activity of ultra-pure platinum nanoparticles. Chem. Europ. J., 2013, 19, (50), 17159–17164. 18. Baumgard, J.; Vogt, A. M.; Kragl, U.; Jahnisch, K.; Steinfeldt, N., Application of microstructured devices for continuous sis of tailored platinum nanoparticles. Chem Eng J 2013, 227, 137-144. 19. Nishioka, M.; Miyakawa, M.; Daino, Y.; Kataoka, H.; Koda, H.; Sato, K.; Suzuki, T. M., Rapid and Continuous Polyol s for Platinum Nanoparticle Synthesis Using a Single-mode ave Flow Reactor. Chem. Lett. 2011, 40, (12), 1327-1329.

Claims (17)

Claims

1. A method of preparing of precious metal nanoparticles of controlled sizes having high surface purity and (100) facets, wherein a precursor substance comprising a us metal salt or precious metal complex, or a mixture of salts and/or complexes of various precious metals, which is contained in a t solution is subjected to a reduction on by a reducing agent contained in the reagent on to provide nanoparticles, wherein the reduction reaction is conducted in absence of a surfactant and with the initial concentration of the precursor substance in the reagent solution from 50 mM to 100 mM, and the reduction reaction is stopped after a pre-determined time t from 14 seconds to 2 hours by rapid lowering of the reaction on temperature at a rate higher than or equal to 0.15°C/s.

2. The process of claim 1, n the reduction reaction is ed by a rapid increase of the reagent solution temperature at a rate higher than or equal to 0.15°C/s, wherein the reagent solution is prepared in advance at the room or lower temperature.

3. The process of claim 1 or claim 2, wherein the reaction is conducted in a flow system comprising interconnected loops, through which the reagent solution and reaction solution flows, wherein said loops are placed respectively in the on and cooling zone of the flow , and a length of the loop in the on zone, where the reagent solution is introduced, and a on flow rate are selected to provide a le reduction reaction time t, while the cooling zone provides rapid cooling of the reaction solution flowing through the loop contained therein.

4. The process of claim 1 or claim 2, wherein the reduction reaction is ted by charging the reagent solution into the loop located in the reaction system, and after a predetermined time t the loop, which contains the reaction solution, is transferred to the cooling system, where rapid lowering of the reaction solution temperature takes place and the reaction solution is subjected to ultrasonication.

5. The process of any one of claims 1 to 4, wherein the obtained nanoparticles are separated from the reaction solution by centrifuging.

6. The process of any one of claims 1 to 5, wherein the us metal is selected from the group comprising platinum, palladium, silver, gold, ruthenium, osmium, iridium and rhodium.

7. The process of any one of claims 1 to 6, wherein the precursor substance comprises a salt selected from the group comprising AgNO3, AgClO4, AgHSO4, Ag2SO4, AgF, AgBF4, AgPF6, Ag, AgCF3SO3, 6, H6Cl2N2Pt, PtCl2, PtBr2, K2PtCl4, Na2[PtCl4], Li2[PtCl4], H2Pt(OH)6, Pt(NO3)2, 3)4]Cl2, [Pt(NH3)4](HCO3)2, [Pt(NH3)4](OAc)2, (NH4)2PtBr6, K2PtCl6, PtSO4, 4)2, Pt(ClO4)2, H2PdCl6, H6Cl2N2Pd, PdCl2, PdBr2, l4], Na2[PdCl4], Li2[PdCl4], H2Pd(OH)6, Pd(NO3)2, [Pd(NH3)4]Cl2, [Pd(NH3)4](HCO3)2, [Pd(NH3)4](OAc)2, (NH4)2PdBr6, (NH3)2PdCl6, PdSO4, Pd(HSO4)2, Pd(ClO4)2, HAuCl4, AuCl3, AuCl, AuF3, (CH3)2SAuCl, AuF, AuCl(SC4H8), AuBr, AuBr3, Na3Au(S2O3)2, HAuBr4, K[Au(CN)2], RuCl2 ((CH3)2SO)4, RuCl3, 3)5(N2)]Cl2, Ru(NO3)3, RuBr3, RuF3, Ru(ClO4)3, OsI, OsI2, OsBr3 , OsCl4, OsF5, OsF6, OsOF5, OsF7, IrF6, IrCl3, IrF4, IrF5, Ir(ClO4)3, K3[IrCl6], K2[IrCl6], Na3[IrCl6], Na2[IrCl6], Li3[IrCl6], Li2[IrCl6], [Ir(NH3)4Cl2]Cl, RhF3, RhF4, RhCl3, [Rh(NH3)5Cl]Cl2, RhCl[P(C6H5)3]3, K[Rh(CO)2Cl2], Na[Rh(CO)2Cl2] CO) 2Cl2], Rh2(SO4)3, Rh(HSO4)3 and Rh(ClO4)3, hydrates thereof or a mixture of salts and/or hydrates f.

8. The process of claim 7, wherein the precursor substance is K2PtCl4.

9. The process of any one of claims 1 to 8, wherein the reducing agent is selected from the group comprising ethylene glycol, hydrazine, ascorbic acid, sodium borohydride, sodium osphite, lithium tetraethyloborohydride, methyl alcohol, 1,2- hexadecanediol, hydroxylamine and dimethylborazane DMAB.

10. The process of claim 9, wherein the reducing agent is ethylene glycol.

11. The s of any one of claims 1 to 10, wherein the reagent solution comprises a solution of the precursor substance in ethylene glycol, said sor substance being dissolved in ethylene glycol at the room or lower temperature.

12. The process of any one of claims 1 to 11, wherein the reduction reaction is conducted at the temperature of from 70°C to 190°C.

13. The process of any one of claims 1 to 12, n the reaction solution ature after the time t is lowered by immersing the solution in a water bath at 0°C.

14. The process of any one of claims 1 to 13, wherein the reagent solution comprises halides, selected from the group comprising des, chlorides, bromides and iodides, and/or pseudohalides, selected from the group comprising cyanides, cyanates, isocyanates and thiocyanates, at a concentration higher than 5 mM, preferably higher than 40 mM, more preferably higher than 250 mM, most preferably 280 mM, or comprises a saturated solution of halide and/or pseudohalide salts, and/or the concentration of halides in the reaction solution increases as a result of precursor substance reduction.

15. Use of nanoparticles prepared by the process as defined in any one of claims 1 to 14, as heterogeneous catalysts.

16. The process of claim 1, as hereinbefore bed with reference to the drawings.

17. The use of nanoparticles of claim 15, as hereinbefore described with reference to the drawings.