Abstract:
This disclosure provides a facial green method for metal cyanides preparation, including the following steps: 1) supported metal nanoparticles and Fenton&#39;s reagent are mixed with nitrile and then stirred to obtain suspension, wherein metal nanoparticles are selected from a nano metal, nano metal oxide and nano metal salt; 2) centrifuging the suspension to obtain a product and drying the product after stirring to obtain the metal cyanides. As prepared metal cyanides have broad application prospects in the fields of sensor, battery, medicine, electroplating and catalysis. This Fenton-improved cyanation (FIC) method may effectively exclude the toxicity from free cyanide anions and get rid of UV-light, being more energy-saving and more feasible for large-scale industrial production of MCs.

Description:
CROSS REFERENCE TO RELATED APPLICATION 
       [0001]    This application is a national stage application of International application number PCT/CN2014/089561, filed Oct. 27, 2014, titled “Fenton&#39;s reagent improved cyanation and usage thereof,” which claims the priority benefit of Chinese Patent Application Nos. 201310522842.9 and 201410571924.7, filed on Oct. 28, 2013 and Oct. 23, 2014, respectively, which is hereby incorporated by reference in its entirety. 
     
    
     TECHNICAL FIELD 
       [0002]    The present disclosure relates to chemical preparation of metal cyanides using Fenton&#39;s reagent. 
       BACKGROUND 
       [0003]    Fenton&#39;s reagent, first found by English chemist Fenton in 1894, is a kind of oxidation system composed of hydrogen peroxide and catalyst Fe 2+ , in which the Fe 2+  ion is mainly used as a homogeneous catalyst, while H 2 O 2  plays the role of oxidant. Fenton&#39;s reagent is more widely used in industrial wastewater treatment, especially wastewater which is difficult to deal with or of biological toxicity (such as cyanide contained wastewater), due to its advantages of rapid response, mild reaction condition and no secondary pollution etc. Generally, in acidic conditions, such as pH=3.5, Fenton&#39;s reagent has strong oxidative property. Organic compounds, such as carboxylic acids, alcohols, esters etc., can be directly oxidized into carbon dioxide and water ( Journal of hazardous materials,  2003, 98, 33-50;  Industrial water treatment,  2014, 3, 22-25). Under the alkaline conditions, Fenton&#39;s reagent was also applied in cyanide contained wastewater treatment ( Environmental Toxicology and Chemistry,  1994, 13, 1719-1726;  Water Treatment Technology,  2012, 38, 114-117). However, applications of Fenton&#39;s reagent in other aspects are rare. 
         [0004]    Metal cyanides are compounds that metal ions and cyano are connected directly, which are of hypertoxicity. Cyanide ions may free out after metal cyanides get into the human body, and then combine with ferric iron of cytochrome oxidase, preventing the reduction of ferric. As a result, the normal cell respiration may be disturbed, causing tissue hypoxia and body suffocation. On the other hand, metal cyanides have a wide range of uses. For example, the use of cyanide in industrial mining of gold, silver and organic synthesis (using metal cyanide to synthesis of nitrile). Meanwhile, metal cyanides also play a vital role in electroplating, dye, and paint industrial process. 
         [0005]    For hundreds of years, there is only one way to synthesis noble metal cyanides and transition metal cyanides, namely the traditional synthesis method ( J. Chem Soc.  1943, 79;  J. am. Chem Soc.  2012, 134, 16387-16400). This method uses NaCN, KCN or HCN as the source and formation of cyano, which react with metal or metal ion directly. In the case of cyanide gold synthesis, the traditional synthesis method is mainly the MacArthur-Forrest process, which is divided into the following two steps: 
         [0000]      4 Au+8 NaCN+O 2 2 H 2 O=4 Na[Au(CN) 2 ]+4 NaOH 
         [0000]      KAu(CN) 2 +HCl═AuCN+HCN+KCl
 
         [0006]    The reaction is related to the free cyanide ion, which is of fatal threat to the environment and human health. Besides, the cyanide ion is easy to combine with the ferric ion to form the iron cyanide, making it difficult to generate other metal cyanide in the presence of iron ions. 
         [0007]    In 2012, the inventors established a UV method for metal cyanide preparation (CN 102274740 A). The UV method overcomes the problem of cyanide ion in the traditional technology, but this method uses relatively expensive UV light, easy to produce light pollution, and it is difficult to achieve industrialization. At the same time, the inventors found that it is difficult to control the cyanation degree during gold cyanide preparation through UV method, and the product quality is unstable, and it is difficult to synthesize multi metal cyanide through this UV method. Therefore, the development of a cheap, simple, efficient, green and controllable method for metal cyanides preparation may be of great significance. 
       SUMMARY 
       [0008]    The conventional preparation of Metal cyanides (MCs), however, utilize high toxic NaCN, KCN or HCN as the cyaniding sources, which may threaten human&#39;s health and environmental safety. For the purpose of green chemistry, this disclosure is aimed to provide a green method for metal cyanides preparation. For the first time, Fenton&#39;s reagent is applied to the cyanation process. It has been proved during this process, the other metal cyanide other than the iron cyanide is surprisingly formed in the presence of iron ions, resulting in breaking certain thinking patterns. 
         [0009]    Fenton&#39;s reagent is applied to the preparation of metal cyanide for the first time in this disclosure. Through this method, mono-metal cyanide (such as gold cyanide, silver cyanide, palladium cyanide, ruthenium cyanide and platinum cyanide), bi-metal cyanide (such as gold silver cyanide, gold copper cyanide, silver copper cyanide and copper aurocyanide) and tri-metal cyanide (such as gold silver copper cyanide) are obtained. This cyanation process, getting rid of toxic CN −  ions and UV-light, is a green method for metal cyanides preparation. 
         [0010]    The specific technical scheme of the disclosure is as follows: 
         [0011]    The first aspect of this disclosure relates to a method for metal cyanide preparation, which concludes following steps: 
         [0012]    1) supported metal nanoparticles and Fenton&#39;s reagent are mixed with nitrile and then stirred to obtain suspension, wherein metal nanoparticles are selected from nano metals, nano metal oxides and nano metal salts, and Fenton&#39;s reagent includes Fenton catalyst (metal ion) and hydrogen peroxide; 
         [0013]    2) centrifuging the suspension to obtain a product and drying the product after stirring to obtain the metal cyanides. 
         [0014]    Cyanation reaction is conducted under neutral environment in this disclosure, namely the pH about 7. If under the acidic environment, cyano may be discharged in the form of hydrocyanic acid, causing environmental pollution; if under the alkaline environment, the metal ion may precipitate out through reacting with hydroxide and the efficiency of hydrogen peroxide may decrease. 
         [0015]    In some implementations, the molar ratio of supported metal nanoparticles, metal ions of the Fenton&#39;s reagent (e.g., Fenton catalyst), and nitrile is 0.01˜0.2:0.01˜0.2:100. If the amount of Fenton catalyst is too little, then cyanation is not complete, on the contrary, resulting in waste; the amount of nitrile is too little or too much will reduce the efficiency of hydrogen peroxide. In some instances, the molar ratio of supported metal nanoparticles and Fenton catalyst is 1:1.5˜5, which ensures reasonable utilization of raw materials. 
         [0016]    In some implementations, supported metal nanoparticles is the complexes of support and metal nanoparticles, and metal nanoparticles are selected from nano metal, nano metal oxide and nano metal salts. The supported metal nanoparticles may be selected from silica, alumina, titania, magnesium oxide, zinc oxide, carbon. In some implementations, the nano metal may be selected from Au, Ag, Pt, Pd, Ru, nano metal oxide is Ag 2 O, nano metal salt is AgNO 3 . 
         [0017]    In some implementations, nitrile used in this disclosure is acetonitrile or propionitrile, serving as solvent and providing cyano group. 
         [0018]    In some implementations, the reaction temperature is 10˜70° C., and the reaction time is more than 30 minutes. The longer reaction time causes the higher degree of cyanation and the more complete degree of reaction. The optimal reaction time is 30 minutes to 48 hours. The optimum temperature of the reaction system of the disclosure is 30˜50° C. The reaction time is 2 hours or more, and the optimal reaction time is 2 hours to 6 hours. If the temperature is lower than 10° C., the rate of reaction may decrease, resulting in time waste; if the temperature is higher than 70° C., the hydrogen peroxide is decomposed seriously and its utilization efficiency may reduce. 
         [0019]    In some implementations, the molar ratio of the Fenton catalyst (metal ion) and hydrogen peroxide in the Fenton&#39;s reagent is 1:10˜200; In some instances, the molar ratio of the Fenton catalyst (e.g., metal ions) and the hydrogen peroxide in the Fenton&#39;s reagent is 1:60˜100. During the cyanation reaction, if the molar ratio of the metal ion and hydrogen peroxide is less than 1:200, and part of the cyano group may be oxidized, reducing the utilization of hydrogen peroxide; if the molar ratio of the metal ion and hydrogen peroxide is higher than 1:10, part of metal ions may hydrolyze, reducing their utilization. 
         [0020]    In some implementations, the Fenton catalyst may be selected from one or more of Fe 2+ , Fe 3+ , Ni 2+ , Co 2+ , Mn 2+  and Cu 2+ . 
         [0021]    In some implementations, formulas of the wherein metal cyanides may be selected from AuCN, AgCN, Pt(CN) 4 , Pd(CN) 2 , Ru(CN) 4 , Au x Ag 1-x CN, Au x Cu 1-x CN, Ag x Cu 1-x CN, CuAu 2 (CN) 4 , and Au x Ag y Cu 1-x-y CN, 0&lt;x, y&lt;1. 
         [0022]    In some implementations, the size of wherein said metal cyanides is in nano-scale. In some instances, the metal cyanides are metal nanoparticles. 
       Advantageous Effects 
       [0023]    Advantages of this disclosure are as follows: 1) getting rid of toxic resource, such as NaCN and KCN, which are often used in conventional technic of metal cyanides preparation; 2) no emission of toxic HCN; 3) broadening the application of Fenton&#39;s reagent to metal cyanides preparation. Fenton&#39;s reagent was applied to the preparation of metal cyanide for the first time in this disclosure. Through this method, a mono-metal cyanide (such as gold cyanide, silver cyanide, palladium cyanide, ruthenium cyanide and platinum cyanide), a bi-metal cyanide (such as gold silver cyanide, gold copper cyanide, silver copper cyanide and copper aurocyanide) and a tri-metal cyanide (such as gold silver copper cyanide) may be obtained. 4) Using the green and cheap raw material (nitril and Fenton&#39;s reagent) and providing an one-step method for metal cyanides preparation, which can be simply conducted under normal conditions, especially easy to achieve industrialization; 5) using the normal supported metal nanoparticles to synthesize the metal cyanides whose particle sizes are controllable; 6) by using green resource and undergoing energy saving pathway, this cyanation method is proved to be environment friendly; 7) breaking a certain thinking pattern, and other metal cyanides (especially the multi metal cyanide) other than the iron cyanide may be formed in the presence of iron ions. 
         [0024]    As prepared metal cyanides have broad application prospects in the fields of sensing, battery, medicine, electroplating and catalysis. For example, gold cyanides can be used to catalyze synthesis of isoflavones, and copper aurocyanide can be used for ammonia gas sensor. 
     
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         [0025]      FIG. 1  illustrates a XRD pattern of example 1 related to AuCN preparation. 
           [0026]      FIG. 2  illustrates a XRD pattern of comparative example 2 related to Au—AuCN complex preparation. 
           [0027]      FIG. 3  illustrates a TEM picture of example 2 related to AuCN preparation. 
           [0028]      FIG. 4  illustrates a XPS pattern of example 3 related to AuCN preparation. 
           [0029]      FIG. 5  illustrates a XRD pattern of example 4 related to AgCN preparation. 
           [0030]      FIG. 6  illustrates a XPS pattern of example 5 related to AgCN preparation. 
           [0031]      FIG. 7  illustrates a XRD pattern of example 14 related to CuAu 2 (CN) 4 preparation . 
           [0032]      FIG. 8  illustrates a XRD pattern of example 16 related to Au 0.5 Ag 0.5 CN preparation. 
           [0033]      FIG. 9  illustrates a FT-IR spectra of example 18 related to Au 1/3 Ag 1/3 CN preparation. 
       
    
    
     DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     Examples 
       [0034]    Further elaboration of the present disclosure combined with specific examples are as follows. To be understood, these Examples are only to illustrate the present disclosure and not to limit the scope of the present disclosure. In addition to be understood, after reading the contents of the teaching of the disclosure, a variety of changes or modifications on disclosure can be made by the technicians in this field, which equivalent forms also falls in the defined range in the appended claims. 
       Example 1 
       [0035]    0.8 mg silica supported Au nanoparticles (AuNPs/SiO 2 ) and 22 mg FeSO 4 .7H 2 O were suspended in 2 mL acetonitrile containing 0.8 mmol H 2 O 2  aqueous solution in air under stirring at 30° C. After 4 h of reaction, a visual color of the suspension was gradually changed from wine red to pale green, and the solid product was obtained by centrifuging and drying, which was proved to be silica supported AuCN.  FIG. 1  is a XRD pattern related to AuCN preparation, which shows the solid product was pure AuCN. AuNPs were fully transformed to AuCN, and no ferricyanide was formed. 
       Comparative Example 1 
       [0036]    0.8 mg AuNPs/SiO 2  and 22 mg FeSO 4 .7H 2 O were suspended in 2 mL acetonitrile containing 0.8 mmol H 2 O 2  and 50 uL 1 mol/L HCl aqueous solution in air under stirring at 30° C. After 10 h of reaction, no AuCN was formed with the solid color unchanged, indicating that AuCN cannot be prepared through this method under an acid solution. 
       Comparative Example 2 
       [0037]    0.8 mg AuNPs/SiO 2  and 22 mg FeSO 4 .7H 2 O were suspended in 2 mL acetonitrile containing 0.8 mmol H 2 O 2  and 50 uL 1 mol/L NaOH aqueous solution in air under stirring at 30° C. After 10 h of reaction, the visual color of the solid was gradually changed from wine red to deep blue. The solid product was obtained by centrifuging and drying, which was proved to be Au—AuCN complex with AuNPs partially transformed to AuCN.  FIG. 2  is a XRD pattern related to Au—AuCN complex preparation. This result indicated that the efficiency of Fenton&#39;s reagent decreased under a base solution and AuNPs may not be completely transformed to AuCN. 
       Comparative Example 3 (UV Method for Metal Cyanide Preparation, CN 102274740 A, which is Incorporated Herein by Reference) 
       [0038]    0.8 mg AuNPs/SiO 2  and 22 mg FeSO 4 .7H 2 O were suspended in 2 mL acetonitrile containing 0.8 mmol H 2 O 2  aqueous solution under stirring with UV irradiation of 350 W mercury lamp. After 3 h of reaction, the visual color of the solid was gradually changed from wine red to yellow. Au 3+  was detected on the surface of the obtained product by XPS characterization, indicating the metal Au is over oxidation. No iron cyanide was detected. 
       Example 2 
       [0039]    2 mg AuNPs/SiO 2  and 3 mg FeSO 4 .7H 2 O were suspended in 3 mL acetonitrile containing 1 mmol H 2 O 2  aqueous solution in air under stirring at 70° C. After 30 min of reaction, the visual color of the solid was gradually changed from wine red to pale green. The solid product was obtained by centrifuging and drying, which was proved to be silica supported AuCN.  FIG. 3  is the TEM picture related to AuCN preparation. No iron cyanide was detected. 
       Example 3 
       [0040]    10 mg AuNPs/SiO 2  and 30 mg FeSO 4 .7H 2 O were suspended in 1.3 mL acetonitrile containing 21 mmol H 2 O 2  aqueous solution in air under stirring at 10° C. After 48 h of reaction, the visual color of the solid was gradually changed from wine red to pale green. The solid product was obtained by centrifuging and drying, which was proved to be silica supported AuCN.  FIG. 4  is the XPS pattern related to AuCN preparation, with two peaks (Au4f 5/2  and Au4f 7/2 ) ascribed to Au(I). No iron cyanide was detected. 
       Example 4 
       [0041]    20 mg AgNO 3 /MgO and 150 mg FeSO 4 .7H 2 O were suspended in 3.5 mL acetonitrile containing 50 mmol H 2 O 2  aqueous solution in air under stirring at 30° C. After 6 h of reaction, the solid product was obtained by centrifuging and drying, which was proved to be MgO supported AgCN (AgCN/MgO).  FIG. 5  is the XRD pattern related to AgCN preparation, which showed the solid product was pure AgCN. No iron cyanide was detected. 
       Example 5 
       [0042]    20 mg AgNPs/ZnO and 100 mg FeSO 4 .7H 2 O were suspended in 4 mL acetonitrile containing 72 mmol H 2 O 2  aqueous solution in air under stirring at 50° C. After 2 h of reaction, the visual color of the solid fades gradually. The solid product was obtained by centrifuging and drying, which was proved to be ZnO supported AgCN (AgCN/ZnO).  FIG. 6  is the XPS pattern related to AgCN preparation, with two peaks (Ag4f 3/2  and Ag4f 5/2 ) ascribed to Ag(I). No iron cyanide was detected. 
       Example 6 
       [0043]    60 mg active carbon supported Au nanoparticles (AuNPs/C) and 200 mg H 2 O.Fe 2 (SO 4 ) 3  were suspended in 10 mL propanenitrile containing 150 mmol H 2 O 2  aqueous solution in air under stirring at 10° C. After 48 h of reaction, the visual color of the solid was gradually changed from wine red to pale green. The solid product was obtained by centrifuging and drying, which was proved to be carbon supported AuCN (AuCN/C). No iron cyanide was detected. 
       Example 7 
       [0044]    30 mg titanium oxide supported nano Ag 2 O (Ag 2 O/TiO 2 ) and 100 mg FeSO 4 .7H 2 O were suspended in 4 mL acetonitrile containing 22 mmol H 2 O 2  aqueous solution in air under stirring at room temperature. After 4 h of reaction, the visual color of the solid was gradually changed from black to grey. The solid product was obtained by centrifuging and drying, which was proved to be titanium oxide supported AgCN (AgCN/TiO 2 ). No iron cyanide was detected. 
       Example 8 
       [0045]    6 mg carbon supported Au nanoparticles (AuNPs/C) and 8 mg FeSO 4 .7H 2 O were suspended in 14 mL acetonitrile containing 2.4 mmol H 2 O 2  aqueous solution in air under stirring at 70° C. After 2 h of reaction, the visual color of the solid was gradually changed from wine red to pale green. The solid product was obtained by centrifuging and drying, which was proved to be carbon supported AuCN. No iron cyanide was detected. 
       Example 9 
       [0046]    5 mg supported PtNPs and 20 mg FeSO 4 .7H 2 O were suspended in 4 mL acetonitrile containing 6 mmol H 2 O 2  aqueous solution in air under stirring at 50° C. After 20 h of reaction, the solid product was obtained by centrifuging and drying, which was proved to be supported Pt(CN) 4 . No iron cyanide was detected. 
       Example 10 
       [0047]    5 mg supported PdNPs and 20 mg FeSO 4 .7H 2 O were suspended in 4 mL acetonitrile containing 7 mmol H 2 O 2  aqueous solution in air under stirring at 50° C. After 20 h of reaction, the solid product was obtained by centrifuging and drying, which was proved to be carbon supported Pd(CN) 2 . No iron cyanide was detected. 
       Example 11 
       [0048]    5 mg RuNPs/C and 20 mg FeSO 4 .7H 2 O were suspended in 4 mL acetonitrile containing 7 mmol H 2 O 2  aqueous solution in air under stirring at 30° C. After 24 h of reaction, the solid product was obtained by centrifuging and drying, which was proved to be carbon supported Ru(CN) 4 . No iron cyanide was detected. 
       Example 12 
       [0049]    5 mg supported AuNPs and 12 mg Ni(NO 3 ) 2 .6H 2 O were suspended in 4 mL acetonitrile containing 7 mmol H 2 O 2  aqueous solution in air under stirring at 50° C. After 2 h of reaction, the solid product was obtained by centrifuging and drying, which was proved to be supported AuCN. 
       Example 13 
       [0050]    5 mg supported AgNO 3  and 12 mg Co(NO 3 ) 2 .6H 2 O were suspended in 4 mL acetonitrile containing 7 mmol H 2 O 2  aqueous solution in air under stirring at 30° C. After 6 h of reaction, the solid product was obtained by centrifuging and drying, which was proved to be supported AgCN. 
       Example 14 
       [0051]    5 mg supported AuNPs and 3 mg Cu(NO 3 ) 2 .3H 2 O were suspended in 4 mL acetonitrile containing 7 mmol H 2 O 2  aqueous solution in air under stirring at 30° C. After 3 h of reaction, the solid product (supported Au 2/3 Cu 1/3 CN) was obtained by centrifuging and drying. If the reaction time was prolonged to 10 h, supported copper aurocyanide (CuAu 2 (CN) 4 ) would be obtained after centrifuging and drying. XRD pattern of copper aurocyanide is shown in  FIG. 7 . 
       Example 15 
       [0052]    5 mg supported AuNPs and 10 mg MnSO 4  were suspended in 4 mL acetonitrile containing 7 mmol H 2 O 2  aqueous solution in air under stirring at 30° C. After 6 h of reaction, AuCN/C solid product was obtained by centrifuging and drying. 
       Example 16 
       [0053]    3 mg AuNPs/SiO 2 , 2.6 mg supported AgNO 3  and 22 mg FeSO 4 .7H 2 O were suspended in 4 mL acetonitrile containing 0.8 mmol H 2 O 2  aqueous solution in air under stirring at 30° C. After 4 h of reaction, the visual color of the solid was gradually changed from red to pale grey. The solid product was obtained by centrifuging and drying, which was proved to be silica supported Au 0.5 Ag 0.5 CN.  FIG. 8  is the XRD pattern of as obtained solid product, and it can be assigned to Au 0.5 Ag 0.5 CN according to literature ( Journal of The American Chemical Society  2012, 134, 16387-16400). 
       Comparative Example 4 (UV Method for Metal Cyanide Preparation, CN 102274740 A) 
       [0054]    3.0 mg AuNPs/SiO 2  and 2.6 mg supported AgNO 3  were suspended in 4 mL acetonitrile containing 0.8 mmol H 2 O 2  aqueous solution in air under stirring under UV-irradiation of 350 W mercury lamp. After 4 h of reaction, the visual color of the solid is changed from wine red to green. The solid product was obtained by centrifuging and drying, which was proved to be the mixture of AuCN and AgCN rather than Au 0.5 Ag 0.5 CN by XRD characterization. 
       Example 17 
       [0055]    12 mg supported AgNO 3  and 13 mg Cu(NO 3 ) 2 .3H 2 O were suspended in 4 mL acetonitrile containing 2 mmol H 2 O 2  aqueous solution in air under stirring at 30° C. After 8 h of reaction, the visual color of the solid was gradually changed from wine red to pale grey. The solid product was obtained by centrifuging and drying, which was proved to be silica supported Ag 0.5 Cu 0.5 CN (Ag 0.5 Cu 0.5 CN/SiO 2 ). 
       Comparative Example 5 (UV Method for Metal Cyanide Preparation, CN 102274740 A) 
       [0056]    12 mg supported AgNO 3  and 13 mg Cu(NO 3 ) 2 .3H 2 O were suspended in 4 mL acetonitrile containing 2 mmol H 2 O 2  aqueous solution in air under stirring with UV-irridiation of 350 W mercury lamp. After 4 h of reaction, the solid product was obtained by centrifuging and drying. XRD results indicated that AgCN without Ag—Cu bi-metal cyanide was formed. 
       Example 18 
       [0057]    3 mg silica supported AuNPs, 2.6 mg AgNO 3  and 4 mg Cu(NO 3 ) 2 .3H 2 O were suspended in 5 mL acetonitrile containing 1.5 mmol H 2 O 2  aqueous solution in air under stirring at 30° C. After 4 h of reaction, the visual color of the solid was gradually changed from red to grass green. The solid product was obtained by centrifuging and drying, which was proved to be silica supported Au 1/3 Ag 1/3 Cu 1/3 CN.  FIG. 9  is the FT-IR spectra related to Au 1/3 Ag 1/3 Cu 1/3 CN preparation. 
       Example 19 
       [0058]    6 mg silica supported AuNPs, 2.6 mg AgNO 3  and 22 mg FeSO 4 .7H 2 O were suspended in 4 mL acetonitrile containing 1.2 mmol H 2 O 2  aqueous solution in air under stirring at 30° C. After 7 h of reaction, the visual color of the solid was gradually changed from red to pale grey. The solid product was obtained by centrifuging and drying, which was proved to be silica supported Au 2/3 Ag 1/3 CN. No iron cyanide was detected. 
       Example 20 
       [0059]    2 mg silica supported AgNO 3  and 13 mg Cu(NO 3 ) 2 .3H 2 O were suspended in 4 mL acetonitrile containing 2 mmol H 2 O 2  aqueous solution in air under stirring at 30° C. After 40 h of reaction, the visual color of the solid was gradually changed from red to pale grey. The solid product was obtained by centrifuging and drying, which was proved to be silica supported Ag 1/6 Cu 5/6 CN (Ag 1/6 Cu 5/6 CN/SiO 2 ). 
       Example 21 
       [0060]    12 mg AuNPs/SiO 2 , 2.6 mg AgNO 3  and 4 mg Cu(NO 3 ) 2 .3H 2 O were suspended in 4 mL acetonitrile containing 1.5 mmol H 2 O 2  aqueous solution in air under stirring at 60° C. After 1 h of reaction, the visual color of the solid was gradually changed from red to grass green. The solid product was obtained by centrifuging and drying, which was proved to be silica supported Au 2/3 Ag 1/6 Cu 1/6 CN. 
       Example 22 
       [0061]    6 mg AuNPs/SiO 2 , 1.3 mg AgNO 3  and 8 mg Ni(NO 3 ) 2 .6H 2 O were suspended in 4 mL acetonitrile containing 1.2 mmol H 2 O 2  aqueous solution in air under stirring at 50° C. After 3 h of reaction, the visual color of the solid was gradually changed from red to grey. The solid product was obtained by centrifuging and drying, which was proved to be silica supported Au 4/5 Ag 1/5 CN. 
       Example 23 
       [0062]    40 mg AuNPs/SiO 2  and 100 mg FeSO 4 .7H 2 O were suspended in 15 mL acetonitrile and 5 mL propionitrile containing 12 mmol H 2 O 2  aqueous solution in air under stirring at 20° C. After 48 h of reaction, the visual color of the solid was gradually changed from red to grass green. The solid product was obtained by centrifuging and drying, which was proved to be AuCN/SiO 2 . No iron cyanide was detected. 
       Example 24 
       [0063]    12 mg PtNPs/SiO 2  and 80 mg Co(NO 3 ) 2 .6H 2 O were suspended in 10 mL acetonitrile containing 5 mmol H 2 O 2  aqueous solution in air under stirring at 37° C. After 25 h of reaction, the solid product was obtained by centrifuging and drying, which was proved to be silica supported Pt(CN) 4 (Pt(CN) 4 /SiO 2 ).