a method for preparing an anode catalyst according to the present invention will now be described in more detail . the metal salts of pt , ru , rh , os and ni are not specifically restricted and chlorides , nitrides and sulfuric salts of these metals may be used . examples of the metal salts include a pt metal salt ( h 2 ptcl 6 . xh 2 o ), a ru metal salt ( rucl 3 . xh 2 o ), a rh metal salt ( rhcl 3 ), an os metal salt ( oscl 3 . xh 2 o ), a ni metal salt ( nicl 2 . xh 2 o ) and so on . although the metal salts used in the present invention were ones available from aldrich , metal salts manufactured by another companies can be used as well . also , another types of metal salts , e . g ., k 2 ptcl 6 , can be used in the present invention . appropriate amounts of metal salts are used according to molar ratio of metals desirably used in the quaternary metal catalysts to be mixed with distilled water , respectively , followed by stirring at room temperature , thereby obtaining respective aqueous solutions of the metal salts . the respective aqueous solutions are mixed and stirred . the ph of a mixed solution is adjusted to be in the range of 7 to 8 , and a reducing agent is added thereto at a time , thereby reducing the metal salts to yield precipitates . the obtained precipitates are washed with distilled water and freeze - dried , thereby finally synthesized metal catalysts . an xrd analysis for the synthesized metal catalysts shows peaks corresponding to the respective metal elements in the xrd pattern , confirming that appropriate quaternary metal catalysts have prepared . usable reducing agents include nabh 4 , n 2 h 4 and hcoona . the quaternary metal catalyst prepared by the above - described method includes pt , ru , m 1 and m 2 . the m 1 and m 2 are different metals selected from the group consisting of rh , ni and os . the composition of the quaternary metal catalyst comprises 40 to 70 % by mole of pt , 10 to 40 % by mole of ru , and each 5 to 20 % by mole of m 1 and m 2 . if the composition is out of the above range , the activity of quaternary catalyst is not good , making it difficult to form a solid solution to function as a quaternary metal catalyst , and it is impossible to take advantage of both bifunctional effect and electronic effects . for comparison of activities to methanol oxidation , onset voltages of the methanol oxidation of the presently invented catalyst in a three - electrode cell using a pt wire as a counter electrode , and ag / agcl as reference electrodes are measured in 0 . 5 m sulfuric acid solution and 2m methanol / 0 . 5 m sulfuric acid solution . even if the same metals are used in synthesizing catalysts , different activities to methanol oxidation are exhibited according to the composition of the metals used . then , changes in current are measured for 30 minutes with applying a constant voltage of 0 . 3 v vs . ag / agcl in 2 m methanol / 0 . 5 m sulfuric acid solution . the measured current values are divided by the initial current value for normalization . the normalized current values are relatively compared , thereby determining stability of the synthesized catalysts under the applied voltage condition . for a catalyst to exhibit excellent performance , the catalyst must meet requirements of having a low onset voltage with respect to a methanol oxidation reaction and maintaining a constant normalized current density from the viewpoints of activity and stability . the method for preparing a quaternary metal catalyst can also be applied to catalyst preparation including impregnating a catalyst in a porous carrier such as carbon black , activated carbon or carbon fiber . the invention is further illustrated by the following examples . all references made to these examples are for the purposes of illustration . it should be understood that the invention is not limited to the specific details of the examples . appropriate amounts of a pt metal salt ( h 2 ptcl 6 . xh 2 o ), a ru metal salt ( rucl 3 . xh 2 o ), a rh metal salt ( rhcl 3 ) and a ni metal salt ( nicl 2 . h 2 o ) were picked in molar ratios of ( a ) 4 : 4 : 1 : 1 , ( b ) 4 : 1 : 1 : 1 , ( c ) 4 : 2 : 2 : 2 , ( d ) 5 : 4 : 0 . 5 : 0 . 5 , ( e ) 6 : 3 : 0 . 5 : 0 . 5 , ( f ) 6 . 5 : 2 . 5 : 0 . 5 : 0 . 5 and ( g ) 4 : 3 : 2 : 1 . each of the metal salts was added to distilled water and stirred for 3 hours at room temperature ( 25 ° c . ), followed by mixing the respective metal salt solutions and stirring for another 3 hours . the ph of the mixed solution of the respective metal salt solutions was adjusted to 8 , and three times excess of stoichiometric demand of a 2 m nabh 4 aqueous solution as a reducing agent was added thereto at a time , thereby reducing the metal salts to yield precipitates . the obtained precipitates were washed with distilled water three times and freeze - dried for 12 hours , thereby finally synthesized metal catalysts . performance tests were carried out on the synthesized metal catalysts . fig2 shows x - ray diffraction ( xrd ) patterns of the synthesized metal catalysts having various molar compositions , in which pt , ru , rh and ni catalysts are mixed in molar ratios of ( a ) 4 : 4 : 1 : 1 , ( b ) 4 : 1 : 1 : 1 , ( c ) 4 : 2 : 2 : 2 , ( d ) 5 : 4 : 0 . 5 : 0 . 5 , ( e ) 6 : 3 : 0 . 5 : 0 . 5 , ( f ) 6 . 5 : 2 . 5 : 0 . 5 : 0 . 5 , and ( 9 ) 4 : 3 : 2 : 1 . xrd analysis shows that there are no independent peaks corresponding to ru , rh and ni , and peaks corresponding to pt contained in the synthesized catalysts are slightly shifted toward higher angles than peaks corresponding to pure pt indicated by dotted lines , confirming that the catalysts have been synthesized in appropriate amount ratios of pt , ru , rh and ni ( a . arico , j . electrochem . soc . 1996 , 143 , 3950 ). table 1 shows onset voltages at which methanol oxidation by the quaternary metal catalysts are initiated . referring to table 1 , onset voltages of the quaternary metal catalysts are lower than that ( 0 . 291 v ) of a conventional pt — ru binary anode catalyst whose performance test was carried out in comparative example 1 to be described later , confirming higher catalytic activity . the above electrochemical analysis was carried out on a three - electrode cell using a pt wire as a counter electrode , and ag / agcl as a reference electrode at room temperature . measurement of the catalytic activity was carried out in 0 . 5 m sulfuric acid solution and 2m methanol / 0 . 5 m sulfuric acid solution for comparison of activities with respect to methanol oxidation . even if the same metals were used in synthesizing the catalysts , different activities to methanol oxidation were exhibited according to the composition of metals used . as listed in table 1 , the onset voltages of the quaternary metal catalysts ( a ) through ( g ) according to the present invention are lower than the onset voltage of the conventional pt — ru binary catalyst , i . e ., approximately 0 . 291 v , providing better catalytic activity than that in the conventional catalyst . fig3 is a graphical representation for comparing changes in current measured for 30 minutes with applying a constant voltage ( 0 . 3 v vs . ag / agcl ) in 2 m methanol / 0 . 5 m sulfuric acid solution , with values obtained by dividing the measured current values by the initial current value for normalization . in fig3 , pt , ru , rh and ni catalysts are mixed in molar ratios of ( a ) 4 : 3 : 2 : 1 , ( b ) 5 : 4 : 0 . 5 : 0 . 5 , ( c ) 6 . 5 : 2 . 5 : 0 . 5 : 0 . 5 , ( d ) 4 : 2 : 2 : 2 , ( e ) 6 : 3 : 0 . 5 : 0 . 5 , ( f ) 4 : 4 : 1 : 1 , and ( g ) 4 : 1 : 1 : 1 . the comparison results showed stability of the synthesized catalysts under the condition of applying voltages to electrodes . for a catalyst to exhibit excellent performance , the catalyst preferably has a lower onset voltage with respect to a methanol oxidation reaction , as listed in table 1 , and also preferably maintains a constant normalized current density , as shown in fig3 . the method for preparing the quaternary metal catalyst according to the present invention can also be applied to catalyst preparation including impregnating a catalyst in a porous carrier such as carbon black , activated carbon or carbon fiber . currently , the method for preparing the quaternary metal catalyst according to the present invention is being applied for a single cell using synthesized catalysts without carriers . however , in order to reduce the amount of catalysts used , research and development of methods for preparing catalysts using the carriers are required in the future . a pt metal salt ( h 2 ptcl 6 . xh 2 o ), a ru metal salt ( rucl 3 . xh 2 o ), a rh metal salt ( rhcl 3 ) and an os metal salt ( oscl 3 . xh 2 o ) were mixed in the same manner as in example 1 to be desired molar ratios , except that the compositions thereof were different , thereby preparing metal catalysts . performance test was carried out on the synthesized metal catalysts . fig4 shows x - ray diffraction ( xrd ) patterns of the synthesized metal catalysts having various molar compositions , in which pt , ru , rh and os catalysts are mixed in molar ratios of ( a ) 7 : 1 : 1 : 1 , ( b ) 6 : 3 : 0 . 5 : 0 . 5 , and ( c ) 6 : 2 : 1 . 5 : 0 . 5 . xrd analysis confirms that four metals are alloyed . table 2 shows onset voltages at which methanol oxidation by the quaternary metal catalysts are initiated , according to various compositions . referring to table 2 , onset voltages of the pt — ru — rh — os quaternary metal catalysts are lower than that of the conventional pt — ru binary anode catalyst which was 0 . 291 v , showing better catalytic activity than the conventional ptru catalyst . fig5 is a graphical representation for comparing normalized current changes at 0 . 3v measured for 30 minutes with applying same condition explained in example 1 . in fig5 , pt — ru — rh — os catalysts are mixed in molar ratios of ( a ) 7 : 1 : 1 : 1 , ( b ) 6 : 3 : 0 . 5 : 0 . 5 , and ( c ) 6 : 2 : 1 . 5 : 0 . 5 . the comparison results showed stability of the synthesized catalysts under the condition of applying voltages to electrodes . a pt metal salt ( h 2 ptcl 6 . xh 2 o ), a ru metal salt ( rucl 3 . xh 2 o ), an os metal salt ( oscl 3 . xh 2 o ) and a ni metal salt ( nicl 2 . xh 2 o ) and were mixed in the same manner as in example 1 to be desired molar ratios , except that the compositions thereof were different , thereby preparing metal catalysts . performance test was carried out on the prepared catalysts . fig6 shows x - ray diffraction ( xrd ) patterns of the synthesized metal catalysts having various molar compositions , in which pt , ru , ni and os catalysts are mixed in molar ratios of ( a ) 5 : 4 : 0 . 5 : 0 . 5 , ( b ) 4 : 4 : 1 : 1 , ( c ) 6 : 1 : 1 : 1 , and ( d ) 5 : 2 : 2 : 1 . fig7 shows normalized current densities for the pt — ru — ni — os quaternary metal catalysts according to the present invention , in which pt , ru , ni and os catalysts are mixed in molar ratios of ( a ) 5 : 2 : 2 : 1 , ( b ) 4 : 4 : 1 : 1 , ( c ) 5 : 4 : 0 . 5 : 0 . 5 , and ( d ) 6 : 1 : 1 : 1 . table 3 shows onset voltages at which methanol oxidation by the quaternary metal catalysts are initiated , according to various compositions . referring to table 3 , onset voltages of the pt — ru — ni — os quaternary metal catalysts are lower than that of the conventional pt — ru binary anode catalyst , which was 0 . 291 v , providing better catalytic activity than the conventional catalyst . fig7 is a graphical representation for comparing normalized current changes at 0 . 3v measured for 30 minutes with applying same condition explained in example 1 . in fig7 , pt — ru — ni — os catalysts are mixed in molar ratios of ( a ) 5 : 4 : 0 . 5 : 0 . 5 , ( b ) 4 : 4 : 1 : 1 , ( c ) 6 : 1 : 1 : 1 , ( d ) 5 : 2 : 2 : 1 , and 6 . 5 : 2 . 5 : 0 . 5 : 0 . 5 . the comparison results showed stability of the synthesized catalysts under the condition of applying voltages to electrodes . performance test of a single cell using pt — ru binary anode catalyst based on the onset voltage results of exampe 1 through 3 , pt — ru — rh — ni ( 5 : 4 : 0 . 5 : 0 . 5 ) showed low onset potential and the stability of current at constant voltage on methnol oxidation was tested on a single cell . this performance data was compared the ptru catalyst prepared by the below synthetic procedure . the pt — ru catalyst in a molar ratio of 1 : 1 was prepared by pouring appropriate amounts of a pt metal salt ( h 2 ptcl 6 . xh 2 o ) and a ru metal salt ( rucl 3 . xh 2 o ) into distilled water , respectively , stirring at room temperature ( approximately 25 ° c .) for 1 hour , followed by mixing the two metal salt solutions to produce a mixed solution thereof , and further stirring for 2 hours . the ph of the mixed solution was adjusted to 8 and 3 times excess of stoichiometric demand of a 2 m nabh 4 aqueous solution as a reducing agent was added thereto at a time , thereby reducing the metal salts to yield precipitates . the obtained precipitates were washed with distilled water three times and freeze - dried for 12 hours , thereby finally synthesized metal catalysts . performance tests were carried out on the synthesized ptru catalysts . the measurement results showed that the onset voltage at which methanol oxidation starts was 0 . 291 v with a standard hydrogen electrode as a reference electrode . the onset voltages of the quaternary metal anode catalysts having combinations of transition metals according to the present invention prepared in examples 1 through 3 , were lower than the onset voltage of the conventional pt — ru binary metal catalyst , showing relatively better performance . fig8 graphically shows results of performance of pt — ru — rh — ni ( 4 : 4 : 1 : 1 ) quaternary metal catalyst according to the present invention , compared with pt — ru synthesized by above procedure under the condition that 2 m methanol is flowed at the anode and the air is flowed at the cathode . the amount of anode and cathode loading is respectively 8 mg / cm 2 synthesized ptru / ptrurhni and 3 mg / cm 2 of pt from johnson matthey plc . the membrane electrode assembly ( mea ) is formed by the hot - press with the membrane ( nafion ™ 115 ) between the anode and cathode . a tested unit cell had a dimension of 10 . 5 cm 2 , and a methanol solution and air were supplied through a graphite channel at flow rates of 0 . 2 - 1 . 0 cc / min and 1000 - 2000 cc / min , respectively . the results in fig8 showed that whereas the use of the pt — ru binary catalyst at 0 . 3 v gave a current density of 144 ma / cm 2 , the use of the pt — ru — rh — ni quaternary catalyst prepared in example 1 gave a current density of 209 ma / cm 2 , that is , improved performance by approximately 45 %. as described above , the pt — ru based quaternary metal catalyst according to the present invention has several advantages that an oxygen source for methanol oxidation is effectively provided , a co bonding strength is weakened by changing the electronic structure between atoms , and methanol adsorption is enhanced to increase the catalytic activity . also , the effective surface of the pt — ru based quaternary metal catalyst according to the present invention can be increased by impregnating the same in a catalyst converter substrate having a wide surface area , thereby reducing the amount of the catalyst used . further , since the onset voltage of a fuel cell having the pt — ru quaternary metal catalyst according to the present invention is lower than that of a fuel cell having the conventional pt — ru binary metal catalyst , a highly efficient direct methanol fuel cell ( dmfc ) can be manufactured . therefore , compared to the conventional pt — ru binary metal catalyst , the pt — ru quaternary metal catalyst according to the present invention can give high power density and can replace conventional catalysts .