US010495601B2 United States Patent ( 10 ) Patent No.: US 10,495,601 B2 Abdulazeez et al. (45 ) Date of Patent : Dec. 3 , 2019 (54 ) RARE EARTH METAL INCORPORATED ( 58 ) Field of Classification Search ZEOLITE MODIFIED ELECTRODES FOR CPC GO1N 27/333 ; GOIN 27/308 ; GOIN 27/48 ; DETECTION AND QUANTIFICATION OF GOIN 27/3277 HEAVY METAL IONS IN AQUEOUS See application file for complete search history . SOLUTION ( 71 ) Applicant: KING FAHD UNIVERSITY OF (56 ) References Cited PETROLEUM AND MINERALS , Dhahran (SA ) FOREIGN PATENT DOCUMENTS CN 100570349 C 12/2009 (72 ) Inventors : Ismail Abdulazeez, Dhahran (SA ) ; CN 103713036 A 4/2014 Abdel -Naser M. Kawde , Dhahran 104020213 A 9/2014 (SA ) ; Oki Muraza , Dhahran (SA ) ; GB 1 262 019 2/1972 Abdul- Rahman Al- Betar , Dhahran (SA ) OTHER PUBLICATIONS (73 ) Assignee : King Fahd University of Petroleum A. Walcarius, et al . “ Zeolite -modified solid carbon paste electrode” , and Minerals , Dhahran (SA ) Journal of Solid State Electrochemistry , 7 ( 10 ) :p . 671-677, Oct. 2003. * ( * ) Notice : Subject to any disclaimer, the term of this E.F. Sousa - Aguiar, et al . “ The role of rare earth elements in zeolites patent is extended or adjusted under 35 and cracking catalysts ” , Catalysis Today, v . 218-219 , p . 115-127 , U.S.C. 154 ( b ) by 387 days . Dec. 2013. * (21 ) Appl. No .: 15 /446,035 (Continued ) ( 22 ) Filed : Mar. 1 , 2017 Primary Examiner — J. Christopher Ball ( 74 ) Attorney, Agent, or Firm — Oblon , McClelland , (65 ) Prior Publication Data Maier & Neustadt, L.L.P. US 2017/0315079 A1 Nov. 2 , 2017 Related U.S. Application Data (57 ) ABSTRACT Electrodes comprising conducting graphite , paraffin oil past (60 ) Provisional application No. 62 /330,627 , filed on May ing liquid , and a rare earth metal impregnated zeolite , such 2 , 2016 . as lanthanum or cerium impregnated mordenite electrodes . (51 ) Int. Ci. Methods and voltammetric applications, such as square GOIN 27/333 ( 2006.01 ) wave anodic stripping voltammetry , of these rare earth metal GOIN 27/48 ( 2006.01) impregnated zeolite modified electrodes for the detection GOIN 27/30 ( 2006.01 ) and quantification of heavy metal ions such as Pb ( II ) and ( 52 ) U.S. CI. Cd ( II ) in aqueous solutions. CPC GOIN 27/333 ( 2013.01 ) ; GOIN 27/308 ( 2013.01 ) ; GOIN 27/48 ( 2013.01) 20 Claims, 76 Drawing Sheets DEL US 10,495,601 B2 Page 2 ( 56 ) References Cited Linyuan Cao , et al . “ Sensitive determination of Cd and Pb by differential pulse stripping voltammetry with in situ bismuth modified zeolite doped carbon paste electrodes” , Electrochimica OTHER PUBLICATIONS Acta , vol . 53 , 2008 , pp . 2177-2182 . Beatriz O. Hincapie , et al ., “ Synthesis of mordenite nanocrystals ” , Microporous and Mesoporous Materials , vol. 67 , 2004 , pp . 19-26 . A. Nezamaedeh - Ejhieh , et al. (“ Voltammetric determination of Hisham M. Aly , et al. , “ Synthesis of mordenite zeolite absence of riboflavin based on electrocatalytic oxidation at zeolite -modified organic template ” , Advanced Powder Technology , vol. 23 , 2012, pp . carbon paste electrodes ” , Journal of Industrial and Engineering 757-760 . Chemistry , 20 ( 4 ) : p . 2146-2152, Jul. 2014.* Georgia Kefala , et al. , “ Polymer- coated bismuth film electrodes for M. Arvand , et al. “ Electrochemical study of atenolol at a carbon the determination of trace metals by sequential- injection analysis / paste electrode modified with mordenite type zeolite ” , Material anodic stripping voltammetry” , Analytica Chimica Acta , vol. 576 , Science and Engineering C , 30 ( 5 ) : p . 709-714 , Jun . 2010. * 2006 , pp . 283-289. A.A. Shaikh, et al. “ Direct hydrothermal crystallization of high Gyoung - Ja Lee , et al ., “ Bismuth nano - powder electrode for trace silica large- port mordenite ” , Zeolites 13 ( 7 ) : Abstract only , Sep. analysis of heavy metals using anodic stripping voltammetry" , 1993.* Electrochemistry Communications, vol. 9 , 2007, pp . 2514-2518 . A. Ismail , et al. , “ Lanthanum -impregnated zeolite modified carbon Watsaka Siriangkhawut, et al. , “ Sequential injection monosegmented paste electrode for determination of Cadmium ( II ) " , Microporous flow voltammetric determination of cadmium and lead using a and Mesoporous Materials , vol. 225, 2016 , pp . 164-173 . bismuth film working electrode ” , Talanta , vol. 79, 2009, pp . 1118 S. Senthilkumar, et al ., “ Electrochemical sensing of cadmium and 1124 . lead ions at zeolite -modified electrodes : Optimization and field measurements ” , Sensors and Actuators B , vol . 141, 2009, pp . 65-75 . * cited by examiner U.S. Patent Dec. 3 , 2019 Sheet 1 of 76 US 10,495,601 B2 more ( +- ) Enc ?? ,? RO more ( - ) Epa more ( + ) potential more ( - ) FIG . 1 U.S. Patent Dec. 3 , 2019 Sheet 2 of 76 US 10,495,601 B2 pe E To Potential (V ) vs. Ag/ Aga FIG . 2 U.S. Patent Dec. 3 , 2019 Sheet 3 of 76 US 10,495,601 B2 Sample period Step AE potential Pulse period FIG . 3 U.S. Patent Dec. 3 , 2019 Sheet 4 of 76 US 10,495,601 B2 Sample period Pulse amplitude Quiet time FIG . 4 U.S. Patent Dec. 3 , 2019 Sheet 5 of 76 US 10,495,601 B2 Sample Potential period Amplitude (E ) AE U.S. Patent Dec. 3 , 2019 Sheet 6 of 76 US 10,495,601 B2 (E- ) (mv ) FIG . 6 U.S. Patent Dec. 3 , 2019 Sheet 7 of 76 US 10,495,601 B2 Oooola FIG.7 U.S. Patent Dec. 3 , 2019 Sheet 8 of 76 US 10,495,601 B2 FIG . 8 U.S. Patent Dec. 3 , 2019 Sheet 9 of 76 US 10,495,601 B2 Zeolite modified carbon paste U.S. Patent Dec. 3 ,? 2019 Sheet 10 of 76 US 10,495,601 B2 Analcime ???????????????????? ???? poos Intensity(a.u.) hemembantulah ???? harmant Luhrenheith???? ??? whenchmahan malaman ninh 20 ( degree ) U.S. Patent Dec. 3 , 2019 Sheet 11 of 76 US 10,495,601 B2 U.S. Patent Dec. 3 , 2019 Sheet 12 of 76 US 10,495,601 B2 FIG . 12 U.S. Patent Dec. 3 , 2019 Sheet 13 of 76 US 10,495,601 B2 20 ur FIG . 13 U.S. Patent Dec. 3 , 2019 Sheet 14 of 76 US 10,495,601 B2 U.S. Patent Dec. 3 , 2019 Sheet 15 of 76 US 10,495,601 B2 6 8 FIG . 15 U.S. Patent Dec. 3 , 2019 Sheet 16 of 76 US 10,495,601 B2 WHwaran non van wherman man ay marahmutphon 150 50 100 150 200 250 Chemical shift ( ppm ) FIG . 16 U.S. Patent Dec. 3 , 2019 Sheet 17 of 76 US 10,495,601 B2 B 20 Current(UA) ??????? ??????????????? -0.2 0.2 0.4 0.8 E / V vs Ag/ AgCl U.S. Patent Dec. 3 , 2019 Sheet 18 of 76 US 10,495,601 B2 50 30 di)vm( 20 30 La -MOR - 15 % U.S. Patent Dec. 3 , 2019 Sheet 19 of 76 US 10,495,601 B2 50 30 Current(LLA) 400 -10 E / V vs Ag/ Age FIG . 19 U.S. Patent Dec. 3 , 2019 Sheet 20 of 76 US 10,495,601 B2 y = 1.73871 +4.0127 R2 = 0.9992 Current(UA) 20 11 0 2 8 18 20 (Scan rate ) 12 FIG . 20 U.S. Patent Dec. 3 , 2019 Sheet 21 of 76 US 10,495,601 B2 Current(UA) 5 0.2 FIG . 21 U.S. Patent Dec. 3 , 2019 Sheet 22 of 76 US 10,495,601 B2 yo 2.948x * 7.8081 FIG . 22 U.S. Patent Dec. 3 , 2019 Sheet 23 of 76 US 10,495,601 B2 140 120 - 100 Current(UA) 60 20 - -0.6 -0.2 E / V vs Ag /AgCI FIG . 23 U.S. Patent Dec. 3 , 2019 Sheet 24 of 76 US 10,495,601 B2 1.3 FIG . 24 U.S. Patent Dec. 3 , 2019 Sheet 25 of 76 US 10,495,601 B2 140 120 100 1 Current(UA) 20 -1.2 -0.8 -0.2 0.0 E / V vs Ag/ AgCI FIG . 25 U.S. Patent Dec. 3 , 2019 Sheet 26 of 76 US 10,495,601 B2 90 Current(1) 90 *************************** 20 170 Accomulation time is FIG . 26 U.S. Patent Dec. 3 , 2019 Sheet 27 of 76 US 10,495,601 B2 Current(PA) 50 ppb EIV vs AgAgci FIG . 27 U.S. Patent Dec. 3 , 2019 Sheet 28 of 76 US 10,495,601 B2 Current(MA) E /Vvs Ag/ AgCI FIG . 28 U.S. Patent Dec. 3 , 2019 Sheet 29 of 76 US 10,495,601 B2 y = 0.11631-3.0945 0 [ C ( IT ) ppb FIG . 29 35 y = 0.0545x + 0.3453 3 2.5 15 good 0 CA (IT ) ppb FIG . 30 U.S. Patent Dec. 3 , 2019 Sheet 30 of 76 US 10,495,601 B2 Current(MA) WA EIVvs AgAga FIG . 31 U.S. Patent Dec. 3 ,? 2019 Sheet 31 of 76 US 10,495,601 B2 {b } Intensity(a.u.) whenhalle????? whethman { } ??????? 5 Ander3 {} 20 ( degree ) FFG.32 U.S. Patent Dec. 3 , 2019 Sheet 32 of 76 US 10,495,601 B2 MOR - 15 FIG . 33 U.S. Patent Dec. 3 , 2019 Sheet 33 of 76 US 10,495,601 B2 2 0 U.S. Patent Dec. 3 ,? 2019 Sheet 34 of 76 US 10,495,601 B2 { }} ?????hahah dulu ????? ????? heruntMandramanmarathon nhanh ??????? homembenanthi mathemahan a ) ???????????? ?????? ????25 35 20 ( degree ) FIG , 35 U.S. Patent Dec. 3 ,? 2019 Sheet 35 of 76 US 10,495,601 B2 haha Intensity(a.u) ????? ???????????halaman Laulman hrada anaand ?????????????? 5 1 2 20 ( degree ) 1.36 U.S. Patent Dec. 3 , 2019 Sheet 36 of 76 US 10,495,601 B2 FIG . 37 U.S. Patent Dec. 3 , 2019 Sheet 37 of 76 US 10,495,601 B2 FIG . 38 U.S. Patent Dec. 3 , 2019 Sheet 38 of 76 US 10,495,601 B2 FIG . 39 U.S. Patent Dec. 3 , 2019 Sheet 39 of 76 US 10,495,601 B2 U.S.