1 寮曡█

鍦ㄥ埗鍌欐薄娉ョ偔閬�(gu貌)绋嬩腑甯稿埄鐢╖nCl2绛夊寲瀛�(xu茅)娲诲寲鍔戦€�(j矛n)琛屾椿鍖栬檿鐞�,浠ュ鍔犲惛闄勫姂鐨勫惛闄勬€ц兘 ,涔熸湁瀛�(xu茅)鑰呭湪鍒跺倷閬�(gu貌)绋嬩腑閫氶亷(gu貌)鎽婚洔杌熼尦绀�銆丯a2CO3鍜孧nO2鎴栧惈閶呮薄娉� 渚�(l谩i)鏀规€ф薄娉ョ偔鎻愰珮鍚搁檮鎬ц兘,鍏朵綔鐢ㄦ(j墨)鐞嗘槸鍌寲鍒嗚В姹℃偿鏈夋(j墨)璩�(zh矛)銆佷績閫�(j矛n)绌嶇偔鍙嶆噳(y墨ng),閫�(j矛n)涓€姝ユ彁楂樻薄娉ュ惛闄勫姂鐨勬瘮琛ㄩ潰绌�.鑰屽虎鑸奪n-C闆绘睜闆绘サ鏉愭枡涓磩鍚�15%~30%鐨凜鏅堕珨鐗╄唱(zh矛)銆�12%~28%鐨勯媴鍜�26%~45%鐨勯尦,鍏朵腑,閶�銆侀尦鍏冪礌涓昏浠ュ洓鏂归珨閶呴尦绀︾祼(ji茅)妲�(g貌u)ZnMn2O4鏅堕珨銆佺珛鏂归珨閻甸尦绀n2O3銆丮n3O4銆丮nO2銆乑nO銆乑n5(OH)2Cl2 路 H2O鍜孼n5(NH3)2Cl2绛夋贩鍚堢墿璩�(zh矛)褰㈠紡瀛樺湪,鍙敤浜庢敼鎬ф薄娉ュ熀娲绘€х偔鐨勫埗鍌�,寰炶€屾浛浠ｉ媴閷宠│鍔戞垨鏄笡灏慫nCl2绛夊寲瀛�(xu茅)娲诲寲鍔戠殑浣跨敤閲�.涔嬪墠鐨勭爺绌剁櫦(f膩)鐝�(xi脿n),閫氶亷(gu貌)鎽婚洔寤㈣垔Zn-C闆绘睜鏉愭枡鍙互椤憲鏀瑰杽姹℃偿鐐殑鍚搁檮鎬ц兘,鍦ㄨ唱(zh矛)閲忔懟闆滄瘮3 鈭� 1鐨勬浠朵笅,纰樺惛闄勫€艰純绱旀薄娉ョ偔鎻愰珮浜�100 mg 路 g-1宸﹀彸,琛ㄦ槑瑭叉硶鍏锋湁涓€瀹氱殑鍙鎬�.鐒惰€�,鍦ㄦ薄娉ョ偔鐨勫埗鍌欓亷(gu貌)绋嬩腑褰遍熆鍏跺惛闄勬€ц兘鐨勫洜绱犺純澶�,鍖呮嫭锛氭椿鍖栧姂婵冨害銆佸浐娑叉瘮銆佺偔鍖栨韩搴︺€佺偔鍖栨檪(sh铆)闁�銆佹椿鍖栨韩搴﹀拰娲诲寲鏅�(sh铆)闁撶瓑 ,閫欎簺宸ヨ棟鍙冩暩(sh霉)鐨勭⒑瀹氬皪(du矛)鏀规€ф薄娉ョ偔鐨勬€ц兘鍎�(y艒u)鍖栧挨鐐洪棞(gu膩n)閸�,涔嬪墠鐨勭爺绌�?j墨)H鐐烘薄娉ュ拰寤㈣垔闆绘睜闆绘サ鏉愭枡鎽婚洔姣斾笅鍠洜绱犵殑鍒濇鍢楄│,鐒�(w煤)娉曟彁渚涙洿澶氱殑鍎�(y艒u)鍖栦俊鎭�,鍥犳,鏈夊繀瑕佸皪(du矛)鍒跺倷宸ヨ棟鍙冩暩(sh霉)閫�(j矛n)琛屽叏闈㈢殑瀵�(sh铆)椹�(y脿n)瑷�(sh猫)瑷�(j矛)鍎�(y艒u)鍖�.

Plackett-Burman(P-B)鏂规硶鏄竴绋閬稿(sh铆)椹�(y脿n)瑷�(sh猫)瑷�(j矛),涓昏閲濆皪(du矛)鍥犵礌杓冨,涓旀湭纰哄畾鐪惧洜瀛愬皪(du矛)浜庨熆鎳�(y墨ng)璁婇噺鐨勯’钁楁€ц€岄噰鐢ㄧ殑瀵�(sh铆)椹�(y脿n)瑷�(sh猫)瑷�(j矛)鏂规硶,鑰岄熆鎳�(y墨ng)闈腑蹇冨京(f霉)鍚堝(sh铆)椹�(y脿n)瑷�(sh猫)瑷�(j矛)(RSM-CCD)鍙敤浜庣⒑瀹氬洜绱犲強鍏朵氦浜掍綔鐢ㄥ湪瀵�(sh铆)椹�(y脿n)閬�(gu貌)绋嬩腑灏�(du矛)鐩(bi膩o)闊挎噳(y墨ng)鍊肩殑褰遍熆,绮剧⒑鍦拌〃杩板悇鍥犵礌鍜岄熆鎳�(y墨ng)鍊间箣闁撶殑闂�(gu膩n)绯�.閫氶亷(gu貌)閫欏叐绋柟娉曠殑绲�(ji茅)鍚�,鍗冲皪(du矛)P-B鏂规硶绡╅伕鐨勪富鍥犵礌閫�(j矛n)琛孯SM-CCD瑷�(sh猫)瑷�(j矛),鍙互瑙ｆ焙鍠洜绱犲(sh铆)椹�(y脿n)鏂规硶涓嶈兘鑰冨療鍥犵礌闁撲氦浜掍綔鐢ㄥ強瀵�(sh铆)椹�(y脿n)閲忓ぇ鐨勫晱(w猫n)椤�.鐐烘,鏈爺绌跺湪宸叉湁鐨勫伐浣滃熀绀�(ch菙)涓�,閲囩敤P-B瑷�(sh猫)瑷�(j矛)鏂规硶鑰冨療鎽婚洔姣斻€佹椿鍖栧姂婵冨害銆佸浐娑叉瘮銆佹椿鍖栨韩搴�銆佹椿鍖栨檪(sh铆)闁撱€佺偔鍖栨韩搴﹀拰鐐寲鏅�(sh铆)闁撶瓑7鍊�(g猫)鍒跺倷宸ヨ棟鍙冩暩(sh霉),閫氶亷(gu貌)绲�(t菕ng)瑷�(j矛)瀛�(xu茅)绡╅伕寰楀嚭鍏朵腑鐨勯棞(gu膩n)閸靛洜绱�,閫�(j矛n)涓€姝ュ埄鐢≧SM-CCD瑷�(sh猫)瑷�(j矛)灏�(du矛)闂�(gu膩n)閸靛洜绱犻€�(j矛n)琛岄熆鎳�(y墨ng)闈㈠劒(y艒u)鍖栧垎鏋�,鏈€绲傜⒑瀹氭渶鍎�(y艒u)鍒跺倷姊濅欢.鍚屾檪(sh铆),缍�(j墨ng)BET銆丼EM-EDX銆乆RD銆丗T-IR銆乑eta闆讳綅鍜岄櫧(y谩ng)闆㈠瓙浜ゆ彌瀹归噺(CEC)绛夎〃寰佹墜娈�,灏�(du矛)鍒跺緱鐨勬敼鎬ф薄娉ョ偔閫�(j矛n)琛屽井瑙€琛ㄥ緛鍒嗘瀽,浠ユ湡鐐烘薄娉ュ拰寤㈣垔Zn-C闆绘睜璩囨簮鍖栫殑鐮旂┒鎻愪緵涓€浜涚悊璜栦緷鎿�(j霉).

2 鏉愭枡鑸囨柟娉�

2.1 鏉愭枡

2.1.1 姹℃偿鍘熸枡

瑭﹂(y脿n)姹℃偿鍙栬嚜寤跺畨甯傛薄姘磋檿鐞�寤犱簩娌夋睜鑴按姹℃偿,缍�(j墨ng)鑷劧鏅惧共鑷冲惈姘寸巼浣庝簬10%,鐮旂（鐮寸閬�(gu貌)100鐩,鍐嶅皣骞叉薄娉ョ矇鏈疆浜庣儤绠变腑浜�105 鈩冩浠朵笅骞茬嚗鑷虫亽閲嶄綔鐐哄師鏂欏倷鐢�.

2.1.2 寤㈣垔Zn-C闆绘睜闆绘サ鏉愭枡

鍙栧競闈笂甯歌(ji脿n)鐨�5铏�(h脿o)寤㈣垔鑿おZn-C闆绘睜,鎸夊湒 1鎵嬪伐鎷嗗垎鍑哄鏂�銆侀噾灞毊銆佸鍦�銆侀泦闆婚妳閲�銆佺⒊妫�銆佺墰鐨礄鍙婇浕瑙ｈ唱(zh矛)鏉愭枡;灏�(du矛)鏀堕泦鐨勯浕瑙ｈ唱(zh矛)鏉愭枡,纰剧（閬�(gu貌)100鐩,娣峰悎鍧囧嫽鐑樺共鍚庝綔鎽婚洔鐗╂枡鍌欑敤.


2.2 瀵�(sh铆)椹�(y脿n)姝ラ

2.2.1 绡╅伕P-B瀵�(sh铆)椹�(y脿n)瑷�(sh猫)瑷�(j矛)

鎳�(y墨ng)鐢―esign Expert 8.0 杌熶欢灏�(du矛)姹℃偿鐐埗鍌欏(sh铆)椹�(y脿n)閫�(j矛n)琛孭-B瑷�(sh猫)瑷�(j矛)(琛� 1).鏍规摎(j霉)鍓嶆湡鐨勬帰绱㈠(sh铆)椹�(y脿n),灏�(du矛)鍒跺倷宸ヨ棟閬�(gu貌)绋嬬殑7鍊�(g猫)褰遍熆鍥犵礌閫�(j矛n)琛岀閬�,鍗虫懟闆滄瘮銆佹椿鍖栧姂婵冨害銆佸浐娑叉瘮銆佹椿鍖栨韩搴�銆佹椿鍖栨檪(sh铆)闁�銆佺偔鍖栨韩搴﹀拰鐐寲鏅�(sh铆)闁�,澶栧姞4鍊�(g猫)铏涙摤璁婇噺.姣忓€�(g猫)璁婇噺鍒嗗垾纰哄畾楂�(+)鍜屼綆(-)鍏╁€�(g猫)姘村钩,鍏遍€�(j矛n)琛�12娆″(sh铆)椹�(y脿n)浠ョ⒑瀹氭瘡鍊�(g猫)鍥犵礌鐨勫奖闊垮洜瀛�.

2.2.2 鍎�(y艒u)鍖朢SM-CCD瀵�(sh铆)椹�(y脿n)瑷�(sh猫)瑷�(j矛)

灏�(du矛)P-B瀵�(sh铆)椹�(y脿n)绡╅伕鍑虹殑3鍊�(g猫)閲嶈鍥犵礌(鎽婚洔姣斻€佺偔鍖栨韩搴�銆佺偔鍖栨檪(sh铆)闁�)閫�(j矛n)琛孯SM-CCD瀵�(sh铆)椹�(y脿n)瑷�(sh猫)瑷�(j矛)(琛� 2),鍏跺畠宸ヨ棟鍙冩暩(sh霉)绲�(t菕ng)涓€瑷�(sh猫)瀹氱偤锛氭椿鍖栧姂婵冨害1 mol 路 L-1,鍥烘恫姣�25%,娲诲寲婧害25 鈩�,娲诲寲鏅�(sh铆)闁�6 h;瑷�(sh猫)瑷�(j矛)鍑虹敱8鍊�(g猫)鍏ㄥ洜瀛愯│椹�(y脿n)銆�8鍊�(g猫)杌稿悜榛�(di菐n)鍜�6鍊�(g猫)绔嬫柟楂旂殑涓績榛�(di菐n)绲勬垚鐨�20娆¤│椹�(y脿n)鐨凜CD,姣忓€�(g猫)杌搁粸(di菐n)璺濅腑蹇冪殑璺濋洟伪鐐洪粯瑾�(r猫n)鍊�2.0,涓績寰�(f霉)鍚堣ō(sh猫)瑷�(j矛)鍚勫洜绱犲強姘村钩瑷�(sh猫)缃琛� 2鎵€绀�.瀵�(sh铆)椹�(y脿n)鐨勭鍚搁檮鍊肩殑闊挎噳(y墨ng)鍊煎彲浠ラ€氶亷(gu貌)濡備笅浜岄殠妯″瀷鎻忚堪:

琛� 2涓績寰�(f霉)鍚堣ō(sh猫)瑷�(j矛)鍚勫洜绱犲強姘村钩瑷�(sh猫)缃�
(1)

寮忎腑,Y鐐烘薄娉ョ偔鎴愬搧鐨勭鍚搁檮鍊奸熆鎳�(y墨ng)鍊�;尾0銆佄瞚銆佄瞚i鍜屛瞚j鍒嗗垾鐐烘摤鍚堝叕寮忕殑甯告暩(sh霉)闋�(xi脿ng)銆佺窔鎬ч爡(xi脿ng)銆佷簩娆￠爡(xi脿ng)鍜屼氦浜掗爡(xi脿ng)绯绘暩(sh霉);Xi銆乆j浠ｈ〃鍚勫洜绱犳按骞崇殑绶ㄧ⒓鍊�,鍗虫懟闆滄瘮銆佺偔鍖栨韩搴﹀拰鐐寲鏅�(sh铆)闁�.

2.2.3 鍒跺倷鏂规硶

鎸夌収涓婅堪瀵�(sh铆)椹�(y脿n)瑷�(sh猫)瑷�(j矛),绋�(ch膿ng)鍙栦笉鍚屾懟闆滄瘮涓嬬殑姹℃偿鍜岄浕姹犵矇鏈師鏂欏苟鍏呭垎娣峰悎,鍦ㄨō(sh猫)瑷�(j矛)鐨刏nCl2婵冨害鍙婂浐娑叉瘮涓嬮€�(j矛n)琛岄潨缃椿鍖�,鐒跺悗灏囨椿鍖栧悗鐨勬薄娉ョ疆浜庣儤绠变腑骞茬嚗鑴按.灏囨椿鍖栬劔姘村悗娣峰悎姹℃偿妯ｅ搧缃簬棣紬鐖�,鍦ㄥ悇鍊�(g猫)鐐寲婧害銆佸崌婧€熺巼銆佺偔鍖栧仠鐣欐檪(sh铆)闁撲笅纰冲寲姹℃偿,纰冲寲绲�(ji茅)鏉熺敤楣介吀姘存憾娑插拰钂搁ぞ姘存礂婊岃嚦涓€у悗骞茬嚗鍐峰嵒,鍗冲緱鍒板虎鑸奪n-C闆绘睜-娲绘€ф薄娉ョ偔鎴愬搧.鎵€鏈夊(sh铆)椹�(y脿n)鍧囩偤3绲勫钩琛屾ǎ,骞跺仛涓嶆坊鍔犻浕姹犵矇鏈殑绌虹櫧妯�.

2.3 姹℃偿鐐€ц兘琛ㄥ緛

灏�(du矛)鍒跺倷鐨勬垚鍝佹脯(c猫)閲忕鍚搁檮鍊�(GB/T122496.8鈥�1999銆婃湪璩�(zh矛)娲绘€х偔瑭﹂(y脿n)鏂规硶纰樺惛闄勫€肩殑娓�(c猫)瀹氥€�),鐢ㄩΜ寮楃垚(SX-8-40,鍖椾含绉戝亯姘歌垐鍎€鍣ㄦ湁闄愬叕鍙�)閫�(j矛n)琛岀偔鍖栨椿鍖�;閲囩敤姣旇〃闈㈢⿳鍙婂瓟寰戝垎甯冩脯(c猫)閲�?j墨)x(鍖椾含閲戝焹璀淰-Sorb 2800P)閫�(j矛n)琛屾瘮琛ㄩ潰绌嶅強瀛斿緫鍒嗗竷娓�(c猫)閲�;妯ｅ搧寰褰㈡厠(t脿i)瀛�(xu茅)璁婂寲鍙婅兘璀滃垎鏋愮敤SEM-EDX(Hitachi S-4800,15kV,鏃ユ湰)瑙€瀵�;绲�(ji茅)妲�(g貌u)銆佺磪澶栧厜璀滃垎鏋愬垎鍒ョ敤XRD(Shimdzu,CuK伪,k=1.5418,鏃ユ湰)鍜岀磪澶栧厜璀滃剙(IR200) 瀹屾垚;鐢ㄥ厓绱犲垎鏋愬剙(VARIO EL CUBE,寰峰湅(gu贸)ELEMENTAR)閫�(j矛n)琛屽厓绱犲垎鏋�,鎿嶄綔妯″紡鐐篊HNS銆丱,娓�(c猫)瀹氭ǎ鍝丆銆丠銆丯銆丱銆丼鍏冪礌璁婂寲;閲囩敤Colloidal-159 Dynamics鍨嬪垎鏋愬剙(缇庡湅(gu贸))娓�(c猫)閲廧eta闆讳綅娓�(c猫)瀹�,骞舵脯(c猫)瀹氶櫧(y谩ng)闆㈠瓙浜ゆ彌瀹归噺(CEC).

3 绲�(ji茅)鏋滆垏瑷庤珫

3.1 P-B瑷�(sh猫)瑷�(j矛)瀵�(sh铆)椹�(y脿n)绲�(ji茅)鏋滃垎鏋�

P-B瀵�(sh铆)椹�(y脿n)瑷�(sh猫)瑷�(j矛)纰樺惛闄勫€肩祼(ji茅)鏋滆(ji脿n)琛� 3.閲囩敤Design Expert 8.0杌熶欢灏�(du矛)琛� 3涓殑纰樺惛闄勫€奸€�(j矛n)琛屽洖姝稿垎鏋�,寰楀埌鍚勫奖闊垮洜瀛愮殑P-B瑷�(sh猫)瑷�(j矛)ANOVA 绲�(ji茅)鏋滃強涓绘晥鎳�(y墨ng)鍒嗘瀽(琛� 4),鍙互鏄庨’鐪嬪嚭,鍥犵礌涓殑鎽婚洔姣�(X1)銆佺偔鍖栨韩搴�(X6)鍜岀偔鍖栨檪(sh铆)闁�(X7)鐐轰富瑕佸奖闊垮洜瀛�(p<0.05) ,瀹冨€戠殑璨㈢嵒(xi脿n)鍊煎垎鍒ョ偤30.22%銆�23.22%鍜�39.11%,鑰屽叾浣欏洜瀛愯并鐛�(xi脿n)鍊艰純浣�.鍚屾檪(sh铆),4鍊�(g猫)铏涙摤鍥犵礌X8~X11灏�(du矛)纰樺惛闄勫€肩殑璨㈢嵒(xi脿n)鐜囧垎鍒ョ偤2.67%銆�0.52%銆�0.47%鍜�0.44%(琛ㄤ腑鏈垪鍑�),琛ㄦ槑鍏跺皪(du矛)纰樺惛闄勫€煎奖闊垮緢浣�,瑾�(shu艒)鏄庝富鍥犵礌鍥炴绶氭€фā鍨嬫槸鍙鐨�,缍�(j墨ng)褰遍熆鍥犵礌绡╅伕,寰楀埌浠ユ薄娉ョ偔纰樺惛闄勫€�(IN,mg 路 g-1)鐐洪熆鎳�(y墨ng)鍊肩殑绶氭€у洖姝告柟绋嬶細

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姝ゅ,鐢辫〃 4涓殑褰遍熆姘村钩鏁�(sh霉)鎿�(j霉)鍙煡,鍥犵礌?f霉)璇玸姣旂殑E(X1)= -119.1,琛ㄦ槑鎽婚洔姣斿皪(du矛)纰樺惛闄勫€肩殑褰遍熆鐐鸿矤(f霉)鍚戠殑,鍗抽毃钁楁懟闆滄瘮鐨勫鍔�,纰樺惛闄勫€煎憟涓嬮檷瓒ㄥ嫝(sh矛),鍥犳,鍦ㄥ悗绻肩殑RSM-CCD鍎�(y艒u)鍖栬│椹�(y脿n)涓噳(y墨ng)瑭查檷浣庢懟闆滄瘮;鍚岀悊,涔熼仼鐢ㄤ簬鐐寲婧害鍙婄偔鍖栨檪(sh铆)闁�.

3.2 RSM-CCD瀵�(sh铆)椹�(y脿n)绲�(ji茅)鏋滃垎鏋�3.2.1 妯″瀷鎿悎鍙婂洜绱犲奖闊�

琛� 5 鏄€氶亷(gu貌)CCD瑭﹂(y脿n)瑷�(sh猫)瑷�(j矛)寰楀埌鐨勬薄娉ョ偔纰樺惛闄勬脯(c猫)閲忓€煎拰闋�(y霉)娓�(c猫)鍊�.鐢辫〃 6鐨勭鍚搁檮鍊煎洖姝哥郴鏁�(sh霉)鐨勮▓(j矛)绠楀€煎彲鐭ワ細鎽婚洔姣�銆佺偔鍖栨韩搴�銆佺偔鍖栨檪(sh铆)闁撳皪(du矛)纰樺惛闄勫€兼湁椤憲绶氬奖闊�,鍏朵腑,鐐寲婧害銆佺偔鍖栨檪(sh铆)闁撻倓鍏锋湁闈炵窔鎬ч’钁椾笖瀛樺湪浜や簰浣滅敤褰遍熆;閫�3鍊�(g猫)鍥犵礌灏�(du矛)闊挎噳(y墨ng)鍊奸兘鏈夐’钁楀奖闊�,鍏朵腑,鐐寲婧害銆佺偔鍖栨檪(sh铆)闁撻€欏叐鍊�(g猫)鍥犵礌鐩稿皪(du矛)褰遍熆鏇村ぇ.纰樺惛闄勫€肩殑闊挎噳(y墨ng)鍊煎闋�(xi脿ng)娆℃摤鍚堝叕寮忓寮�(3) 鎵€绀�,鍏舵焙瀹氱郴鏁�(sh霉)鐐�0.9220,瑾�(shu艒)鏄庢ā鍨嬬殑鎿悎绋嬪害杓冨ソ.鐢辫〃 7妯″瀷鏂瑰樊鍒嗘瀽鍙煡,妯″瀷F鍊肩偤13.14,p鍊肩偤0.001(p <0.05) ,鍚屾檪(sh铆),妯″瀷澶辨摤涓嶉’钁�(p=0.201 > 0.01) ,涔熻〃鏄庢ā鍨嬮珮搴﹂’钁�,鍙互闋�(y霉)娓�(c猫)闊挎噳(y墨ng)鍊�.


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3D闊挎噳(y墨ng)鍊兼洸闈㈠湒 2(鏈’绀哄洜绱犵偤0姘村钩)鐩磋鍦拌〃寰佷簡涓夊洜绱犱氦浜掑奖闊垮皪(du矛)纰樺惛闄勬€ц兘鐨勫奖闊�.鍙互娓呮鍦扮湅鍑�,闅ㄨ憲鎽婚洔姣旂殑澧炲姞,闊挎噳(y墨ng)鍊奸檷浣�,鍙兘鏄亷(gu貌)澶氱殑鍔犲叆闆绘睜鏉愭枡,鐩稿皪(du矛)鏈�(hu矛)闄嶄綆绺界殑鏈夋(j墨)纰冲惈閲�;鍙﹀,鍦ㄥ(sh铆)椹�(y脿n)鐨勫彇鍊艰寖鍦嶅収(n猫i),鐐寲鏅�(sh铆)闁撳拰鐐寲婧害鍧囧皪(du矛)鎳�(y墨ng)鏈夋渶鍎�(y艒u)姊濅欢鐨勯熆鎳�(y墨ng)榛�(di菐n).鐢卞湒涓彲浠ョ湅鍑�,鐐寲婧害鍜岀偔鍖栨檪(sh铆)闁撲氦浜掍綔鐢ㄩ’钁�,闅ㄨ憲鐐寲婧害鐨勫崌楂樺拰鐐寲鏅�(sh铆)闁撶殑寤堕暦(zh菐ng)娲诲寲绋嬪害閫愭鍔犳繁,鏈夊埄浜庡井瀛斿拰涓瓟褰㈡垚,闊挎噳(y墨ng)鍊间篃閫愭鍗囬珮,鍙互閬�(d谩)鍒板(sh铆)椹�(y脿n)涓殑妤靛ぇ鍚搁檮鍊�;浣嗛毃钁楃偔鍖栨韩搴︿笉鏂峰崌楂樺拰鐐寲鍋滅暀鏅�(sh铆)闁撶殑寤堕暦(zh菐ng),娲绘€х偔鐨勭啽鏀剁府鏈�(hu矛)鐮村褰㈡垚鐨勫瓟绲�(ji茅)妲�(g貌u),寰瓟琚摯(ku貌)瀛斿舰鎴愪簡涓瓟骞朵即鏈夐儴鍒嗙噿澶�,灏�(d菐o)鑷存瘮琛ㄩ潰绌嶄笅闄�,鏈�(hu矛)闄嶄綆娲绘€х偔纰樺惛闄勫€�(Rozada et al., 1998; Encinar et al., 2005).


3.2.2 妯″瀷鏈€鍎�(y艒u)鍖栧(sh铆)椹�(y脿n)

缍�(j墨ng)閬�(gu貌)妯″瀷鏈€鍎�(y艒u)鍖栭爯(y霉)娓�(c猫),鐣�(d膩ng)鍥犵礌姘村钩鐐烘懟闆滄瘮10%銆佺偔鍖栨韩搴�350 鈩冨拰鐐寲鏅�(sh铆)闁�20 min鏅�(sh铆),鍙緱鍒版サ澶у€奸熆鎳�(y墨ng)鍊�543.1 mg 路 g-1.鎸夌収涓婅堪鍥犵礌姘村钩閫�(j矛n)琛屽(sh铆)椹�(y脿n)椹�(y脿n)璀�,3娆″钩琛屽(sh铆)椹�(y脿n)鐨勭祼(ji茅)鏋滃垎鍒ョ偤512.6銆�557.8鍜�519.9 mg 路 g-1,鍗�(530.1卤24.3) mg 路 g-1,鎴愬搧鐨勭敘(ch菐n)鐜囩偤60.5% 卤3.7%.闋�(y霉)娓�(c猫)绮惧害閬�(d谩)鍒�97.6%,妯″瀷杓冨ソ鍦伴爯(y霉)娓�(c猫)浜嗘懟闆滃虎鑸婇浕姹犳敼鎬ф薄娉ョ偔鐨勭鍚搁檮鍊�,鐢辨鍙(ji脿n),灏嘡SM-CCD鐢ㄤ簬鍎�(y艒u)鍖栨敼鎬ф薄娉ョ偔鍒跺倷鐮旂┒鏄彲琛岀殑.

3.3 姹℃偿鐐〃寰佸垎鏋�

3.3.1 BET銆丼EM-EDX鍙婂厓绱犲垎鏋�

鍒╃敤姣旇〃闈㈢⿳鍎€灏�(du矛)鍎�(y艒u)鍖栨浠朵笅鍒跺倷鐨勭敘(ch菐n)鍝侀€�(j矛n)琛屾€ц兘鍒嗘瀽,妯ｅ搧鐨勬瘮琛ㄩ潰绌嶇偤429.5 m2 路 g-1,绺藉瓟瀹�0.305 cm3 路 g-1,寰瓟瀹�0.179 cm3 路 g-1,骞冲潎瀛斿緫3.9 nm;鍎�(y艒u)鍖栨浠朵笅鍒跺緱鐨勬敼鎬ф薄娉ョ偔妯ｅ搧涓瓟瀛斿緫涓昏闆嗕腑鍦�3~5 nm鑼冨湇,鑸囦箣鍓嶇殑鐮旂┒涓€鑷�,鏇撮仼鍚堝惛闄勫ぇ鍒嗗瓙鐗╄唱(zh矛).

鐢辨ǎ鍝佺殑闆婚彙鎺冩弿鍦� 3鍙(ji脿n),鍘熸薄娉ユǎ鍝�(鍦� 3a)鐨勮〃闈㈣純鐐哄厜婊�,鐒�(w煤)绺殭鍛堝堡鐙€绲�(ji茅)妲�(g貌u),鐢盓DX鍏冪礌鍒嗘瀽鍙煡(琛� 8),鍏禖鍚噺楂橀仈(d谩)60%;鍦� 3b鐐哄埗鍌欑殑绱旀薄娉ョ偔闆婚彙鎺冩弿鍦�,姹℃偿缍�(j墨ng)閬�(gu貌)娲诲寲纰冲寲鍚�,鍏惰〃闈㈠嚭鐝�(xi脿n)浜嗗ぇ閲忕⒊鍖栫殑椤嗙矑,澶уぇ澧炲姞浜嗗叾琛ㄩ潰绌�,鍚屾檪(sh铆)涔熷嚭鐝�(xi脿n)浜嗗瓟娲炵祼(ji茅)妲�(g貌u);鐩告瘮绱旀薄娉ョ偔,鏀规€у悗姹℃偿鐐櫎鍏峰倷涓婅堪鐗瑰緛澶�,鍏惰〃闈㈤倓鍛堢従(xi脿n)澶ч噺涓嶈(gu墨)鍓囩殑澶氬瓟绲�(ji茅)妲�(g貌u)(鍦� 3c),閫�(j矛n)涓€姝ユ彁鍗囦簡鍏跺惛闄勬€ц兘.姹℃偿銆佺磾姹℃偿鐐拰鏀规€ф薄娉ョ偔妯ｅ搧缍�(j墨ng)鍏冪礌鍒嗘瀽,C鍚噺鍒嗗垾鐐�56.53%銆�52.38%銆�51.89%;H鍚噺鐐�5.36%銆�3.16%銆�1.89%;O鍚噺鍒嗗垾鐐�27.82%銆�25.76%銆�24.95%.鍙(ji脿n),鏀规€у悗鐨勬ǎ鍝�3绋厓绱犲潎鏈変笉鍚岀▼搴︿笅闄�,閫欎篃瑾�(shu艒)鏄庡虎鑸奪n-C闆绘睜鏉愭枡鐨勫姞鍏ュ偓鍖栦篃鍒嗚В浜嗘薄娉ユ湁姗�(j墨)璩�(zh矛),閫�(j矛n)鑰屾彁楂樻薄娉ュ惛闄勫姂鐨勬瘮琛ㄩ潰绌�.灏�(du矛)姣旂磾姹℃偿鐐拰鏀规€ф薄娉ョ偔鐨凟DX鍏冪礌鐩稿皪(du矛)鍚噺鍙煡(琛� 7),C銆丱鍚噺杓冮珮,鑸囧厓绱犲垎鏋愬熀鏈竴鑷�,鑰屽虎鑸奪n-C闆绘睜鏉愭枡鐨勬懟闆滃皪(du矛)鏀规€ф薄娉ュ叾瀹冨厓绱犲奖闊夸笉澶�.


3.3.2 XRD銆丗T-IR鍒嗘瀽

鐢盭RD鍦� 4涓彲鐭�,姹℃偿闄iO2鏅堕珨澶�,閭勫瓨鍦–aCO3琛嶅皠宄�;鑰岀磾姹℃偿鐐拰鏀规€ф薄娉ョ偔妯ｅ搧鍥犳椿鍖�銆佺⒊鍖栧拰閰稿寲铏曠悊涓嶅惈瑭叉櫠楂旇灏勫嘲.涔嬪墠鐮旂┒涔熺櫦(f膩)鐝�(xi脿n),姹℃偿鐐富瑕佸瓨鍦⊿iO2鏅堕珨琛嶅皠宄�,C绲�(ji茅)妲�(g貌u)灞笉瑕�(gu墨)鍓囩祼(ji茅)鏅剁祼(ji茅)妲�(g貌u)(浠绘剾(脿i)鐜茬瓑,2006; 鐗涘織鐫跨瓑,2014b). 鏀规€ф薄娉ョ偔妯ｅ搧涓笉鍚媴閷崇瓑鏅堕珨鐗╄唱(zh矛),绲�(ji茅)鍚圗DX鍒嗘瀽鍙互鎺ㄦ柗,闆绘睜涓殑ZnMn2O4銆丮n2O3銆乑n5(OH)2Cl2 路 H2O鍜孼n5(NH3)2Cl2绛夊惈閶呴尦鏅舵牸鐗╄唱(zh矛)鍦ㄦ薄娉ョ偔鍒跺倷娲诲寲閬�(gu貌)绋嬫垨鐐寲閬�(gu貌)绋嬩腑鍙冭垏浜嗗弽鎳�(y墨ng),杞�(zhu菐n)璁�?y艒u)妤︻彎濮垮礇鑺╊啨鍚瑰闀攟(zh矛),灏�(du矛)鍚搁檮鎬ц兘鐨勬彁楂樿捣鍒颁簡绌嶆サ鐨勪綔鐢�.鍚屾檪(sh铆),鍦ㄧ⒑淇濆惛闄勬€ц兘鐨勫墠鎻愪笅,娲诲寲鍔慫nCl2婵冨害鐢�5 mol 路 L-1闄嶄綆鐐�1 mol 路 L-1,鏈夋晥鍦伴檷浣庝簡娲诲寲鍔戠殑浣跨敤閲�.

鐢盕T-IR 鍦栬瓬(鍦� 5)鍒嗘瀽鍙煡,姹℃偿鐐湪3500~3200 cm-1鍗€(q奴)鍩熷嚭鐝�(xi脿n)杓冨鐨勫惛鏀跺嘲鐐哄垎瀛愰枔姘嵉O鈥擧浼哥府鎸嫊(d貌ng)鍚告敹宄�;3200~2800 cm-1鍗€(q奴)鍩�?y脿n)闀冣€擧浼哥府鎸嫊(d貌ng)鍚告敹宄�;1300~1000 cm-1鍑虹従(xi脿n)C鈥擮浼哥府鎸嫊(d貌ng);880~680 cm-1鍗€(q奴)鍩�?y脿n)闀冣€擧闈㈠褰庢洸鎸嫊(d貌ng);鍦�600~500 cm-1鍗€(q奴)鍩�?y脿n)闀冣€擟l浼哥府鎸嫊(d貌ng)(Sabio et al., 2004; Yang et al.,2010; Lin et al., 2012).姝ゅ,鏀规€у悗姹℃偿鐐湪1730 cm-1鍜�1570 cm-1铏曢倓鍑虹従(xi脿n)浜咰 O 鍚告敹宄板拰C C 楠ㄦ灦鎸嫊(d貌ng),鏀规€ф薄娉ョ偔缍�(j墨ng)娲诲寲銆佺偔鍖栫祼(ji茅)鍚堟垚C鈥擧銆丆 C銆丆鈥擮銆丱鈥擧鍜孋鈥擟l绛夊畼鑳藉湗(tu谩n).

3.3.3 Zeta闆讳綅銆丆EC鍒嗘瀽

鍓嶆湡鐮旂┒琛ㄦ槑,姹℃偿鐐惈鏈塁鈥擧銆丆 C銆丆鈥擮鍜孫鈥擧绛夊畼鑳藉湗(tu谩n),鏀规€у悗瀛樺湪閰�銆侀啔鍜屽収(n猫i)閰熀鍦�(tu谩n),琛ㄩ潰缇ч吀鍩哄湗(tu谩n)鐨勫惈閲忚純澶�,灏�(du矛)閲戝爆闆㈠瓙鐨勫惛闄勮兘鍔涜純寮�(qi谩ng).鍦ㄨ⿻(p铆ng)鍍�(ji脿)鍚搁檮鍔戝惛闄勯噸閲戝爆闆㈠瓙鎬ц兘鏅�(sh铆),甯哥敤Zeta闆讳綅鍜孋EC浣滅偤閲嶈鐨勬寚妯�(bi膩o),鍚搁檮鍔戣〃闈㈢殑闆昏嵎鏈�(hu矛)褰遍熆姹℃煋鐗╃殑鍘婚櫎,鑰孋EC鍓囦唬琛ㄥ皪(du矛)閲戝爆闄�(y谩ng)闆㈠瓙鐨勫惛闄勮兘鍔�.瀵�(sh铆)椹�(y脿n)娓�(c猫)瀹氫簡鍎�(y艒u)鍖栨敼鎬ф薄娉ョ偔鍜岀磾姹℃偿鐐殑Zeta闆讳綅鍒嗗垾鐐�-15.50銆�-11.36 mV,CEC鍒嗗垾鐐�30.9脳10-2銆�18.9脳10-2 mmol 路 g-1.閫欐剰鍛宠憲鎽婚洔闆绘睜鏉愭枡鏀规€х殑姹℃偿鐐璟eta闆讳綅杓冧綆鍚搁檮閲戝爆闆㈠瓙鍚庡舰鎴愮殑鑶犲湗(tu谩n)鏇寸┅(w臎n)瀹�,鑰屽叾CEC鍊煎ぇ鍓囧惛闄勯噾灞洟瀛愭€ц兘鏇村劒(y艒u)銆�

4 绲�(ji茅)璜�

1) P-B鏂规硶寰炲奖闊挎薄娉ョ偔鍚搁檮鎬ц兘鐨勫鍊�(g猫)宸ヨ棟鍙冩暩(sh霉)涓湁鏁堢閬稿嚭闂�(gu膩n)閸靛洜绱�,鍗筹細鎽婚洔姣�銆佺偔鍖栨韩搴﹀拰鐐寲鏅�(sh铆)闁�.

2) RSM-CCD瀵�(sh铆)鐝�(xi脿n)浜嗛棞(gu膩n)閸靛洜绱犵殑鍚堢悊鍎�(y艒u)鍖�,鍦ㄦ渶鍎�(y艒u)姊濅欢涓�,纰樺惛闄勫€奸仈(d谩)鍒�530.1 mg 路 g-1,鐢�(ch菐n)鐜囩偤60.5%,涓斿ぇ骞呴檷浣庝簡ZnCl2娲诲寲鍔戠殑浣跨敤閲�.

3) BET銆丼EM銆乆RD銆乑eta闆讳綅鍜孋EC鍒嗘瀽琛ㄦ槑,鍎�(y艒u)鍖栧悗鐨勫虎鑸奪n-C闆绘睜-姹℃偿鐐€ц兘鎻愬崌,鏇撮仼鍚堥噾灞洟瀛愮殑鍚搁檮.