銆€銆€闅ㄨ憲宸ヨ静(n贸ng)妤�(y猫)鐨勭櫦(f膩)灞�,鍦颁笅姘翠腑纭濋吀楣芥薄鏌撳凡缍�(j墨ng)鎴愮偤閲嶈鐨勭挵(hu谩n)澧冨晱(w猫n)椤�. 纭濋吀楣藉湪姘翠腑婧惰В搴﹂珮銆佺┅(w臎n)瀹氭€уソ,鍌崇当(t菕ng)绲︽按铏曠悊宸ヨ棟鎶€琛�(sh霉)闆ｄ互灏囧叾鍘婚櫎. 杩戝勾渚�(l谩i)鎻愬嚭鐨勫偓鍖栧弽纭濆寲鏄竴绋稉(j墨ng)鍙鐨勮劔姘柟娉�. 寰峰湅(gu贸)瀛�(xu茅)鑰匳orlop K. D. 绛�(1989)鏈€鏃╂彁鍑哄湪Pd2Cu闆欓噾灞偓鍖栧姂浣滅敤涓�, H2鑳藉皣纭濋吀楣介倓鍘熸垚姘�?d煤)楗ｈ櫖閽�? NO-3 鐨勮綁(zhu菐n)鍖栨柟绋嬪紡鍙互琛ㄧず鐐�:2NO-3 + 5H2 =N2 + 2OH- + 4H2O (1)NO-3 + 4H2 =NH+4 + 2OH- +H2O (2)闅ㄥ悗鐨勫ぇ閲忕爺绌�(Horold et al. , 1993; Ilinitchet al. , 2000; Chen Yingxue et al. , 2003)涔熻瓑瀵�(sh铆)浜哖d2Cu闆欓噾灞偓鍖栧姂浣滅敤涓嬬閰搁菇鐨勫幓闄ょ巼鍙互閬�(d谩)鍒�80%锝�95%,浣嗗弽鎳�(y墨ng)鍚屾檪(sh铆)瀛樺湪钁楀壇鐢�(ch菐n)鐗㎞H+4 . 濡備綍鏈夋晥鍦版姂鍒跺壇鐢�(ch菐n)鐗㎞H+4 鐨勭敘(ch菐n)鐢�,骞舵彁楂樺偓鍖栧姂娲绘€ф槸鐩墠鍌寲閭勫師鍘婚櫎纭濋吀楣界殑鎶€琛�(sh霉)闆ｉ粸(di菐n). Prüsse U 绛�(2000)閫氶亷(gu貌)鐮旂┒瑾�(r猫n)鐐�,婧舵恫pH鍊兼槸褰遍熆纭濋吀楣藉偓鍖栭倓鍘熷弽鎳�(y墨ng)娲绘€у拰閬告搰鎬х殑閲嶈鍥犵礌. 鍦ㄧ敤H2浣滈倓鍘熷姂閭勫師纭濋吀楣界殑閬�(gu貌)绋嬩腑,闅ㄨ憲鍙嶆噳(y墨ng)鐨勯€�(j矛n)琛�,婧舵恫鐨刾H鍊奸毃涔嬩笂鍗�,鐢辨灏�(d菐o)鑷村弽鎳�(y墨ng)鐨勬椿鎬ф垨閬告搰鎬т笅闄�. 杩戝勾渚�(l谩i)鍑虹従(xi脿n)瑷卞瑙ｆ焙閫欏€�(g猫)鍟�(w猫n)椤岀殑鏂规硶,涓€绋柟娉曟槸浣跨敤鑳介檷浣庤級楂斿瓟鍏�(n猫i)鐗╄唱(zh矛)鎿�(ku貌)鏁ｉ檺鍒剁殑杓夐珨鏉愭枡,渚嬪浣跨敤鑶�(Strukul et al. , 2000)銆佸竷绾栫董(Daub et al. , 1999).鍙︿竴绋柟娉曟槸浣跨敤鑳界敘(ch菐n)鐢熼吀鎬т綅鐨勯噾灞矤(f霉)杓夌殑闆㈠瓙浜ゆ彌鍔戜綔鐐鸿級楂�(Gasparovicova et al. , 1999). 浣嗛€欎簺鍔姏閮戒笉鏄緢鏈夋晥. NaCOOH鐒�(w煤)姣掔劇(w煤)瀹�,浣滅偤閭勫師鍔戝湪鏈夋(j墨)鍚堟垚涓父琚噳(y墨ng)鐢�,琛ㄧ従(xi脿n)鍑鸿壇濂界殑閭勫師鎬�. 鑰屼笖NaCOOH鍦ㄥ偓鍖栧姂浣滅敤涓嬫彁渚汬鐨勫悓鏅�(sh铆)鐢�(ch菐n)鐢烠O2 ,涓拰鍙嶆噳(y墨ng)閬�(gu貌)绋嬩腑鐢�(ch菐n)鐢熺殑OH- ,鍙互瑙ｆ焙H2浣滅偤閭勫師鍔戞檪(sh铆)寮曡捣鐨勬憾娑瞤H姊害鍟�(w猫n)椤�,鏈夊埄浜庢彁楂樺偓鍖栨椿鎬у拰閬告搰鎬�,浣嗙洰鍓嶅皻鏈鎳�(y墨ng)鐢ㄥ埌纭濋吀楣界殑閭勫師鍙嶆噳(y墨ng)涓�.鍥犳,鏈枃鎻愬嚭浠� NaCOOH浣滅偤閭勫師鍔�,閫�(j矛n)琛屼簡鍌寲閭勫師纭濋吀楣界殑瑭﹂(y脿n)鐮旂┒,鎺㈣◣浜嗗偓鍖栨椿鎬у拰閬告搰鎬х殑褰遍熆鍥犵礌,鏃ㄥ湪灏嬫眰涓€姊濆畨鍏ㄣ€佺啊(ji菐n)鍠槗琛岀殑楂樻晥鍘婚櫎鍦颁笅姘翠腑纭濋吀楣界殑閫斿緫.

銆€銆€1銆€瀵�(sh铆)椹�(y脿n)閮ㄥ垎( Experiments)

銆€銆€1. 1銆€瑭﹀姂鑸囧剙鍣�

銆€銆€γ2姘у寲閶�, 100 锝�200 鐩�,璩�(g貌u)鑷笂娴烽櫢閮藉寲瀛�(xu茅)瑭﹀姂寤�;姘寲閳€鐐哄垎鏋愮磾,澶╂触甯傚痉铇簿绱�(x矛)鍖栧伐寤�;纭濋吀閵呯偤鍒嗘瀽绱�,澶╂触鍖栧(xu茅)瑭﹀姂涓夊粻. 鍏跺畠瑭﹀姂鍧囩偤鍒嗘瀽绱�,瀵�(sh铆)椹�(y脿n)婧舵恫鐨嗙敤鍘婚洟瀛愭按閰嶅埗.姣旇〃闈㈢⿳(BET)娓�(c猫)瀹氬湪缇庡湅(gu贸)搴峰鍏徃鐢熺敘(ch菐n)鐨凬OVA - 2000姣旇〃闈㈢⿳鍙婂瓟闅欏害鍒嗘瀽鍎€涓婇€�(j矛n)琛�;绛夐洟瀛愰珨鐧�(f膩)灏勫厜璀�( ICP)鐢ㄧ編鍦�(gu贸)Jarreell2A sh鍏徃鐢熺敘(ch菐n)鐨処CAP29000 (N +M) 绛夐洟瀛愰珨鐧�(f膩)灏勫厜璀滃剙娓�(c猫)瀹�; X - 琛嶅皠(XRD)娓�(c猫)閲忕敤鏃ユ湰宄舵触鐞嗗(xu茅)闆绘(j墨)鍏徃鐨凞 /Max22500X灏勭窔琛嶅皠鍎€閫�(j矛n)琛�(Cu闈禟α绶�) ;閫忓皠闆诲瓙椤井閺�( TEM)娓�(c猫)閲忓湪鑽疯槶鑿插埄娴﹀叕鍙哥殑T20ST閫忓皠闆诲瓙椤井閺′笂閫�(j矛n)琛�; X灏勭窔鑳借瓬鍒嗘瀽鐢ㄨ嵎铇彶鍒╂郸鍏徃鐨刋灏勭窔鑳介噺鍒嗘暎璀滃剙( EDX)閫�(j矛n)琛�; 752N鍨嬬传澶栧彲瑕嬪垎鍏夊厜搴﹁▓(j矛)鐐轰笂娴风簿瀵嗙瀛�(xu茅)鍎€鍣ㄦ湁闄愬叕鍙哥敓鐢�(ch菐n),鐢ㄤ締(l谩i)娓�(c猫)閲忔憾娑蹭腑NO -3 銆丯H+4 鍜孨O -
2 婵冨害.

銆€銆€1. 2銆€鍌寲鍔戠殑鍒跺倷

銆€銆€閲囩敤娴告棘娉曞埗鍌欏偓鍖栧姂. 浠�γ2Al2O3鐐哄偓鍖栧姂杓夐珨,鍦�500鈩冧笅鐓呯噿娲诲寲5h鍚庡倷鐢�. 鍓嶉珨鐗㏄dCl2缍�(j墨ng)鍓嶈檿鐞�( Simonov et al. , 1997 ) 鍚庨厤鍒惰垏Cu (NO3 ) 2·3H2O鐨勬贩鍚堟憾娑�100 mL,浣縋d2 +婵冨害鐐�2 g·L - 1 , Cu2 +婵冨害鐐�0. 5g·L - 1 ;鐒跺悗鍔犲叆4. 75 g宸茶檿鐞嗛亷(gu貌)鐨�γ2Al2O3 ,鏀媽鍧囧嫽闈滅疆閬�(gu貌)澶�,鍦�70鈩冩按娴翠腑鏀媽鑴按,骞茬嚗鍚庣Щ鍏ラΜ寮楃垚,浜�350鈩冪伡鐕�2 h;鑷劧鍐峰嵒鍚庣敤閬�(gu貌)閲忕殑KBH4閭勫師,鏈€鍚庣稉(j墨ng)鍏呭垎娲楁粚銆侀洟蹇�銆佸共鐕ュ嵆寰楀埌璨�(f霉)杓夊瀷鍌寲鍔慞d2Cu /γ2Al2 O3 ,ICP娓�(c猫)瀹氬叾涓璓d銆丆u鍚噺鍒嗗垾鐐�3. 97%銆�1. 04%.

銆€銆€1. 3銆€鍌寲鍔戠殑琛ㄥ緛鐢˙ET灏�(du矛)鍌寲鍔戦€�(j矛n)琛屾瘮琛ㄩ潰绌�銆佸瓟瀹瑰瓟闅欏垎鏋�. 鐢╔RD灏�(du矛)鍌寲鍔戦€�(j矛n)琛岀墿鐩稿垎鏋�, CuKα杓诲皠婧�,鐭冲ⅷ鍠壊鍣�,绠￠浕澹撶偤50 kV, 绠￠浕娴佺偤100 mA,鎺冩弿鑼冨湇2θ= 3锝�80°,鎺冩弿閫熷害4°·min- 1 ;娓�(c猫)瑭︽檪(sh铆)灏囩矇鏈ǎ鍝佺疆浜庤級鐜荤墖涓婂鍒舵垚鐗囩媭,鐢═EM鎶€琛�(sh霉)瑙€瀵熷偓鍖栧姂琛ㄩ潰褰㈣矊浠ュ強鍌寲鍔戣〃闈㈤噾灞垎甯冪媭娉�. 鐢‥DX灏�(du矛)鍌寲鍔戣〃灞ら€�(j矛n)琛岀祫鍒嗗垎鏋�.

銆€銆€1. 4銆€鍌寲閭勫師鍙嶆噳(y墨ng)瀵�(sh铆)椹�(y脿n)

銆€銆€鍌寲閭勫師鍙嶆噳(y墨ng)瑁濈疆鐢辩鍔涙敧鎷屽櫒鍜�250 mL鐜荤拑鍙嶆噳(y墨ng)鍣ㄧ祫鎴�. 鍚戝弽鎳�(y墨ng)鍣ㄤ腑鎶曞姞0. 4 g鐨凱d2Cu /γ2Al2O3鍌寲鍔戝拰600 mg·L - 1鐨凬aCOOH婧舵恫190 mL,鐢�0. 4 mol·L - 1鐨凥COOH瑾�(di脿o)绡€(ji茅)鍒濆pH鍊肩偤415鍚庨€歂2 30 min鎺掗櫎姘翠腑婧惰В姘�;鐒跺悗鍔犲叆2000 mg·L - 1鐨勭閰搁菇婧舵恫10mL浣挎湁鏁堢殑鍙嶆噳(y墨ng)楂旂⿳鐐�200 mL,楂旂郴涓璑O-3 鍒濆婵冨害鐐�100 mg·L - 1 ,鍦�500 r·min- 1涓嬮€ｇ簩(x霉)蹇€熸敧鎷屽弽鎳�(y墨ng). 瀹氭檪(sh铆)鍙�3锝�5 mL姘存ǎ缍�(j墨ng)0. 45μm鐨勬烤鑶滈亷(gu貌)婵惧悗娓�(c猫)瀹歂O-3 銆丯H+4 鍜孨O-2 婵冨害. NO-3 婵冨害鐢ㄧ传澶栧垎鍏夊厜搴︽硶娓�(c猫)瀹�,NH+4 婵冨害鐢ㄧ磵姘忚│鍔戞硶娓�(c猫)瀹�,NO-2 婵冨害鐢�α - 钀樿兒姣旇壊娉曟脯(c猫)瀹�.鍌寲鍔戞椿鎬ф槸鎸囧柈浣嶆檪(sh铆)闁撳柈浣嶈唱(zh矛)閲忛噾灞偓鍖栧姂浣滅敤涓嬬閰搁菇鐨勫幓闄ら噺(mg·g- 1·min- 1 ). 鍙嶆噳(y墨ng)閬告搰鎬х敤鍓敘(ch菐n)鐗╂皑姘殑鐢�(ch菐n)鐜囦締(l谩i)琛ㄧず,姘ㄦ爱鐢�(ch菐n)鐜囪秺浣庡墖鍙嶆噳(y墨ng)閬告搰鎬у氨瓒婇珮,鐩稿弽姘ㄦ爱鐢�(ch菐n)鐜囪秺楂樺墖鍙嶆噳(y墨ng)閬告搰鎬ц秺浣�.

銆€銆€2銆€绲�(ji茅)鏋� (Results)

銆€銆€2. 1銆€鍌寲鍔戠殑琛ㄥ緛

銆€銆€琛�1鐐哄偓鍖栧姂Pd2Cu /γ2Al2O3鍙婂叾杓夐珨γ2Al2O3鐨勬瘮琛ㄩ潰绌�銆佸瓟瀹瑰拰瀛斿緫鍙冩暩(sh霉). 鐢辫〃鍙互鐪嬪嚭,鍌寲鍔戣級楂斿叿鏈夎純澶х殑姣旇〃闈㈢⿳鍜屽瓟瀹�,灞簬涓瓟姘у寲閶�. 璨�(f霉)杓変笂娲绘€ч噾灞悗鍌寲鍔戞瘮琛ㄩ潰绌�銆佸瓟瀹�銆佸瓟寰戠暐鏈変笅闄�, γ - Al2O3鐨勭祼(ji茅)妲�(g貌u)鎬ц兘鏈櫦(f膩)鐢熻畩鍖�. 瀛斿緫鐢卞師渚�(l谩i)鐨�6nm闄嶅埌4. 6 nm,瑾�(shu艒)鏄庤級楂�γ- Al2O3鍏�(n猫i)琛ㄩ潰褰㈡垚浜嗗潎鍕荤殑绱嶇背閲戝爆钖勫堡,鏈嚭鐝�(xi脿n)鏄庨’鍦�(tu谩n)鑱氬拰鍫靛杓夐珨鐨勫瓟绲�(ji茅)妲�(g貌u).琛�1銆€鍌寲鍔戝強鍏惰級楂旂殑姣旇〃闈㈢⿳銆佸瓟瀹瑰拰瀛斿緫鍙冩暩(sh霉)
Table 1 銆€The specific surface area of the catalyst and support  鍌寲鍔� 姣旇〃闈㈢⿳/ (m2·g -1 )  瀛斿/ ( cm3·g - 1 )  瀛斿緫/ nm  γ2A l2O3 Pd Cu /γA l2O3  144 131  0. 22 0. 19  6 4 6 
XRD鍒嗘瀽绲�(ji茅)鏋滆〃鏄�,γ2Al2O3鍜孭d2Cu /γ2Al2O3鐨刋RD 璀滃湒娌掓湁鏄庨’鍗€(q奴)鍒�, 涓昏琛嶅皠宄板潎鐐�γ2Al2O3 ,鏈娓�(c猫)鍒癙d鍜孋u鐨勮灏勫嘲. 鍥犺€岄€�(j矛n)涓€姝ュ皪(du矛)鍌寲鍔戦€�(j矛n)琛屼簡TEM鍜孍DX鍒嗘瀽. 鍦�1鐐哄偓鍖栧姂Pd2Cu /γ2Al2O3鐨凾EM鐓х墖,鍦栦腑榛戣壊鐗╄唱(zh矛)鐐洪噾灞绮�,鍙互鐪嬪嚭,鍌寲鍔戠殑娲绘€х祫鍒嗗潎鍕诲垎甯冧簬杓夐珨琛ㄩ潰. 鍦�2鐐哄偓鍖栧姂Pd2Cu /γ2Al2O3鐨凟DX鑳借瓬鍦�,鍙互鐪嬪嚭,鍌寲鍔戣〃闈㈤噾灞厓绱犵偤Pd鍜孋u.

鍦�1銆€鍌寲鍔慞d2Cu /γ2Al2O3鐨勯€忓皠闆婚彙( TEM)鐓х墖F(xi脿n)ig. 1銆€TEM photograph of Pd2Cu /γ2Al2O3 catalyst

銆€銆€鍦�2銆€鍌寲鍔慞d2Cu /γ2Al2O3鐨凟DX鑳借瓬鍦朏ig. 2 銆€EDX Spectrum of Pd2Cu /γ2Al2O3 catalyst

銆€銆€2. 2銆€鍌寲閭勫師鍙嶆噳(y墨ng)

銆€銆€鍦�3鐐哄偓鍖栧姂Pd2Cu /γ2Al2O3浣滅敤涓�,NaCOOH浣滅偤閭勫師鍔戣劔闄O-3 鐨勬檪(sh铆)闁撴洸绶�. 鍙互鐪嬪嚭,鍙嶆噳(y墨ng)鍓�30min鍏�(n猫i)NO-3 鍘婚櫎閫熺巼杓冮珮,NO-3 婵冨害骞句箮鍛堢窔鎬ф笡灏�. 鍙嶆噳(y墨ng)瀛樺湪涓枔鐢�(ch菐n)鐗㎞O-2 鍜屽壇鐢�(ch菐n)鐗㎞H+4 .NO-3 鍦�75min 鏅�(sh铆)杞�(zhu菐n)鍖栧畬鍏�,鍙嶆噳(y墨ng)绲�(ji茅)鏉熸檪(sh铆)妾㈡脯(c猫)涓嶅埌NO-2 ,NH+4 鐨勭敘(ch菐n)鐜囩偤13% , 姘殑鑴櫎鏁堢巼鍙互閬�(d谩)鍒�87%.

銆€銆€鍦�3銆€鐢查吀閳夊偓鍖栭倓鍘烴O -3 鐨勬檪(sh铆)闁撴洸绶欶ig. 3 銆€Temporal curves of catalytic reduction of nitrate bysodium formate2. 3銆€涓嶅悓鍙嶆噳(y墨ng)姊濅欢涓嬬殑鍌寲閭勫師鍙嶆噳(y墨ng)鎸�1. 4绡€(ji茅)鐨勬柟娉曚緷娆℃敼璁婂弽鎳�(y墨ng)鍒濆pH鍊�銆佸偓鍖栧姂鎶曞姞閲忓拰閭勫師鍔慛aCOOH 婵冨害閫�(j矛n)琛屽偓鍖栭倓鍘熷弽鎳�(y墨ng),瑷�(j矛)绠楀弽鎳�(y墨ng)30min鏅�(sh铆)鐨勫偓鍖栨椿鎬у拰姘ㄦ爱鐢�(ch菐n)鐜�.鍦�4鐐轰笉鍚屽垵濮媝H鍊煎皪(du矛)NO-3 鍌寲閭勫師鍙嶆噳(y墨ng)鐨勫奖闊�. 鍙互鐪嬪嚭,鍒濆pH鍊奸亷(gu貌)楂樻垨閬�(gu貌)浣庨兘涓嶅埄浜庢彁楂樺偓鍖栧姂娲绘€�,鍒濆pH鍊肩偤4鏅�(sh铆)鍌寲鍔戝叿鏈夋渶楂樼殑娲绘€�;鍙嶆噳(y墨ng)閬告搰鎬ч毃钁楀垵濮媝H鍊肩殑鍗囬珮鑰屽鍔�.鍦�5鐐轰笉鍚屽偓鍖栧姂鎶曞姞閲忓皪(du矛)鍌寲閭勫師鍙嶆噳(y墨ng)鐨勫奖闊�,鍙互鐪嬪嚭,闅ㄨ憲鍌寲鍔戞姇鍔犻噺澧炲姞鍌寲娲绘€х暐鏈夐檷浣�,鑰屽弽鎳�(y墨ng)閬告搰鎬у墖椤憲鍗囬珮. 鍦�6 鐐篘aCOOH婵冨害灏�(du矛)鍌寲閭勫師鍙嶆噳(y墨ng)鐨勫奖闊�,鍙互鐪嬪嚭,闅ㄨ憲NaCOOH婵冨害澧炲姞,鍌寲娲绘€ч€愭几澧炲姞,浣哊aCOOH婵冨害>600 mg·L - 1鍙嶆噳(y墨ng)閬告搰鎬у嵒鏄庨’闄嶄綆. 缍滀笂鎵€杩�,鍘婚櫎100 mg·L - 1 NO-3 ,鍒濆pH鍊�4. 5,鍌寲鍔戞姇鍔犻噺2 g·L - 1 ,鐢查吀閳夋績搴�600 mg·L - 1鐐烘渶浣崇殑鍙嶆噳(y墨ng)姊濅欢.

鍦�4銆€鍒濆pH鍊煎皪(du矛)NO -3 鍌寲閭勫師鍙嶆噳(y墨ng)鐨勫奖闊縁ig. 4銆€Effect of initial pH value on catalytic reduction of nitrate

鍦�5銆€鍌寲鍔戞姇鍔犻噺灏�(du矛)NO -3 鍌寲閭勫師鍙嶆噳(y墨ng)鐨勫奖闊縁ig. 5銆€Effect of catalyst amount on catalytic reduction of nitrate