謝金伶,蒲佳興,李思域,黃 麗,龔小波,2*

鈷錳硫化物活化過硫酸鹽強(qiáng)化降解鹽酸四環(huán)素

謝金伶1,蒲佳興1,李思域1,黃 麗1,龔小波1,2*

(1.四川師范大學(xué)化學(xué)與材料科學(xué)學(xué)院,四川 成都 610066；2.特種廢水處理四川省高校重點(diǎn)實(shí)驗(yàn)室,四川 成都 610066)

采用簡(jiǎn)單兩步法制備了鈷錳雙金屬硫化物(MnCo2S4).通過掃描電子顯微鏡,X射線衍射,X射線光電子能譜等表征手段對(duì)MnCo2S4的形貌,晶體結(jié)構(gòu),組成成分等進(jìn)行分析.探究了MnCo2S4/PMS體系中鹽酸四環(huán)素的降解效能和降解路徑,結(jié)果表明,MnCo2S4和PMS投加量為0.1g/L,TC的降解率在30min達(dá)到88%,在較寬的pH值范圍內(nèi)(3～9)均具有較高的降解率,這歸因于MnCo2S4中金屬活性位點(diǎn)Mn2+,Co2+的持續(xù)供應(yīng)和鈷錳的協(xié)同作用.淬滅實(shí)驗(yàn)和電子順磁共振(EPR)技術(shù)表明MnCo2S4/PMS體系主要是SO4?-,?OH和1O2共同作用降解TC.本研究為PMS的活化和抗生素等難降解污染物的去除提供了新的催化劑構(gòu)建策略.

雙金屬硫化物；鹽酸四環(huán)素；過一硫酸鹽；催化降解

抗生素是一類廣譜性的抗菌劑,被廣泛應(yīng)用于人類疾病治療,畜牧業(yè)等領(lǐng)域.其中,鹽酸四環(huán)素(TC)是最常用的抗生素之一,約70%的鹽酸四環(huán)素通過食物鏈排入環(huán)境,由于其具有水溶性高,生物不可降解性和潛在的致癌性等特點(diǎn)對(duì)生態(tài)環(huán)境和人類健康造成了嚴(yán)重的威脅,為了解決TC對(duì)環(huán)境可能造成的污染,包括芬頓氧化,光電催化氧化,臭氧氧化在內(nèi)的化學(xué)法引起了科研工作者的廣泛關(guān)注[1-2].

基于過硫酸鹽的高級(jí)氧化技術(shù)因其成本低,操作簡(jiǎn)單,易于控制,被廣泛應(yīng)用于處理難降解污染物[3].過硫酸鹽主要包括過一硫酸鹽(PMS)和過二硫酸鹽(PDS)兩種氧化劑,與PDS相比,PMS結(jié)構(gòu)不對(duì)稱,產(chǎn)生活性物種所需的能量低,因此,更容易被包括熱[4],堿[5],紫外線照射[6]及金屬等活化方式激活,產(chǎn)生多種活性物種.在眾多活化方式中,金屬活化因其能耗低,效果顯著且催化劑回收利用潛力大而備受關(guān)注.常見的金屬離子催化劑有鐵[7-8],鈷[9],錳[10],銅[11],銀[12]等.研究表明,鈷離子(Co2+)是對(duì)PMS最敏感的金屬離子[13],能有效活化PMS產(chǎn)生SO4?-等活性物種[14],然而Co2+對(duì)人類健康和環(huán)境均會(huì)造成嚴(yán)重危害,這也限制了Co2+的應(yīng)用.因此,進(jìn)一步研究鈷基非均相催化劑,以減少鈷離子溶出,降低其對(duì)生態(tài)環(huán)境危害是十分必要的.與鈷基非均相催化劑相比,錳基催化劑具有毒性低,天然豐度高,環(huán)境友好等特點(diǎn).已有研究通過調(diào)節(jié)CoMn2O4中元素組成比例,進(jìn)一步誘導(dǎo)尖晶石中最活躍的Co2+和Mn3+的調(diào)節(jié),從而促進(jìn)電子轉(zhuǎn)移和催化性能的提高[15].

此外,與單金屬催化劑相比,雙金屬催化劑可通過協(xié)同作用,提高PMS的催化活化性能.雙金屬硫化物被廣泛應(yīng)用于電容器等電子設(shè)備中,具有高比容量,高倍率性能和優(yōu)異的循環(huán)穩(wěn)定性能等特點(diǎn),然而,關(guān)于其在過硫酸鹽技術(shù)中的應(yīng)用相對(duì)較少.不同于雙金屬氧化物,雙金屬硫化物在激活PMS產(chǎn)生活性物種后,金屬離子由低價(jià)變?yōu)楦邇r(jià),而雙金屬硫化物中的S2-具有很強(qiáng)的還原性可促進(jìn)金屬離子高價(jià)與低價(jià)間的轉(zhuǎn)換,進(jìn)而實(shí)現(xiàn)催化反應(yīng)的循環(huán)[16-17],提升PMS活化效能.

因此,本研究通過構(gòu)建鈷錳雙金屬硫化物MnCo2S4高效活化PMS,以TC作為模型污染物,以評(píng)估其催化降解性能.利用掃描電子顯微鏡,X射線衍射,X射線光電子能譜儀等表征手段對(duì)MnCo2S4的形貌,晶體結(jié)構(gòu),組成成分等進(jìn)行分析;探究了一系列操作條件對(duì)TC降解的影響;利用淬滅實(shí)驗(yàn)和電子順磁共振技術(shù)對(duì)MnCo2S4/PMS體系的活性物種進(jìn)行探究,并對(duì)降解的可能中間產(chǎn)物進(jìn)行分析,為水中抗生素的高效去除提供新的方法.

1 材料與方法

1.1 材料

過一硫酸鹽(PMS),氫氧化鈉(NaOH),鹽酸(HCl),糠醇(FFA), 5,5-二甲基-1-吡咯啉-N-氧化物(DMPO), 4-氨基-2,2,6,6-四甲基哌啶(TEMP)均購(gòu)于上海阿拉丁生化科技股份有限公司,四水乙酸鈷(Co(OAc)2·4H2O),尿素(CH4N2O),聚乙烯吡咯烷酮(PVP),硫代乙酰胺(TAA),乙醇(Ethanol),甲醇(MeOH),叔丁醇(TBA)均購(gòu)買于成都市科隆化學(xué)品有限公司,四水乙酸錳(Mn(OAc)2·4H2O)購(gòu)于天津市大茂化學(xué)試劑廠,所有試劑均為分析純,無(wú)需進(jìn)一步純化.實(shí)驗(yàn)過程中用水均為超純水.

1.2 催化劑的制備

1.2.1 Mn-Co前驅(qū)體制備稱取0.422g四水乙酸錳,0.858g四水乙酸鈷,3.000g聚乙烯吡咯烷酮和尿素溶于200mL無(wú)水乙醇中,混合均勻后在85℃的條件下冷凝回流2h;冷卻至室溫后,離心收集沉淀物,用無(wú)水乙醇洗滌3次并置于50℃的真空烘箱中干燥即得前驅(qū)體.

1.2.2 MnCo2S4的制備稱取多于0.160g的Mn-Co前驅(qū)體和0.240g硫代乙酰胺均勻分散至80mL無(wú)水乙醇中;將其轉(zhuǎn)移到水熱反應(yīng)釜中120℃下反應(yīng)6h;冷卻至室溫,用無(wú)水乙醇和蒸餾水離心洗滌3次,最后在50℃的真空烘箱中干燥,所得產(chǎn)物為MnCo2S4.

1.3 催化劑的表征

采用掃描電鏡(SEM,FEI quanta250,美國(guó))分析樣品的微觀形貌.X射線衍射(XRD,Neo-Confucianism Rigaku Smartlab,日本)被用于分析樣品的晶體構(gòu)型.使用X射線光電子能譜儀(XPS,Escalab Xi,美國(guó))觀察樣品的分子結(jié)構(gòu).污染物降解的中間產(chǎn)物的鑒定主要通過液相-質(zhì)譜聯(lián)用儀(LC-MS,Waters Thermo F.S./LCQ Fleet,美國(guó))實(shí)現(xiàn).電子順次共振技術(shù)(EPR, Bruker EMX nano,德國(guó))被用于檢測(cè)體系中主要活性物種.

1.4 實(shí)驗(yàn)方法

MnCo2S4活化PMS降解TC實(shí)驗(yàn)均在250mL燒杯中進(jìn)行,并使用NaOH(0.1mmol/L)和HCl (0.1mmol/L)調(diào)節(jié)TC溶液(20mg/L)初始pH值.降解實(shí)驗(yàn)無(wú)特殊說(shuō)明均在25℃的室溫下進(jìn)行.當(dāng)加入一定量的MnCo2S4和PMS進(jìn)行反應(yīng)時(shí),間隔特定時(shí)間,取3mL反應(yīng)液并用0.22μm的濾膜過濾,在濾液中加入1mL甲醇作為反應(yīng)終止劑,所得溶液使用紫外-可見風(fēng)光光度計(jì)(佑科750)進(jìn)行TC含量的分析.使用甲醇,叔丁醇,L-組氨酸等自由基猝滅劑來(lái)鑒定MnCo2S4/PMS體系中的活性物種并利用EPR技術(shù)進(jìn)一步佐證.此外,探究了尿素?fù)诫s量,催化劑投加量, PMS投加量,初始pH值,溫度等對(duì)TC降解的影響.所有數(shù)據(jù)均為三次實(shí)驗(yàn)的平均值,用C/0表示污染物的降解效率,C為反應(yīng)時(shí)間后,溶液中TC的含量,0為未反應(yīng)的溶液中的TC濃度.

2 結(jié)果與討論

2.1 催化劑表征

2.1.1 形貌分析 從圖1(a)可以觀察到MnCo2S4分散較為均勻,形成了不規(guī)則的微小顆粒,且生長(zhǎng)密集,存在少量的團(tuán)聚現(xiàn)象.從圖1(b)可觀察到催化劑表面附著了許多小顆粒,這有利于增加材料的比表面積,為反應(yīng)提供了更多的活性位點(diǎn),從而提升催化劑活化PMS的性能.

2.1.2 晶相分析 MnCo2S4的XRD譜圖如圖2所示,MnCo2S4的特征峰位于16.2°,26.5°,31.5°,38.2°和50.4°,分別對(duì)應(yīng)MnCo2S4的(111),(220),(311),(400)和(511)晶面[18],這表明成功合成了鈷錳雙金屬硫化物催化劑MnCo2S4,其余高強(qiáng)度峰與標(biāo)準(zhǔn)卡片中CoSO4·6H2O (JCPDS No.16-0304)對(duì)應(yīng),且匹配度較高,這說(shuō)明所制備的催化劑中含有CoSO4?6H2O,其原因可能是洗滌不充分導(dǎo)致的.

圖1 MnCo2S4的SEM譜圖

圖2 MnCo2S4的XRD譜圖

2.1.3 元素分析 MnCo2S4的元素組成和價(jià)態(tài)通過XPS檢測(cè)和分析.通過對(duì)XPS全譜的分析,可明顯觀察到Mn2p,Co2p,S2p的峰,具體的元素含量如表1所示.進(jìn)一步對(duì)Mn2p、Co2p和S2p的峰進(jìn)行擬合,如圖3(b)所示,峰值為641.5和653.3eV分別代表Mn2p3/2和Mn2p1/2,兩個(gè)衛(wèi)星峰分別出現(xiàn)在644.1eV和655.1,這表明MnCo2S4中有Mn3+和Mn2+的存在[19],可作為活化PMS的有效活性位點(diǎn).圖3(c)為Co2p的精細(xì)譜圖分析,在781.6和797.7eV處分別出現(xiàn)了Co 2p3/2和Co2p1/2的峰,此外,有兩個(gè)明顯的衛(wèi)星峰出現(xiàn)在785.4和802.4eV, 這證明MnCo2S4中Co2+和Co3+的存在,它們不僅可作為活性位點(diǎn)還可與錳離子形成協(xié)同作用,促進(jìn)催化性能的提升.如圖3(d)所示,有兩個(gè)強(qiáng)度較弱的峰值分別位于163.2eV (S2p1/2)和161.6eV (S2p3/2),兩個(gè)強(qiáng)度明顯的衛(wèi)星峰分別位于168.4和169.6eV[20],這表明MnCo2S4中存在S2-,S2-具有很強(qiáng)的還原性可以促進(jìn)金屬離子以高的活性進(jìn)入低的價(jià)態(tài),從而促進(jìn)了反應(yīng)的循環(huán)[21].

表1 MnCo2S4中各元素的組成和質(zhì)量比

2.2 MnCo2S4催化活化PMS性能

2.2.1 MnCo2S4催化PMS降解TC 分別探究了單獨(dú)PMS和MnCo2S4,以及MnCo2S4/PMS體系中TC的去除率.如圖4所示,當(dāng)體系中僅存在PMS且濃度為0.1g/L,TC的降解率可達(dá)41%,可能有以下兩點(diǎn)原因:(1)PMS可直接與TC反應(yīng),TC溶液中加入PMS后呈弱酸性環(huán)境,這時(shí)TC以質(zhì)子態(tài)形式存在,可與PMS中的HSO5-相互吸引,HSO5-的氧化電位為1.75V,對(duì)TC有一定的氧化作用[22];(2)PMS自身可產(chǎn)生單線態(tài)氧等活性物種,可有效促進(jìn)TC的降解[23].單獨(dú)投加20mgMnCo2S4,對(duì)TC的吸附率約為20%,表明MnCo2S4具有較差的吸附性能.當(dāng)體系中MnCo2S4和PMS均加入時(shí), MnCo2S4/PMS體系對(duì)TC的降解率在30min內(nèi)達(dá)到88%.通過上述不同體系的對(duì)比,表明MnCo2S4具有較高的催化性能,能夠有效活化PMS產(chǎn)生活性物質(zhì)降解鹽酸四環(huán)素.

2.2.2 尿素?fù)诫s量影響 制備過程中尿素添加量對(duì)MnCo2S4的催化性能有較大影響.由圖5(a)可知,分別設(shè)置尿素投加量為0,0.5,1.0,1.5,2.0g,當(dāng)尿素投加量為1.5g時(shí), MnCo2S4的催化性能最好,10min,TC的降解率可達(dá)到80%,繼續(xù)增加尿素投加量至2.0g,TC的降解率明顯降低,其原因可能是:尿素可有效改善材料制備過程中的還原環(huán)境,材料制備的過程中投加適量的尿素使溶液呈弱堿性,在弱堿性環(huán)境中有利于緩慢形成納米級(jí)的沉淀,這可促進(jìn)催化劑與污染物的接觸.投加過量的尿素使溶液的堿性增強(qiáng)雖然可促進(jìn)反應(yīng)的進(jìn)行但容易形成大顆粒沉淀,不利于污染物與催化劑的接觸.

圖3 MnCo2S4的XPS全譜圖和元素譜圖

圖4 不同體系中TC的去除效率

2.2.3 MnCo2S4投加量影響 由圖5(b)可知,當(dāng)MnCo2S4投加量從0g/L增加至0.1g/L時(shí),反應(yīng)30min,TC的降解率從40%增加至80%,繼續(xù)增加MnCo2S4投加量至0.2g/L,雖然30min后TC的降解率無(wú)明顯增加,但前8min,TC的降解速率明顯加快,這歸因于MnCo2S4的投加量增加,導(dǎo)致活性位點(diǎn)增加,這有利于活性物種的產(chǎn)生.

2.2.4 PMS投加量影響 如圖5(c)所示,PMS投加量分別為0.025,0.075,0.1和0.125g/L時(shí),反應(yīng)8min,TC的降解率分別為54%,74%,81%和83%,增加PMS投加量,對(duì)TC的降解有明顯的促進(jìn)作用,其原因可能是更多的PMS投加量可促進(jìn)更多活性物種的產(chǎn)生.反應(yīng)15min后,隨著PMS投加量的增多,TC的降解效果并沒有明顯提升,可能是由于PMS發(fā)生自猝滅導(dǎo)致的(式1)[24-25].

2.2.5 初始pH值對(duì)TC降解影響 溶液初始pH值會(huì)影響體系中活性物種的形成,如圖6(a)所示,在較寬的pH值范圍內(nèi)(3～9),反應(yīng)30min,TC的降解率均在80%以上,說(shuō)明MnCo2S4/PMS體系在寬的pH值范圍內(nèi)均保持較高催化活性,但在不同pH值條件下仍存在差異.溶液初始pH值由3增加至9,TC的降解效果在前期有明顯提升,說(shuō)明溶液初始pH值能影響TC的降解速度.在酸性條件下,抑制TC降解速度的主要原因可能是: PMS在酸性條件下更穩(wěn)定,不容易產(chǎn)生活性物種,同時(shí)PMS中的氧單鍵與H+結(jié)合形成氫鍵,阻礙了PMS與MnCo2S4間的相互作用.此外,H+會(huì)與產(chǎn)生的活性物種反應(yīng),從而減弱TC的降解效果[26-27].在堿性條件下TC降解速率被明顯提升的原因可能是:pH值與TC的解離常數(shù)(pa=3.3)有緊密的聯(lián)系[28],水溶液中TC的存在形式主要有五種,分別是TCH3+, TCH20,TCH-,TC2-和TC3-,在堿性溶液中,TC主要以去質(zhì)子化狀態(tài)存在,這也使其更易被自由基氧化,因此,堿性條件下有助于提升TC的降解速率,但通過延長(zhǎng)反應(yīng)時(shí)間,最終均會(huì)達(dá)到幾乎相同的降解效果.

2.2.6 溫度對(duì)TC降解影響 為了探究溶液溫度對(duì)TC降解的影響,本研究設(shè)置了3組不同的溫度梯度進(jìn)行實(shí)驗(yàn).由圖6(b)可知,溫度由15℃升高至35℃時(shí),TC的降解率由85%增長(zhǎng)至89%,盡管降解率相差不大,但在反應(yīng)前6min,TC的降解速率明顯加快.這可能是由于溫度升高使得分子間的布朗運(yùn)動(dòng)加快,從而增加了活性物質(zhì)與TC的有效碰撞,此外,溫度增加,PMS能更快速的生成活性物質(zhì),即高溫能加快PMS中O—O鍵的斷裂,從而促進(jìn)活性物質(zhì)產(chǎn)生[29].

圖5 尿素?fù)诫s量,MnCo2S4和PMS投加量對(duì)TC降解的影響

2.3 MnCo2S4活化PMS機(jī)制分析

本研究使用甲醇,叔丁醇,L-組氨酸作為捕獲劑,分別捕獲硫酸根自由基(SO4?-)和羥基自由基(?OH),羥基自由基,單線態(tài)氧(1O2)以確定MnCo2S4/PMS體系中產(chǎn)生的活性物種類型.結(jié)果如圖7所示,當(dāng)分別加入0.5mol/L甲醇和叔丁醇,對(duì)TC均有明顯抑制作用,與未加抑制劑相比,對(duì)TC的降解分別降低了58%和22%,這表明在MnCo2S4/PMS體系中,硫酸根自由基和羥基自由基對(duì)TC的降解做出了重要貢獻(xiàn).L-組氨酸常被用于捕獲單線態(tài)氧,加入20mmol/ L L-組氨酸,TC的降解率為僅為53%左右,與未加抑制劑相比,TC的降解率被抑制了35%,這表明MnCo2S4/PMS體系中存在單線態(tài)氧.因此,在MnCo2S4/PMS體系中,自由基和非自由基共同作用降解TC.

圖7 不同猝滅劑對(duì)TC降解的影響

進(jìn)一步通過電子順磁技術(shù)論證上述觀點(diǎn).在該技術(shù)中,TEMP作為捕獲劑被用于單線態(tài)氧的檢測(cè),圖8(a)顯示了明顯的3個(gè)1:1:1的TEMP-1O2特征峰,表明體系中存在1O2.相似的,DMPO被用于檢測(cè)SO4?-和?OH,圖8(b)顯示了明顯的近似1:2:1:2:1:2:1的DMPOX的特征峰,這是被自由基二次氧化造成的,間接證明MnCo2S4/PMS體系中存在大量SO4?-和?OH[30-31].

綜上所述并結(jié)合XPS譜圖分析, MnCo2S4活化PMS的降解TC的可能氧化機(jī)制如圖9所示.PMS自氧化可產(chǎn)生單線態(tài)氧等活性物種(式2),在該過程中也可能存在自由基的進(jìn)一步反應(yīng)式(3)～式(4),同時(shí)金屬離子可有效激活PMS產(chǎn)生SO4?-和?OH(式5-6),SO4?-和?OH也可相互轉(zhuǎn)化(式7-8).在該過程中,低價(jià)金屬離子被氧化至高價(jià)導(dǎo)致活性降低,一方面,S2-因其較強(qiáng)的還原性可進(jìn)一步將高價(jià)態(tài)金屬還原成低價(jià)態(tài)金屬,形成循環(huán),另一方面,雙金屬間的協(xié)同有利于自由基的產(chǎn)生,從而促進(jìn)污染物的降解(式9-11)

圖9 MnCo2S4激活PMS降解TC的機(jī)制

2.4 TC降解路徑分析

LC-MS被用于分析MnCo2S4/PMS體系中TC可能的降解中間產(chǎn)物.如圖10所示,共發(fā)現(xiàn)3條可能的降解路徑.路徑Ⅰ:TC被活性物種進(jìn)攻發(fā)生去氨基化,去羥基化反應(yīng)得到產(chǎn)物P1,隨后,發(fā)生開環(huán)反應(yīng)得到P2.路徑Ⅱ:TC發(fā)生氧化還原反應(yīng)得到產(chǎn)物P3和P4,P4通過去甲基化反應(yīng)得到P5,進(jìn)一步發(fā)生氧化反應(yīng),羥基被氧化成羰基則得到P6,若P4發(fā)生開環(huán)裂解氧化則得到P7.路徑Ⅲ:TC依次發(fā)生開環(huán)氧化,去羥基化反應(yīng)得到P8和P9,而后發(fā)生開環(huán)反應(yīng)得到P10,P11.這些中間產(chǎn)物進(jìn)一步被氧化分解,最終礦化為CO2,H2O,NO3-,NH4+等無(wú)機(jī)小分子[32].

3 結(jié)論

3.1 兩步法制備雙金屬硫化物(MnCo2S4)具有較好的催化性能,當(dāng)MnCo2S4和PMS濃度為0.1g/L,TC的降解率在30min就可達(dá)到88%.

3.2 在MnCo2S4/PMS體系中,自由基和非自由基共同作用降解TC.

3.3 S2-的強(qiáng)還原性可促進(jìn)高價(jià)金屬離子向低價(jià)金屬離子的轉(zhuǎn)變,從而實(shí)現(xiàn)活性位點(diǎn)的再生,同時(shí),錳、鈷的協(xié)同作用可促進(jìn)MnCo2S4催化性能的提升.

圖10 MnCo2S4/PMS體系中TC可能的降解途徑

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Enhanced degradation of tetracycline hydrochloride by cobalt-manganese sulfide activated peroxymonosulfate.

XIE Jin-ling1, PU Jia-xing1, LI Si-yu1, HUANG Li1, GONG Xiao-bo1,2*

(1.College of Chemistry and Materials Science, Sichuan Normal University, Chengdu 610066, China；2.Key Laboratory of Special Waste Water Treatment, Sichuan Province Higher Education System, Chengdu 610066, China)., 2023,43(2)：544～551

Manganese and cobalt bimetallic sulfide (MnCo2S4) was prepared by a simple two-step method. The morphology, crystal structure and composition of MnCo2S4were analyzed by scanning electron microscope, X-ray diffraction and X-ray photoelectron spectroscopy, respectively. Degradation efficiency and pathways of tetracycline hydrochloride in MnCo2S4/PMS system were explored. The degradation efficiency of TC reached 88% in 30min whenconcentrations of MnCo2S4and PMS were both 0.1g/L. The degradation efficiency of TC remained high in wide pH value range (3～9), which was attributed to the continuous supply of metal active sites of Mn2+and Co2+in MnCo2S4and the synergistic effect of cobalt and manganese. Quenching experiment and electron paramagnetic resonance (EPR) technology provided that SO4?-, ?OH and1O2were the main active species in MnCo2S4/PMS system. This research gives a new strategy for bimetallic sulfide catalyst construction to activate PMS and treat refractory pollutants.

bimetallic sulfide；tetracycline hydrochloride；peroxymonosulfate；catalytic degradation

X703.5

A

1000-6923(2023)02-0544-08

謝金伶(1997-),女,四川綿陽(yáng)人,四川師范大學(xué)碩士研究生,主要從事環(huán)境污染控制化學(xué)方向研究.發(fā)表論文3篇.

2022-06-27

國(guó)家自然科學(xué)基金資助項(xiàng)目(52170090)

* 責(zé)任作者, 副教授, gxb@sicnu.edu.cn