鄭懷禮,劉旺清,安延嚴(yán),陳 偉,孫 強(qiáng),萬(wàn)鑫源,趙 瑞

聚烯丙基磺酸鈉接枝空心玻璃微珠的制備及其吸附性能研究

鄭懷禮1*,劉旺清1,安延嚴(yán)1,陳 偉2,孫 強(qiáng)1,萬(wàn)鑫源1,趙 瑞1

(1.重慶大學(xué)環(huán)境與生態(tài)學(xué)院,重慶 400044；2.四川農(nóng)業(yè)大學(xué)土木工程學(xué)院,四川 成都 611830)

通過(guò)將烯丙基磺酸鈉(SAS)和硅烷偶聯(lián)劑接枝到空心玻璃微珠表面,制備出新型空心玻璃微珠基吸附劑(KNH-g-PSAS)并采用掃描電子顯微鏡,能量分散光譜,X射線光電子能譜,傅里葉變換紅外光譜,熱重分析和X射線衍射儀等對(duì)其進(jìn)行了充分的表征,顯示了SAS的成功接枝.此外,系統(tǒng)地研究了溶液的pH值,接觸時(shí)間,初始濃度和溫度對(duì)KNH-g-PSAS吸附陽(yáng)離子染料的影響.準(zhǔn)二級(jí)動(dòng)力學(xué)模型和Langmuir等溫線模型分別很好地描述了吸附動(dòng)力學(xué)和吸附等溫線,表明吸附是發(fā)生在吸附劑表面且均勻的單層吸附. 吸附實(shí)驗(yàn)表明,在最佳條件下,KNH-g-PSAS對(duì)堿性品紅、金胺O、結(jié)晶紫和孔雀石綠的吸附能力分別為2247.19mg/g, 2317.46mg/g, 2557.54mg/g,2808.98mg/g.KNH-g-PSAS具有出色的自上浮性能和回收表現(xiàn).

染料吸附；接枝共聚；π-π堆積；靜電相互作用；氫鍵

隨著經(jīng)濟(jì)快速發(fā)展,工業(yè)廢水排放量也日益增大,其成分復(fù)雜,有毒有害物質(zhì)多,對(duì)水環(huán)境影響大,其中染料及相關(guān)行業(yè)產(chǎn)生的印染廢水頗具代表性[1-2].數(shù)據(jù)顯示,全球紡織業(yè)染料的消耗量已超十萬(wàn)t每年,印染工藝中的硝化、磺化等過(guò)程產(chǎn)生的大量廢氣、廢液和廢渣,成分復(fù)雜,處理難度大[3-4].目前的處理方法有電化學(xué)法[5]、生化法[6]、膜處理法[7]、混凝法[8-9]、吸附法[10-11]、光催化法[12]等技術(shù),其中吸附法因其成本低,處理效果好,對(duì)環(huán)境友好,可重復(fù)利用等優(yōu)點(diǎn)被廣泛研究[13-15].目前,可作為吸附劑的材料主要有殼聚糖、沸石、活性炭、粉煤灰、石墨烯、木屑等[16-18].鄧維鈞等[19]、王艷等[20]、Xu等[21]、An等[22]分別制備出氧化鈰空心球、改性纖維素、改性殼聚材料、改性空心玻璃微珠并用于去除染料,結(jié)果發(fā)現(xiàn)對(duì)染料的去除均有一定的效果,但存在吸附容量不高、難以從溶液中分離、重復(fù)使用效果不佳、處理時(shí)間過(guò)長(zhǎng)等[23-26],導(dǎo)致無(wú)法推廣使用.因此,研發(fā)一種吸附能力強(qiáng),分離速度快,環(huán)境適應(yīng)力強(qiáng),可重復(fù)使用的吸附劑具有重要意義.

空心玻璃微珠(HGM)是一種主要由二氧化硅構(gòu)成的新型材料,因其高強(qiáng)度、低導(dǎo)熱、耐腐蝕、低導(dǎo)電、熱穩(wěn)定等優(yōu)點(diǎn)廣泛應(yīng)用于航空航天、冶金、建材軍事等領(lǐng)域[27-28],但目前,少有研究針對(duì)其低密度這一特性將其用于水處理領(lǐng)域.本研究以空心玻璃微珠為載體,通過(guò)硅烷偶聯(lián)劑(KH-550)改性后,在其表面接枝聚烯丙基磺酸鈉(PSAS)引入大量官能團(tuán),創(chuàng)造性地制備出自上浮吸附劑聚烯丙基磺酸鈉接枝空心玻璃微珠KNH-g-PSAS并用于去除堿性品紅(FB)、金胺O(BY2)、結(jié)晶紫(CV)、孔雀石綠(MG)四種具有代表性的陽(yáng)離子染料;對(duì)吸附劑進(jìn)行了全面的表征,考察了吸附性能,分析了吸附機(jī)理,最后研究了循環(huán)使用和自上浮性能,為其投產(chǎn)使用提供理論依據(jù).

1 材料與方法

1.1 材料

金胺O (>99.7%)、孔雀石綠 (>99.7%)、堿性品紅 (>99.7%)、結(jié)晶紫 (>99.7%)、氫氧化鈉 (>97.0%)購(gòu)自成都米氏化工有限公司(中國(guó)成都)、硅烷偶聯(lián)劑 (>98.0%)、無(wú)水乙醇(>99.7%)、過(guò)硫酸鉀(>99.0%)和烯丙基磺酸鈉 (>98.0%)購(gòu)自上海麥克林化工有限公司(中國(guó)上海).鹽酸(36.0～38.0%)購(gòu)自國(guó)藥化學(xué)試劑有限公司(中國(guó)上海),原裝使用.空心玻璃微球iM16K購(gòu)自3M?Center,MN(中國(guó)上海).用MILI-Q超純水(18.2MΩ)在中性pH條件下制備水溶液.

1.2 吸附劑制備

稱取適量空心玻璃微珠粉與NaOH溶液混合均勻,在80℃水浴鍋中攪拌1.5h,待溶液冷卻后交替用無(wú)水乙醇和超純水洗滌并過(guò)濾,烘干濾液得到經(jīng)NaOH腐蝕的HGM產(chǎn)品(NH).

稱取適量NH、硅烷偶聯(lián)劑(KH-550)、無(wú)水乙醇與超純水混合均勻,在80℃水浴鍋中繼續(xù)攪拌2h,待溶液冷卻后用超純水洗滌并過(guò)濾,烘干濾液得到經(jīng)KH-550改性的NH產(chǎn)品(KNH).

稱取適量KNH與超純水混合均勻,通入氮?dú)?N2)5min后向其中加入適量0.04g/mL過(guò)硫酸鉀(KPS)溶液并迅速密封瓶口,在80℃水浴鍋中攪拌10min;設(shè)置水浴鍋溫度為70℃,加入適量SAS溶液(50wt%),通入N25min并再次迅速密封瓶口,連續(xù)攪拌3h,待溶液冷卻后用超純水洗滌并過(guò)濾,烘干濾液得到新型吸附劑聚烯丙基磺酸鈉接枝空心玻璃微珠KNH-g-PSAS.制備過(guò)程如圖1所示.

圖1 KNH-g-PSAS合成示意

1.3 吸附實(shí)驗(yàn)

式中:0和e是染料的初始和平衡濃度;(g)吸附劑投加質(zhì)量;(L)是溶液體積.

1.4 上浮實(shí)驗(yàn)

為評(píng)價(jià)KNH-g-PSAS的自上浮性能,進(jìn)行了上浮實(shí)驗(yàn).具體方法為:稱取250mgKNH-g-PSAS、250mL超純水均勻混合于250mL量筒中,在50mm高度處每隔5min測(cè)量懸浮液濁度,以同樣的實(shí)驗(yàn)方法測(cè)量100mm、150mm高度處懸浮液的濁度.

2 結(jié)果和討論

2.1 表征分析

2.1.1 SEM分析 由圖2(a)可見,HGM呈光滑的球形,大小均勻,這種形貌與文獻(xiàn)報(bào)道[29]的一致.由其中少許的碎片可知,HGM是中空的球體,這也是其密度較小的主要原因.由圖2(b)可見,NH的表面更加粗糙,這說(shuō)明NaOH腐蝕了HGM表面并增加其比表面積.由圖2(c)可見,由于硅烷偶聯(lián)劑填充在了NH表面,其形貌明顯發(fā)生變化,粗糙程度介于HGM和NH之間,這說(shuō)明NH表面又增加了新的物質(zhì).KNH-g- PSAS的表面最為粗糙,這是由于在KNH表面接枝了聚烯丙基磺酸鈉導(dǎo)致的.由比表面積測(cè)試(BET)可得,4種材料的比表面積分別為2.152,21.624,16.594, 22.035m2/g,這說(shuō)明NaOH腐蝕HGM表面大量增加其比表面積和粗糙程度,硅烷偶聯(lián)劑填充在NH表面的凹陷中使得比表面積有所降低,而由于PSAS的成功接枝使得比表面積又有所增加.

圖2 HGM(a)、NH(b)、KNH(c)、KNH-g-PSAS(d)的掃描電鏡圖(×4000)

2.1.2 FTIR分析 由圖3(a)可見,四種產(chǎn)品都存在共同的特征峰:在1406cm-1處為C-H非對(duì)稱彎曲振動(dòng)峰[23],在1400-1650cm-1范圍內(nèi)存在少量C=C特征峰,在969cm-1處為Si-O-C反對(duì)稱伸縮運(yùn)動(dòng)峰,在793cm-1處為Si-O-C彎曲振動(dòng)峰[24].特別地,只有KNH-g-PSAS在1037cm-1[30]處出現(xiàn)-SO3H的特征峰,這說(shuō)明所制備吸附劑上有磺酸基的存在,上述特征峰表明PSAS成功接枝在KNH表面.另外,由圖3(b)可以看出,SAS在1641cm-1處存在大量的C=C,但在KNH-g-PSAS中C=C巨幅減少,這說(shuō)明在反應(yīng)過(guò)程中,SAS中的C=C打開發(fā)生了聚合反應(yīng),這從另一個(gè)角度說(shuō)明了SAS的成功接枝.

2.1.3 TGA-DSC分析 由圖4(a)可見,在25～1000℃范圍內(nèi),HGM幾乎沒(méi)有質(zhì)量損失,這是由于SiO2穩(wěn)定的晶體結(jié)構(gòu),具有良好的熱穩(wěn)定性[31-32].而KNH和KNH-g-PSAS具有兩個(gè)明顯的失重階段:在25-283.2℃時(shí),合成過(guò)程中分子鏈中的親水性基團(tuán)中的結(jié)合水蒸發(fā)[33];在283.2-634.1℃時(shí),KNH的熱失重約為3.72%,主要是酰胺基團(tuán)的亞胺化和硅醇基的分解[34-35],KNH-g-PSAS熱失重約為8.82%,失重更快是因?yàn)榛撬峄鶊F(tuán)的熱分解和共聚物主鏈的熱分解.當(dāng)溫度升高至634.1℃,兩種材料均趨向于穩(wěn)定,總失重分別為7.19%,12.44%.由圖4(b)可見, KNH-g-PSAS的熱重-差熱曲線(TGA-DSC)顯示出明顯的兩個(gè)吸熱峰,分別出現(xiàn)在217.6℃,375.8℃,是KNH-g-PSAS熱重曲線拐點(diǎn)的導(dǎo)數(shù)值.以上結(jié)果表明,KNH-g-PSAS的熱穩(wěn)定性在25～283.2℃之間.

2.1.4 XRD分析 由圖5可見,HGM, NH, KNH, KNH-g-PSAS在17～25°之間均存在明顯的寬峰,說(shuō)明合成過(guò)程中SiO2晶體結(jié)構(gòu)得到了保留,而NH在29.5°、36.2°、39.6°、43.4°、47.7°、48.7°處有硅酸鈉的對(duì)應(yīng)晶面[36-37]對(duì)應(yīng)的衍射峰,硅酸鈉是由NaOH和SiO2反應(yīng)所得.隨著反應(yīng)的進(jìn)行,NH表面覆蓋了無(wú)定形的KH-550和PSAS后,X射線透過(guò)率降低,大部分衍射峰并未在KNH,KNH-g-PSAS上檢測(cè)出,這說(shuō)明了KH-550和PSAS的成功包覆和接枝.

圖5 HGM、NH、KNH、KNH-g-PSAS的XRD分析

2.1.5 XPS分析 由圖6可見,HGM、NH、KNH、KNH-g-PSAS都存在O、Ca、C、Si元素,相較于HGM和NH, KNH和KNH-g-PSAS增加了N1s峰,這是來(lái)自KH-550中的N元素,僅在KNH-g-PSAS中檢測(cè)到的S2s峰和S2p來(lái)自SAS上的-SO3H[38],這說(shuō)明-SO3H成功的被接枝到KNH表面,且由于PSAS的接枝,原有來(lái)自硅烷偶聯(lián)劑的N1s被減弱.

圖6 HGM、NH、KNH、KNH-g-PSAS的XPS全掃描光譜

2.2 吸附特性

2.2.1 pH值影響 pH值與溶液中的離子形態(tài),吸附劑表面電荷信息和活性中心息息相關(guān),因此pH值是評(píng)價(jià)其吸附性能的關(guān)鍵指標(biāo).文獻(xiàn)報(bào)道FB (pa3.9)、BY2(pa9.8)、CV(pa9.4)、MG(pa6.9)能在水溶液中電離并以離子形態(tài)存在[39-42];經(jīng)測(cè)定,FB、BY2、CV、MG的最大吸收波長(zhǎng)在pH=2～10范圍內(nèi)均沒(méi)有變化,這也說(shuō)明了染料以離子形態(tài)存在于水溶液中.

由圖8可見,KNH-g-PSAS的Zeta電位為負(fù)值且隨著pH值增大而減小,這是因?yàn)椤猄O3H的接枝提供了大量負(fù)電荷,且在堿性環(huán)境下其電負(fù)性更強(qiáng);在較寬pH值范圍內(nèi),KNH-g-PSAS對(duì)染料有非?？捎^的吸附容量,原因是其表面的—SO3H與染料表面的陽(yáng)離子之間的靜電相互作用,這與FTIR表征中觀測(cè)到KNH-g-PSAS存在大量—SO3H的結(jié)果是一致的.具體而言,在低pH值環(huán)境下,KNH-g-PSAS表面的—SO3H和FB、BY2、CV、MG表面的氨基等質(zhì)子化,從而使兩者之間的靜電相互作用減弱;在pH值為5左右,氨基開始發(fā)生去質(zhì)子化,吸附容量開始急劇增長(zhǎng),另一方面,染料中存在π-π共軛體系,π-π共軛體系間的作用力與—SO3H的疏水作用產(chǎn)生了分散力會(huì)促進(jìn)染料的自組織[43],這同樣增加了KNH-g-PSAS對(duì)染料的吸附.π-π共軛體系間的作用力在堿性環(huán)境下逐漸減弱,因此在pH值為8時(shí),MG吸附容量逐漸穩(wěn)定,pH值為9時(shí),FB、BY2、CV吸附容量逐漸穩(wěn)定,這與KNH-g-PSAS的Zeta電位在pH值為8之后的下降趨勢(shì)減緩的結(jié)果是一致的.相關(guān)文獻(xiàn)報(bào)道,染料初始pH值越低,溶液中游離的H3O+濃度越高,相應(yīng)的對(duì)OH-的吸附能力越強(qiáng)[19],經(jīng)測(cè)試四種染料溶液在相同條件下的初始pH值分別為FB(5.34),BY2(2.39),CV(4.26),MG(2.31),因此,BY2和MG有負(fù)電荷更敏感的表現(xiàn),吸附容量高于FB和CV.

圖7 陽(yáng)離子染料分子結(jié)構(gòu)

圖8 不同pH條件下KNH-g-PSAS的Zeta電位及對(duì)染料的吸附容量

2.2.2 投加量影響和吸附等溫線 由圖9a可見,KNH-g-PSAS的吸附容量隨染料初始濃度的增加而增加.較低初始濃度是影響固液相間染料傳質(zhì)阻力的關(guān)鍵因素,因此初始濃度在0～1400mg/L范圍內(nèi)平衡吸附容量增速顯著,而增長(zhǎng)至1600mg/L時(shí),吸附容量增速大幅減緩,這可能是由于KNH-g- PSAS表面的吸附位點(diǎn)已趨近于飽和.

為探討KNH-g-PSAS對(duì)染料的吸附過(guò)程和吸附機(jī)理,本研究選取Langmuir、Freundlich、Temkin等溫線模型分析KNH-g-PSAS的吸附數(shù)據(jù)[44].非線性方程表達(dá)如下:

式中:(min)為接觸時(shí)間,e(mg/g)為吸附平衡時(shí)的吸附容量,e(mg/L)為吸附平衡時(shí)的溶液濃度L、F、T分別為對(duì)應(yīng)模型的吸附常數(shù),為衡量吸附能力的均質(zhì)因子,m為飽和吸附容量,為吸附熱相關(guān)參數(shù),L為無(wú)量綱因子,可以用來(lái)預(yù)測(cè)是否對(duì)吸附有利:不利的(L>1),有利的(0

表1 KNH-g-PSAS吸附陽(yáng)離子染料的等溫線參數(shù)

2.2.3 吸附時(shí)間影響和吸附動(dòng)力學(xué) 由圖10可見,在0～70min時(shí),KNH-g-PSAS對(duì)染料進(jìn)行迅速吸附,這主要是由于兩者之間的靜電相互作用力強(qiáng), KNH-g-PSAS的表面在吸附初期存在大量的吸附位點(diǎn);隨著大量吸附位點(diǎn)被占據(jù),吸附速率逐漸降低,FB在100min左右達(dá)到吸附平衡,BY2、CV、MG在200min左右達(dá)到吸附平衡.

圖10 接觸時(shí)間對(duì)KNH-g-PSAS吸附陽(yáng)離子染料的影響及其對(duì)應(yīng)的準(zhǔn)二級(jí)動(dòng)力學(xué)擬合曲線

通過(guò)準(zhǔn)一級(jí)動(dòng)力學(xué),準(zhǔn)二級(jí)動(dòng)力學(xué)和顆粒內(nèi)擴(kuò)散模型三種吸附動(dòng)力學(xué)模型對(duì)吸附數(shù)據(jù)進(jìn)行擬合,非線性方程[45]表達(dá)如下:

式中:(min)為接觸時(shí)間;t(mg/g)為時(shí)間時(shí)的吸附量;qe(mg/g)為飽和吸附容量;1(min-1),2(g/ (mg·min)),p(mg/(g·min0.5))分別為三種模型的速率常數(shù);為邊界層厚度相關(guān)常數(shù)(mg/g).將各模型所擬合的吸附數(shù)據(jù)計(jì)算并匯總至表2中.

表2 KNH-g-PSAS吸附陽(yáng)離子染料的動(dòng)力學(xué)參數(shù)

準(zhǔn)二級(jí)動(dòng)力學(xué)模型能更好地描述KNH-g- PSAS對(duì)FB, BY2, CV, MG的吸附行為,其2值分別為0.9996,0.9991,0.9985,0.9991,遠(yuǎn)高于其余兩種模型,這表明化學(xué)吸附機(jī)理控制吸附過(guò)程速率,同時(shí)吸附速率與吸附劑表面的染料濃度有關(guān).

2.2.4 溫度影響和吸附熱力學(xué) 由圖11可見,溫度的升高有利于KNH-g-PSAS對(duì)染料的去除,其中對(duì)MG的去除受到溫度的影響最大.

圖11 溫度對(duì)KNH-g-PSAS吸附陽(yáng)離子染料的影響

2.2.5 離子濃度影響 由圖12可見,染料去除效率隨離子強(qiáng)度的增加而降低.這是因?yàn)閹д姷腘a+不僅降低了陰離子染料的電負(fù)性,使得染料與KNH- g-PSAS之間的靜電相互作用被削弱,其本身也通過(guò)占據(jù)了部分吸附位點(diǎn)抑制了吸附,但值得注意的是,在干擾離子濃度(1mol/L)遠(yuǎn)遠(yuǎn)大于染料濃度(FB: 0.0029mol/L、BY2:0.0033mol/L、CV0.0026mol/ L、MG0.0028mol/L)的情況下,KNH-g-PSAS依然表現(xiàn)出了優(yōu)異的針對(duì)染料的吸附效果(FB1392.26mg/ g,BY21981.63mg/g,CV1231.27mg/g,MG1456.75mg/g),說(shuō)明其是一種抗干擾能力優(yōu)異的吸附劑.

表3 KNH-g-PSAS吸附陽(yáng)離子染料的熱力學(xué)參數(shù)

圖12 NaCl濃度對(duì)KNH-g-PSAS吸附陽(yáng)離子染料的影響

2.2.6 再生性和循環(huán)性能 由圖13可見,經(jīng)過(guò)6次吸附-解吸循環(huán)實(shí)驗(yàn)后,以第一次的吸附容量為100%計(jì),KNH-g-PSAS的吸附容量逐漸降低,這可能是因?yàn)樵诮馕^(guò)程中,仍然有少量染料分子殘留在吸附劑表面,但總體而言對(duì)染料的去除率還是在初次利用時(shí)的70%以上,第6次實(shí)驗(yàn)對(duì)FB、BY2、CV、MG的去除率仍舊高達(dá)第一次實(shí)驗(yàn)的84%, 80%,70%,73%,因此認(rèn)為其重復(fù)利用性能好,有較高潛力用于去除印染廢水.

圖13 KNH-g-PSAS對(duì)陽(yáng)離子染料的循環(huán)使用效率

2.3 自上浮性能

經(jīng)測(cè)定,KNH-g-PSAS的平均密度為0.366g/ cm3,這從理論上表明其可以從與水的混合液中上浮至表面,由圖14可見,在0～20min內(nèi),100mm以下的KNH-g-PSAS快速上浮,濁度下降至500NTU以下,80%KNH-g-PSAS完成自上浮;40min左右,90%以上的KNH-g-PSAS都上浮到量筒表面.這表明KNH-g-PSAS能在較快的時(shí)間內(nèi)完成上浮,便于分離回收.

圖14 KNH-g-PSAS上浮實(shí)驗(yàn)

3 結(jié)論

3.1 KNH-g-PSAS對(duì)染料的吸附符合準(zhǔn)二級(jí)動(dòng)力學(xué)和Langmuir模型,為吸附過(guò)程發(fā)生在KNH- g-PSAS表面的單分子層吸附,KNH-g-PSAS對(duì)FB、BY2、CV、MG的飽和吸附容量分別為2247.19, 2317.46, 2557.54, 2808.98mg/g.

3.2 大量的-SO3H基團(tuán)被引入到KNH表面,提供了大量的吸附位點(diǎn),-SO3H所帶的負(fù)電荷與染料所帶的正電荷間的靜電相互作用是吸附的主要因素,同時(shí)氫鍵對(duì)吸附起到了一定的作用.

3.3 KNH-g-PSAS的抗干擾能力優(yōu)異,自上浮性能和重復(fù)使用性能較好.

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Synthesis of polyallyl sodium sulfonate grafted hollow glass microbeads and its adsorption properties research.

ZHENG Huai-li1*, LIU Wang-qing1, AN Yan-yan1, CHEN Wei2, SUN Qiang1, WAN Xin-yuan1, ZHAO Rui1

(1.Faculty of Environment and Ecology, Chongqing University, Chongqing 400044, China；2.Faculty of Civil Engineering, Sichuan Agricultural University Chengdu 611830, China)., 2021,41(11)：5177～5186

A noval hollow glass bead-based adsorbent (KNH-g-PSAS) was successfully fabricated by grafting sodium allyl sulfonate (SAS) and silane coupling agent onto the surface of hollow glass beads. KNH-g-PSAS was characterized by scanning electron microscope, energy dispersion spectroscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis and X-ray diffractometer, showing the successful grafting of SAS. In addition, the effects of pH value, reaction time, initial concentration and temperature on the adsorption of cationic dyes by KNH-g-PSAS were systematically studied. The pseudo-order kinetic model and Langmuir isotherm model fitted the kinetics and isotherm data well, indicating that the adsorption were determined by chemsorption and uniform monolayer adsorption. Adsorption experiment showed that the adsorption capacity of KNH-g-PSAS for basic fuchsin, auramine O, crystal violet and malachite green were 2247.19mg/g, 23174.61mg/g, 2557.54mg/g and 2808.98mg/g, respectively. In addition, KNH-g-PSAS had excellent self-floating performance and recovery performance.

dye adsorption；graft copolymerization；π-π stacking；electrostatic interaction；hydrogen bonding

X703

A

1000-6923(2021)11-5177-10

鄭懷禮(1957-),男,教授,博士,主要從事水處理及水處理劑研究.發(fā)表論文400余篇.

2021-04-02

國(guó)家自然科學(xué)基金資助項(xiàng)目(21677020),重慶市技術(shù)創(chuàng)新與應(yīng)用示范專項(xiàng)重點(diǎn)研發(fā)項(xiàng)目(cstc2018jszx-zdyfxmX0002)

* 責(zé)任作者, 教授, zhl@cqu.edu.cn