石墨烯基有序介孔金屬氧化物復(fù)合材料的制備及研究進(jìn)展-黃徽

石墨烯基有序介孔金屬氧化物復(fù)合材料的制備及研究進(jìn)展_黃徽（完整版）實(shí)用資料(可以直接使用，可編輯完整版實(shí)用資料，歡迎下載）

石墨烯基有序介孔金屬氧化物復(fù)合材料的制備及研究進(jìn)展_黃徽（完整版）實(shí)用資料(可以直接使用，可編輯完整版實(shí)用資料，歡迎下載）DOI:石墨烯基有序介孔金屬氧化物復(fù)合材料的制備及研究進(jìn)展黃徽1,2,楊平*2(1.南通職業(yè)大學(xué)化學(xué)與生物工程學(xué)院南通2260072.蘇州大學(xué)材料與化學(xué)化工學(xué)部蘇州215123摘要:石墨烯作為一種新型的二維晶體結(jié)構(gòu)碳納米材料,具有獨(dú)特的物理化學(xué)性質(zhì)如高的導(dǎo)電性能、良好的穩(wěn)定性、大的比表面積及較強(qiáng)的表面化學(xué)活性。石墨烯基有序介孔金屬氧化物復(fù)合材料具有完整的晶光生電子-殊的3D作了展望。關(guān)鍵詞:中圖分類號:TQ426.64文獻(xiàn)標(biāo)志碼:A1,2*2ocationalUniversity,Nantong226007,ChinaAbstract:structureofmesoporousmetaloxidesandthesupporterofgraphene,aswellasthebothsynergies,theseriesnovelgraphene-basedmesoporousmetaloxidecompositeshavebeenexplored.Inthispaper,wereviewedthepreparation,formationmechanismandtheapplicationsinvariousfieldsofgraphene-basedmesoporousmetaloxides.Thefuturedevelopmentsofgraphene-basedmesoporousmetaloxidematerialshavealsobeenprospected.Keywords:graphene;orderedmesoporousmaterials;metaloxide;composites;preparation收稿日期:2021-07-13;錄用日期:2021-07-22;網(wǎng)絡(luò)出版時(shí)間:網(wǎng)絡(luò)出版地址:基金項(xiàng)目:國家自然科學(xué)基金項(xiàng)目(No.21373143資助和江蘇省青藍(lán)工程(批準(zhǔn)號:蘇教師〔2021〕16號的資助通訊作者:楊平,博士,教授,博士生導(dǎo)師,研究方向?yàn)榇呋虏牧?光催化;太陽能轉(zhuǎn)化。Tel:86-512-65880361E-mail:引用格式:黃徽,楊平.石墨烯基有序介孔金屬氧化物納米復(fù)合材料的制備及研究進(jìn)展[J].復(fù)合材料學(xué)報(bào),2021,33(x:xxx-xxx.HuangHui,YangPing.Preparationandreserchprogressofgraphenebasedorderedmesoporousmentaloxide[J].ActaMateriaeCompositaeSinica,2021,33(x:xxx-xxx.文章第一作者,等:中文題名石墨烯作為一種新型二維平面納米材料,其內(nèi)部的π電子相互連接在同平面碳原子層的上下,形成大π鍵。這種離域的π電子可以在平面碳網(wǎng)內(nèi)自由流動(dòng),類似自由電子,具有類似于金屬的導(dǎo)電性和導(dǎo)熱性。由于石墨烯出眾的電學(xué),力學(xué),光學(xué)和熱學(xué)性能,迅速成為材料科學(xué)領(lǐng)域最為活躍的研究前沿[1-5]。近期,科學(xué)家將金屬納米粒子(Ag,Pd,Sn,Si、不同結(jié)構(gòu)的金屬氧化物(CuO2,Fe3O4,SnO2,WO3以及鹽類(Ag2S,BiVO4,Sr2Ta2O7與石墨烯結(jié)合制備出功能化石墨烯基復(fù)合材料[6-16]。其中,有序介孔金屬氧化物材料以其高的比表面積、規(guī)則有序的孔道結(jié)構(gòu)、孔徑大小可調(diào)及內(nèi)表面可修飾等特點(diǎn)而備受青睞[17,18]。隨著有序介孔金屬氧化物催化功能化、孔道尺寸調(diào)變、原位譜學(xué)表征和分子設(shè)計(jì)等關(guān)鍵問題的解決,許多具有不同形貌特征、介孔結(jié)構(gòu)、骨架成分的有序介孔金屬氧化物被成功合成[19-22]。眾多研究表明,以2D結(jié)構(gòu)的石墨烯作為載體,利用有序介孔金屬氧化物有序的3D結(jié)構(gòu),以及兩者共存產(chǎn)生的協(xié)同效應(yīng)制備的石化學(xué)、傳感和能量儲存等領(lǐng)域[23-25]。1圖1石墨烯基有序介孔金屬氧化物復(fù)合材料的制備Fig.1Preparationofgraphenebasedorderedmesoporousmetaloxide有序介孔金屬氧化物的合成主要采用模板法(軟模板法和硬模板法。目前,制備石墨烯基復(fù)合材料主要是先讓氧化石墨與其它材料復(fù)合再將氧化石墨還原;或先將石墨烯改性再與其它材料復(fù)合得到石墨烯基復(fù)合材料(如圖1。近年來,科學(xué)家們通過材料設(shè)計(jì)與合成路徑控制來開發(fā)功能化石墨烯基復(fù)合材料。本文綜述了石墨烯基WO3、Nb2O5、CeO2和In2O3等幾種典型的有序介孔金屬氧化物的最新研究進(jìn)展,詳細(xì)闡述了其合成方法、合成過程、合成機(jī)制及應(yīng)用研究。1.1石墨烯基介孔TiO2圖2一步法合成石墨烯基大孔-介孔TiO2[31]2[31]圖TiO2/石墨烯復(fù)合材料的TEM照片[34]basedmesoporousTiO2[34]自1972年Fujishima和Honda發(fā)現(xiàn)在TiO2電極上光致分解水以來,TiO2作為一種光催化劑在污水處理、空氣凈化、保潔除菌等方面應(yīng)用廣泛[26-28]。由于TiO2帶隙較寬(3.2eV,只有小于387nm光才能誘發(fā)光催化反應(yīng),而太陽光中只有大約5%的紫外光,大大限制了對太陽光的利用[29,30]。2021年,杜江等[31]利用石墨烯獨(dú)特的物理化學(xué)性質(zhì),采用一步法把石墨烯直接加入大孔-介孔TiO2合成過程,制得大孔-介孔TiO2/石墨烯復(fù)合光催化劑(如圖2。Yan等[32]采用紫外光協(xié)助照射法,以TiO2微球和氧化石墨烯為前驅(qū)物制備介孔TiO2微球/石墨烯復(fù)合材料,合成過程中加入氨基丙基三甲氧基硅烷(APTMS來促進(jìn)介孔TiO2微球/石墨烯復(fù)合材料的形成。Lavanya等[33]利用靜電紡絲技術(shù)合成了介孔TiO2納米纖維/石墨烯復(fù)合材料,顯示出優(yōu)異的光催化性能。2021年,張金龍課題組[34]利用葡萄糖中羥基和石墨烯表面的羥基、羧基等基團(tuán)間的脫水作用,實(shí)現(xiàn)了單晶納米TiO2在石墨烯表面的原位生長(如圖3,最終形成高分散介孔TiO2/三維石墨烯復(fù)合材料。研究發(fā)現(xiàn)葡萄糖的多羥基作用可以抑制(001面的生長,使TiO2單晶同時(shí)具有高分散性與暴露的文章第一作者,等:中文題名(001高能面,大大提升了復(fù)合材料的電子轉(zhuǎn)移效率。1.2石墨烯基介孔WO3WO3作為一種功能材料已廣泛應(yīng)用于催化、電致變色、電極材料、儲能及微波材料等領(lǐng)域[35-38]?？蒲泄ぷ髡邆儼l(fā)現(xiàn)將WO3制成孔道結(jié)構(gòu)規(guī)則大比表面積的有序介孔材料,可以有效拓展WO3的應(yīng)用范圍。許多文獻(xiàn)報(bào)道了以磷鎢酸為鎢源,介孔SiO2(KIT-6為硬模板,制備出比表面積大、晶型完整、孔道規(guī)則的有序介孔WO3[39,40]。2021年,Lee課題組[41]采用一步法,以PS-b-PEO為結(jié)構(gòu)導(dǎo)向劑合成的介孔WO3/碳納米復(fù)合材料,其比表面積高達(dá)123m2g-1,顯示出更高的電容容量和較快的電子傳輸速率。黃等[42]以KIT-6為模板,采用紫外光協(xié)助照射法合成了m-WO3-RGO復(fù)合型光催化劑,展示出優(yōu)異的分解水制氧性能(如圖4。Liu等[43]采用模板法成功制備了2D結(jié)構(gòu)的介孔WO3/石墨烯片,其擁有的垂直傳輸通道可以促進(jìn)電子和鋰離子的擴(kuò)散,大大提高電池容量與耐久性。圖4石墨烯基介孔WO3[42]33-RGO[42]1.3石墨烯基介孔2O3In2O3作為一種n(Eg=2.8eV,具有電池、氣敏元件等光電子器件領(lǐng)域中得到廣泛應(yīng)用[44-48]。1998年楊培東等[49]首先以三嵌段共聚物(P123為模板,制備出具有介孔結(jié)構(gòu)的氧化銦前驅(qū)物,未能得到具有有序介孔結(jié)構(gòu)的In2O3。2003年趙東元課題組[50]采用一步納米澆注法,在合成介孔SiO2的過程中加入前軀體In(NO33,促使有機(jī)模板劑與In2O3充分混合,成功合成了結(jié)構(gòu)有序、結(jié)晶度高的介孔In2O3。2021年Sreethawong等[51]以陽離子表面活性劑十二烷基氯化銨為導(dǎo)向劑,采用溶膠-凝膠法合成出具有雙孔徑分布的介孔In2O3。2021年,Zhao等[52]利用KIT-6為模板合成了高度結(jié)晶有序的介孔In2O3,將其與石墨烯復(fù)合之后,大大提升了有序介孔In2O3的性能,避免了鋰電池可逆容量急劇下降的缺陷。黃等[53]以有序介孔三氧化二銦(m-In2O3和還原氧化石墨烯(RGO為原料,采用紫外光照射法合成了介孔In2O3/還原氧化石墨烯復(fù)合光催化劑(m-In2O3-RGO,發(fā)現(xiàn)m-In2O3與RGO良好的界面接觸以及m-In2O3-RGO對可見光的良好響應(yīng),協(xié)同提高了m-In2O3-RGO的光催化活性(如圖5。圖5照片[53]2O3[53]Nb2O5O5是一種典型的n型半導(dǎo)體金屬氧化物材導(dǎo)纖維以及鍍膜材料等方面[54-57]。1996年,Ying等[58]研究發(fā)現(xiàn)采用伯胺類、磷酸酯類等強(qiáng)堿性或接觸性好的表面活性劑作為模板導(dǎo)向劑容易制得結(jié)構(gòu)規(guī)則的六方相介孔Nb2O5。通過改變表面活性劑與金屬的配比,又可得到六方相、立方相和層狀結(jié)構(gòu)的介孔Nb2O5。同年,該課題組又以月桂胺表面活性劑為模板劑,合成了比表面積為423m2/g、平均孔徑為2.7nm的介孔Nb2O5。2002年Domen課題組[59]首次以NbCl5為鈮源,嵌段共聚物P85為模板導(dǎo)向劑,采用軟模板法制得3D有序的介孔Nb2O5。2003年趙東元課題組[60]以NbCl5和Nb(OC2H55的混合物作為鈮源,P123為模板劑,制得高度有序的介孔Nb2O5薄膜,其平均孔徑在6nm左右,比表面積高達(dá)190m2/g。為了充分利用石墨烯基介孔材料大比表面積、活性位點(diǎn)多的優(yōu)點(diǎn),楊平課題組[61]采用一步法制備了介孔Nb2O5微球/石墨烯復(fù)合材料,由于介孔Nb2O5微球和石墨烯之間的良好表面接觸產(chǎn)生了積極的協(xié)同作用,增強(qiáng)了Nb2O5的分解水制氫性能(如圖6。《復(fù)合材料學(xué)報(bào)》Jan.152021Vol.32No.x圖6石墨烯基介孔五氧化二鈮微球復(fù)合材料的制備及SEM照片[61]Fig.6PreparationandSEMphotographsofgraphenebasedNb2O5micro-spherecomposite[61]綜上所述,在石墨烯的微小面積上排列有序規(guī)則的介孔金屬氧化物,可提高光捕獲效率及拓展其光響應(yīng)范圍,光生電荷經(jīng)有序介孔金屬氧化物的孔道結(jié)構(gòu)表面向石墨烯表面轉(zhuǎn)移,同時(shí)石墨烯作為電子受體將光生電子由石墨烯傳輸至目標(biāo)分子,有效減少光生電子的復(fù)合幾率,為開發(fā)新型石墨烯基復(fù)合材料提供理論參考依據(jù)。2石墨烯基有序介孔金屬氧化物的應(yīng)用2.1在光催化分解水中的應(yīng)用重要來源之一。自1972和Honda首次報(bào)導(dǎo)TiO2[26]。20世紀(jì)80年代,[62]。進(jìn)入21Cheng課題組[63]TiO2納米球/石墨烯復(fù)合材料。復(fù)合材料中的介孔TiO2納米球與石墨烯的有效結(jié)合促進(jìn)了載流子的分離和產(chǎn)氫量的提高。在可見光照射下,介孔TiO2納米球/石墨烯復(fù)合光催化劑的產(chǎn)氫量是納米TiO2的2.3倍。Cao課題組[24]通過微波照射法制備出介孔SnO2/石墨烯復(fù)合光催化劑,研究發(fā)現(xiàn)介孔SnO2均勻的分散在石墨烯表面形成的異質(zhì)結(jié)結(jié)構(gòu)和緊密的界面接觸,介孔SnO2/石墨烯復(fù)合光催化劑的產(chǎn)氫速率比納米SnO2提高了1倍。2021年黃等[42]以有序介孔WO3(m-WO3和還原石墨烯氧化物(RGO為原料采用紫外光協(xié)助照射法合成了m-WO3-RGO復(fù)合光催化劑,m-WO3與RGO的有效結(jié)合促進(jìn)了載流子的分離和產(chǎn)氧量的提高。在可見光照射下,m-WO3-RGO-6光催化劑的產(chǎn)氧量可達(dá)437.3μmol·g-1,為m-WO3的5.1倍。m-WO3-RGO可見光型催化劑的成功合成實(shí)現(xiàn)了太陽能向化學(xué)能的轉(zhuǎn)化,展現(xiàn)了一種全新的復(fù)合材料催化體系。2.2在光催化降解有機(jī)污染物中的應(yīng)用近20年來,光催化降解污染物成為極具發(fā)展?jié)摿Φ囊豁?xiàng)高效、節(jié)能的綠色環(huán)保新興技術(shù),光催化劑可用于降解水體中和大氣中的有機(jī)污染物。與傳統(tǒng)處理污染的措施相比較,光催化法的優(yōu)點(diǎn)是可將污染物徹底氧化分解為水、CO2等無[64,65]。目前研究較多的TiO2,但由于其太陽-空穴復(fù)合率高,限制了[31]把石墨烯直接加入到TiO2的自組裝過程中制得的大孔-2/-介孔TiO2的172021年,Yu課題組[66]成功合成了大孔-介孔TiO2/石墨烯復(fù)合材料用于光催化降解空氣中的丙酮,發(fā)現(xiàn)摻入0.05wt.%石墨烯的復(fù)合材料光催化活性最佳,約為納米TiO2的1.7倍。2.3在傳感領(lǐng)域的應(yīng)用近年來,介孔材料以其高的比表面積、規(guī)則的孔道結(jié)構(gòu)以及可修飾的內(nèi)表面等特性在傳感器領(lǐng)域科得到廣泛關(guān)注?？茖W(xué)研究表明,介孔材料,特別是介孔金屬氧化物的大比表面積可以有效增加活性位,大幅提高化學(xué)傳感器的工作效率。將石墨烯與介孔金屬氧化物材料制成復(fù)合材料用作傳感器,在生物醫(yī)藥領(lǐng)域具有良好的應(yīng)用前景。Wang等[67]采用電化學(xué)法合成了石墨烯基金納米復(fù)合材料具有較高的電催化活性、穩(wěn)定性、選擇性和抗干擾能力,作為葡萄糖生物傳感器用于對糖尿病、高血糖等疾病的糖分定量檢測。2021年,Gan等[23]采用簡單的碾磨法合成了介孔MnO2/氧化石墨烯復(fù)合材料。研究表明介孔MnO2/氧化石墨烯復(fù)合材料作為電化學(xué)傳感器來測定鄰苯二酚與對苯二酚,其陽極峰電位為115mV,表現(xiàn)出較高的吸附容量及催化活性。同年,該課題組又成功合成了介孔TiO2/石墨烯復(fù)合文章第一作者,等:中文題名材料并應(yīng)用于伏安傳感器來測定食品中微量的著色劑。介孔TiO2/石墨烯復(fù)合材料顯示出超強(qiáng)的聚集能力、催化性能和靈敏度,該方法簡單方便、成本低廉[68]。2.4在能源領(lǐng)域的應(yīng)用近年來,具有電磁性質(zhì)的金屬氧化物常用于各種固體電池材料如鎳電池、鋰電池、超級電容電池和燃料電池材料等[69]。將石墨烯與介孔金屬氧化物材料制成石墨烯基介孔金屬氧化物材料用作新型燃料電池和太陽能電池,在儲能領(lǐng)域具有良好的發(fā)展前景。岳等[70]制備了石墨烯包覆的介孔Co3O4復(fù)合材料,發(fā)現(xiàn)金屬氧化物具有較高的理論可逆容量,可作為鋰離子電池的電極材料。其中,介孔金屬氧化物以其較大的比表面積和特殊的孔結(jié)構(gòu),相比塊體材料其電容量更高、循環(huán)性能更好。石墨烯又是目前最好的導(dǎo)電材料之一,通過在石墨烯表面負(fù)載金屬氧化物可以有效的改善其循環(huán)性能。Zhao等[52]以KIT-6為模板合成的有序介孔In2O3作為前驅(qū)物,采用逐步共凝聚法來制備有序介孔In2O3/石墨烯復(fù)合材料,發(fā)現(xiàn)該復(fù)合材料的其電化學(xué)性能明顯優(yōu)于納米In2性能穩(wěn)定。3總結(jié)與展望動(dòng)新材料技術(shù)的飛速發(fā)展。參考文獻(xiàn):[1]GeimAK,NovoselovKS.Theriseofgraphene[J].NatureMaterials,2007,6:183-191.[2]DatoA,RadmilovicV,LeeZ,etal.Substrate-freegas-phasesynthesisofgraphenesheets[J].NanoLetters,2021,8:2021-2021.[3]BalandinAA,GhoshS,BaoW,etal.Superiorthermalconductivityofsingle-layergraphene[J].NanoLetters,2021,8:902-907.[4]XiangQJ,YuJG,JaroniecM,Graphene-basedsemiconductorphotocatalysts[J].ChemicalSocietyReviews,2021,41:782-796.[5]StankovichS,DikinDA,DommettGH,etal.Graphene-basedcompositematerials[J].Nature,2006,442:282-286.[6]WangZ,ZhangH,LiN,etal.Laterallyconfinedgraphenenanosheetsandgraphene/SnO2compositesashigh-rateanodematerialsforlithium-ionbatteries[J].NanoReserach,2021,3:748-756.[7]PasrichaR,GuptaS,SrivastavaAK.AfacileandnovelsynthesisofAg-graphene-based[8]?miyauracoupling–graphenepapercompositesfor3O4-graphenenanocompositeswithimprovedlithiumstorageandmagnetismproperties[J].TheJournalofPhysicalChemistryC,2021,115:14469-14477.[12]LiB,CaoH,YinG,etal.Cu2O@reducedgrapheneoxidecompositeforremovalofcontaminantsfromwaterandsupercapacitors[J].JournalofMaterialsChemistry,2021,21:10645-10648.[13]GuoJ,LiY,ZhuS,etal.SynthesisofWO3@Graphenecompositeforenhancedphotocatalyticoxygenevolutionfromwater[J].RSCAdvances,2021,2:1356-1363.[14]PanS,LiuX,WangX.PreparationofAg2Sgraphenenanocompositefromasinglesourceprecursoranditssurface-enhancedramanscatteringandphotoluminescentactivity[J].MaterialsCharacterization,2021,62:1094-10101.[15]WangHW,HuZA,ChangYQ,etal.DesignandsynthesisofNiCO2O4reducedgrapheneoxidecompositesforhighperformancesupercapacitors[J].JournalofMaterialsChemistry,2021,21:10504-10511.[16]NgYH,IwaseA,KudoA,etal.Reducinggrapheneoxideonavisible-lightBiVO4《復(fù)合材料學(xué)報(bào)》Jan.152021Vol.32No.x[17][18][19][20][21][22][23][24][25][26][27]photocatalystforanenhancedphotoelectrochemicalwatersplitting[J].TheJournalofPhysicalChemistryLetters,2021,1:2607-2612.CieslaU,SchüthF.Orderedmesoporousmaterials[J].MicroporousandMesoporousMaterials,1999,27:131-149.RenY,MaZ,BrucePG.Orderedmesoporousmetaloxides:synthesisandapplications[J].ChemicalSocietyReviews,2021,41:49094927.ShiYF,WanY,ZhaoDY.Orderedmesoporousnon-oxidematerials[J].ChemicalSocietyReviews,2021,40:3854-3878.WangY,YangCM,SchmidtW,etal.WeaklyferromagneticorderedmesoporousCo3O4synthesizedbynanocastingfromvinylfunctionalizedcubicIa3dmesoporoussilica[J].AdvancedMaterials,2005,17:53-56.JiaoE,JumasJC,WbmesM,etal.SynthesisoforderedmesoporousFe3O4andgamma-Fe2O3withcrystallinewallsusingpost-te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