Header Page of 148 I HC HU TRNG I HC S PHM NG TH QUNH LAN NGHIấN CU TNG HP V NG DNG CA MT S VT LIU KHUNG KIM LOI-HU C LUN N TIN S HểA HC HU-NM 2015 Footer Page of 148 Header Page of 148 I HC HU TRNG I HC S PHM NG TH QUNH LAN NGHIấN CU TNG HP V NG DNG CA MT S VT LIU KHUNG KIM LOI-HU C Chuyờn ngnh: Húa lý thuyt v húa lý Mó s: 62.44.01.19 LUN N TIN S HểA HC NGI HNG DN KHOA HC PGS.TS V Anh Tun PGS.TS Dng Tun Quang HU-NM 2015 Footer Page of 148 Header Page of 148 LI CAM OAN Tụi xin cam oan õy l cụng trỡnh nghiờn cu ca riờng tụi, cỏc s liu v kt qu nghiờn cu nờu lun ỏn l trung thc, c cỏc ng tỏc gi cho phộp s dng v cha tng cụng b bt k cụng trỡnh no khỏc Tỏc gi ng Th Qunh Lan Footer Page of 148 Header Page of 148 LI CM N Trc ht, tụi xin c t lũng bit n sõu sc n PGS.TS V Anh Tun v PGS.TS Dng Tun Quang, cỏc thy ó tn tỡnh hng dn, h tr v giỳp tụi hon thnh lun ỏn Tụi xin chõn thnh cm n TS H Vn Thnh, TS Hong Vinh Thng ó giỳp tụi sut quỏ trỡnh nghiờn cu Tụi xin chõn thnh cm n th cỏn b phũng Húa lý B mt- Vin Húa hc- Vin Hn lõm Khoa hc v Cụng ngh Vit Nam, quý thy cụ thuc khoa Húa trng i hc S phm Hu v trng i hc Khoa hc ó giỳp tụi quỏ trỡnh thc hin lun ỏn Tụi xin chõn thnh cm n Tnh y, UBND Tnh Tha Thiờn Hu, cm n Ban giỏm hiu trng Cao ng S phm ó quan tõm v to iu kin thun li cho tụi thc hin ti nghiờn cu Cui cựng, tụi xin cm n gia ỡnh, bn bố, cỏc ng nghip ó ng viờn giỳp tụi hon thnh lun ỏn ny ng Th Qunh Lan Footer Page of 148 Header Page of 148 MC LC Trang Trang ph bỡa i Li cam oanii Li cm n iii Mc lc.iv Danh mc cỏc ch vit tt vi Danh mc cỏc bngvii Danh mc cỏc hỡnh vviii M U.1 CHNG 1: TNG QUAN TI LIU18 1.1.Gii thiu chung v vt liu khung kim loi - hu c (Metal-OrganicFrameworksMOFs). 18 1.2.Cỏc phng phỏp tng hp MOFs24 1.3.Gii thiu v cỏc vt liu nghiờn cu25 1.4.Gii thiu v quỏ trỡnh hp ph 36 .Phn ng Fenton 40 1.5.1.Quỏ trỡnh oxi húa Fenton d th40 .2.Quỏ trỡnh quang Fenton 41 .3.ng dng ca Fenton x lý nc thi dt nhum 42 1.6.Hp ph asen44 1.6.1.Tớnh c hi ca asen.44 1.6.2.C ch ca quỏ trỡnh hp ph asen.46 CHNG M C TI U, N I DUNG, PHNG PH P NGHI N CU V TH C NGHIM 47 2.1.Mc tiờu 47 2.2.Ni dung.47 2.3.Phng phỏp nghiờn cu .47 2.3.1.Phng phỏp ph hng ngoi FT-IR 47 2.3.2.Phng phỏp nhiu x Rnghen (X-ray diffraction, XRD).48 2.3.3.Phng phỏp ph quang in t tia X (XPS) 50 2.3.4.Phng phỏp ph tỏn sc nng lng tia X (EDX).51 2.3 .Phng phỏp phõn tớch nhit (TGA) 52 2.3.6.Phng phỏp hin vi in t truyn qua (TEM) 53 2.3.7.Phng phỏp hin vi in t quột (SEM).54 2.3.8.Phng phỏp ng nhit hp ph- kh hp ph nitrogen (BET) 54 2.3.9.Phng phỏp ph hp th t ngoi v kh kin 56 Footer Page of 148 Header Page of 148 2.3.10.Phng phỏp quang ph hp th nguyờn t (AAS) 58 2.4.Thc nghim 59 2.4.1.Húa cht..59 2.4.2.Tng hp vt liu Cr-MIL-101 .60 2.4.3.Tng hp vt liu MIL- 3(Fe)..62 2.4.4.Tng hp vt liu MIL-88B 65 2.4 .Tng hp vt liu Fe-Cr-MIL-10166 2.4.6.Xỏc nh im ng in ca MIL-53(Fe)67 2.4.7.ỏnh giỏ kh nng hp ph asen67 2.4.8.Phn ng quang húa Fenton.68 CHNG K T QU V TH O LU N 69 3.1.Tng hp vt liu Cr-MIL-101.69 3.1.1.Nghiờn cu cỏc yu t nh hng n quỏ trỡnh tng hp vt liu Cr-MIL-101 69 3.1.2.c trng vt liu Cr-MIL-101 76 3.2.Tng hp vt liu MIL- 3(Fe).80 3.2.1.Nghiờn cu cỏc yu t nh hng n quỏ trỡnh tng hp MIL- 3(Fe)80 3.2.2.c trng vt liu MIL- 3(Fe)85 3.3.Tng hp vt liu MIL-88B.89 3.3.1.Nghiờn cu cỏc yu t nh hng n quỏ trỡnh tng hp MIL-88B 89 3.3.2.c trng vt liu MIL-88B92 3.4.Tng hp vt liu th ng hỡnh Cr b ng Fe MIL-101.97 .Nghiờn cu kh nng hp ph v xỳc tỏc quang húa Fenton ca vt liu Cr-MIL101, Fe-Cr-MIL-101, MIL-53(Fe), MIL88B103 .1.Kh nng hp ph thuc nhum RR19 trờn vt liu Cr-MIL-101, Fe-Cr-MIL101, MIL-53(Fe), MIL88B104 .2.Kh nng xỳc tỏc quang húa Fenton ca vt liu Cr-MIL-101 v Fe-Cr-MIL101106 3.6.Kh nng hp ph As(V) trờn cỏc vt liu nghiờn cu .112 3.7.Nghiờn cu ng hc quỏ trỡnh hp ph asen ca vt liu MIL- 3(Fe) v MIL-88B 114 3.7.1.im ng in ca MIL-53(Fe).114 3.7.2.Nghiờn cu cỏc yu t nh hng n quỏ trỡnh hp ph.116 3.7.3.Kho sỏt ng ng nhit hp ph120 3.7.4.ng hc quỏ trỡnh hp ph124 K T LU N129 Footer Page of 148 Header Page of 148 DANH M C C C BI B O LI N QUAN N LU N N TI LIU THAM KH O PH L C Footer Page of 148 Header Page of 148 DANH MC CC CH VIT TT TRONG LUN N AAS Ph hp ph nguyờn t (Atomic Adsorption Spectroscopy) BET Brunauer-Emmett-Teller COD Nhu cu oxi húa hc (Chemical Oxygen Demand) CUS S phi trớ cha bóo hũa (Coordinated Unsaturated Site) DTA Phõn tớch nhit vi sai (Differental Thermal Analysis) FT-IR Ph hng ngoi (Fourier Transform Infrared) EDX Tỏn x tia X (Energy Dispersive X-ray) HKUST-1 HongKong University of Science and Technology- HPHH Hp Ph Húa Hc HPVL Hp Ph Vt Lý IUPAC International Union of Pure and Applied Chemistry MCM Mobil Composition of Matter MIL Material Institute Lavoisier MOFs Metal Organic Frameworks SBA Santa Barbara Amorphous SBUs Cỏc n v cu trỳc th cp (Secondary Building Units) SEM Hin vi in t quột (Scanning Electron Microscopy) TEM Hin vi in t truyn qua (Transmission Electron Microscopy) TGA Phõn tớch nhit trng (Thermogravimetric Analysis) TMAOH Tetramethyl Ammonium Hydroxide UV-Vis Ph t ngoi-kh kin (Ultra Violet Visible) VOC Hp cht hu c d bay hi (Volatile Organic Compound) XPS Ph quang in t tia X (X-ray Photoelectron Spectroscopy) XRD Nhiu x tia X (X-Ray Diffraction) Footer Page of 148 Header Page of 148 DANH MC CC BNG Bng 2.1 Cỏc loi húa cht chớnh dựng lun ỏn .59 Bng 2.2 Ký hiu tờn cỏc mu Cr-MIL-101 tng hp cú t l H2BDC/Cr3+ khỏc .61 Bng 2.3 Ký hiu cỏc mu Cr-MIL-101 tng hp cú t l HF/Cr(NO3)3 khỏc .61 Bng 2.4 Ký hiu cỏc mu Cr-MIL-101 tng hp cú thi gian gia nhit khỏc .62 Bng Ký hiu cỏc mu MIL- 3(Fe) tng hp cú t l H2BDC/FeCl3 khỏc .64 Bng 2.6 Ký hiu cỏc mu MIL- 3(Fe) tng hp cú t l DMF khỏc .64 Bng 2.7 Ký hiu cỏc mu MIL-88B tng hp cú t l H2BDC/FeCl3 khỏc .65 Bng 2.8 Ký hiu tờn cỏc mu MIL-88B tng hp cú t l DMF khỏc .66 Bng 2.9 Ký hiu tờn cỏc mu MIL-88B tng hp cú nhit kt tinh khỏc .66 Bng 3.1 nh hng t l H2BDC/Cr(NO3)3 i vi tinh khit ca vt liu Cr-MIL-101 70 Bng 3.2 Thnh phn húa hc ca Cr-MIL-101 v Fe-Cr-MIL-101 98 Bng 3.3 Mt s tớnh cht húa lý ca Cr-MIL-101 v Fe-Cr-MIL-101 100 Bng 3.4 Mt s tớnh cht ca vt liu nghiờn cu 104 Bng Thnh phn húa hc ca cỏc vt liu nghiờn cu 112 Bng 3.6 So sỏnh dung lng hp ph As(V) ca cỏc cht hp ph khỏc nhau114 Bng 3.7 S ph thuc ca qt vo thi gian hp ph t 119 Bng 3.8 Cỏc giỏ tr Ce , qe, v Ce/qe, theo cỏc nng khỏc ca MIL- 3(Fe) v MIL-88B 121 Bng 3.9 Cỏc giỏ tr, logqe v logCe theo cỏc nng khỏc ca MIL- 3(Fe) v MIL-88B 123 Bng 3.10 Cỏc thụng s ca phng trỡnh ng nhit Langmuir v Freundlich ca MIL-53(Fe) 124 Bng 3.11 Cỏc thụng s ca phng trỡnh ng nhit Langmuir v Freundlich ca MIL-88B .124 Bng 3.12 Mt s tham s ca phng trỡnh ng hc biu kin bc nht 127 Bng 3.13 Mt s tham s ca phng trỡnh ng hc biu kin bc hai 127 Footer Page of 148 Header Page 10 of 148 DANH MC CC HèNH Hỡnh 1.1 Cỏch xõy dng khung MOF chung 18 Hỡnh 1.2 Mt s cu ni hu c MOFs .19 Hỡnh 1.3 Vớ d v cỏc SBU ca vt liu MOFs t cacboxylat a din kim loi mu xanh; O ; C mu en Cỏc a giỏc hoc a din c xỏc nh bi cỏc nguyờn t carbon ca nhúm cacboxylat (im m rng cú mu ) 20 Hỡnh 1.4 S lng cỏc cụng trỡnh cụng b v MOFs 12 nm gn õy 21 Hỡnh C ch hp ph cỏc cht c hi trờn vt liu MOFs 23 Hỡnh 1.6 Cỏc phng phỏp tng hp MOFs .24 Hỡnh 1.7 Quỏ trỡnh hỡnh thnh MIL-53(Fe) v MIL-88B b ng s to mm 25 Hỡnh 1.8 (a) Xõy dng khung ca MIL-101, 3D-[Cr3(O)(BDC)3(F)(H2O)2] 25H2O, (b) n v xõy dng th cp ca MIL101{Cr3(O)(F)(H2O)2} gm cỏc nhúm cacboxylat liờn kt vi nguyờn t Cr, (c) cỏc ca s ang m rng ln nht xung quanh cỏc lng mao qun, (d) kt ni ca ca ng giỏc v lc giỏc, (e) lng mao qun khung 3D 27 Hỡnh 1.9 Cu trỳc tinh th ca MIL- 3(Fe) gm bỏt din FeO6 liờn kt vi nhúm cacboxylic (cựng mt trc) 28 Hỡnh 1.10 Hiu ng th ca vt liu MIL-88(A,B,C,D) 29 Hỡnh 1.11 Cu trỳc tinh th MIL-88B, (a) cựng trc b v (b) cựng trc c 30 Hỡnh 1.12 c tớnh hớt th ca MIL-53(Fe) 34 Hỡnh 1.13 C ch ca quỏ trỡnh hp ph As(V) trờn vt liu cú cha Fe 46 Hỡnh 2.1 S chựm tia ti v chựm tia nhiu x trờn tinh th 49 Hỡnh 2.2 tự ca pic phn x gõy kớch thc ht 49 Hỡnh 2.3 Quỏ trỡnh phỏt quang in t 50 Hỡnh 2.4 Nguyờn tc phỏt x tia X dựng ph 52 Hỡnh Cỏc dng ng ng nhit hp ph-kh hp ph theo phõn loi IUPAC 55 Hỡnh 2.6 Bc chuyn ca cỏc electron phõn t .57 Hỡnh 2.7 Mi quan h gia cng vch ph A v nng cht Cx .59 Hỡnh 2.8 S tng hp vt liu MIL-53(Fe) 63 10 Footer Page 10 of 148 Header Page 135 of 148 organic coordination polymers prepared by solvothermal method and their application in efficient As(V) removal from aqueous solutions, Journal of Physical Chemitry C, 116 (15), pp 86018607 21 Bing L., Yongchun D., Zhizhong D., Yiming X., and Chi Z (2013), Renovation and reuse of reactive dyeing effluent by a novel heterogeneous Fenton system based on metal modified PTFE fibrous catalyst/H2O2, International Journal of Photoenergy, Article ID 169493, 10 pages 22 Bourrelly S., Llewellyn P L., Serre C., Millange F., Loiseau T., Fộrey G (2005), How hydration drastically improves adsorption selectivity for CO2, Journal of the American Chemical Society, 127, pp 13519-13521 23 Camilla Catharina Scherb (2009), Controlling the surface growth of metalorganic frameworks, Dissertation for 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Fộrey G., Hong D.Y., Hwang Y.K., Serre C (2009), Porous chromium terephthalate MIL-101 with coordinatively unsaturated sites Advanced Functional Materials, 19, pp 15371552 29 Chen C., Meng Z., Qingxin G., Wei L (2012), Kinetic and thermodynamic studies on the adsorption of xylenol orange onto MIL101(Cr), Chemical Engineering Journal, 183, pp 6067 30 Chen Y F., Babarao R., Sandler S I., Jiang J W (2010), Metal Organic Framework MIL-101 for adsorption and effect of terminal water molecules simulation, Langmuir, 26 (11), pp 8743 8750 31 Christian S., Sandrine B., Alexandre V., Naseem A R, Guillaume M., Philip L L, Marco D., Yaroslav F., Olivier L., Paul B., Gộrard F (2007), An explanation for the very large breathing effect of a metalorganic framework during CO2 adsorption, Advanced Functional Materials, 19, pp 22462251 32 Christoph J and Jana K.V (2010), MOFs, MILs and more concepts, properties and applications for porous coordination networks (PCNs), New Journal of Chemistry, 34, pp 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Xiu-Ping Y (2010), Metalorganic framework MIL-101 for high-resolution gas-chromatographic separation of xylene isomers and Ethylbenzene, Angewandte Chemie-International Edition, 49, pp 1477 1480 147 Footer Page 147 of 148 Header Page 148 of 148 148 Footer Page 148 of 148 Header Page 149 of 148 149 Footer Page 149 of 148 ... trung nghiên cứu tổng hợp vật liệu khung kim loại - hữu (Metal-Organic-Framework, kí hiệu MOFs) Vật liệu khung kim loại - hữu (MOFs) mạng không gian đa chiều, tạo nên từ kim loại oxit kim loại. .. thực vật Để nghiên cứu cách có hệ thống trình tổng hợp khả hấp phụ đặc biệt vật liệu MOFs, chọn đề tài Nghiên cứu tổng hợp ứng dụng số vật liệu khung kim loại - hữu cơ Nhiệm vụ luận án - Nghiên. .. 2.4.2 .Tổng hợp vật liệu Cr-MIL-101 ……………………………………………….60 2.4.3 .Tổng hợp vật liệu MIL- 3(Fe)……………………………………….……….62 2.4.4 .Tổng hợp vật liệu MIL-88B…………………………………………… 65 2.4 .Tổng hợp vật liệu Fe-Cr-MIL-101……………………………………………66