Electronic Supplementry Mteril (ESI) for Nnoscle. This journl is The Royl Society of Chemistry Supporting Informtion A Dul-Emitting d-f Nnocrystlline Metl-Orgnic Frmework s Self- Clirting Luminescent Sensor for Indoor Formldehyde Pollution Ji-N Ho nd Bing Yn* Shnghi Key L of Chemicl Assessment nd Sustinility, Deprtment of Chemistry, Tongji University, Siping Rod 39, Shnghi 9, Chin. Experimentl detils Mterils nd Methods. The slts of Eu(NO 3 ) 3 H O were prepred y dissolving the corresponding oxide compounds in excess nitric cid followed y evportion nd crystlliztion. Zirconium tetrchloride nd pyromellitic cid ws purchsed from Adms nd used directly without further purifiction. All the other strting mterils nd regents were ll AR nd used s purchsed. Powder X-ry diffrction (XRD) ptterns were otined on Bruker D Focus diffrctometer with Cu K rdition (λ =. Å, continuous, kv, ma, increment =. ). The gs dsorption/desorption isotherms for N t 77 K were performed on Tristr 3 nlyzer. Trnsmission electron microscopy (TEM) ws crried out using JEOL JEM-F electron microscope nd operted t kv. X-ry photoelectron spectroscopy (XPS) experiments were crried out on RBD upgrded PHI-C ESCA system (Perkin Elmer) with MgK rdition (hυ = 3. ev). Inductively coupled plsm-mss spectrometry (ICP-MS) dt were collected on n X-7 series inductively coupled plsm-mss spectrometer (Thermo Elementl, Cheshire, UK). The Fourier trnsform infrred (FT-IR) spectr were recorded on Nexus 9 AO infrred spectrum spectrophotometer with KBr pellets within the cm - region. The fluorescence spectr were mesured on n Edinurgh FLS9 fluorescence spectrophotometer, equipped with W Xe lmp s the excittion source. The solute externl luminescent quntum efficiency ws determined employing n integrting sphere ( mm dimeter, BSO coting) from n Edinurgh FLS9 phosphorimeter. Preprtion of Uio-(Zr)-(COOH) (). To synthesize the title compound, mixture of,,,-enzenetetrcroxylic cid (H tec,.3 g,.7 mol), Zirconium tetrchloride (ZrCl,.3 g,. mol), nd distilled wter ( ml) were plced in roundottom flsk equipped with reflux condenser nd mgnetic stirrer. This mixture ws refluxed ( C) under ir for h resulting in white gel, which ws seprted y centrifugtion nd wshed thoroughly severl times with distilled wter. To remove the orgnic species encpsulted within the pores s much s possile, the ctivtion ws further crried out y dispersing the smple in the distilled wter (~ ml per g of product) nd heted under reflux for h. The solid ws then recovered y centrifugl seprtion, wshed with cetone nd dried t 3 C under vcuum, yielding ~. g of white powder. Synthesis of Ag + /Eu 3+ ( ). Luminescent heterometllic co-doped MOFs were prepred y introducing the silver ions nd europium ions into the pores of compound. mg of the s-prepred were soked in ml of distilled wter contining Eu(NO 3 ) 3 H O (. mmol) nd different mounts of AgNO 3 (,,, 3, mmol). After one dy sokge under stirring nd drk condition, the solid ws then collected y centrifugtion, extensively wshed with wter, nd dried t 3 C under vcuum. For convenience, the s-otined smples with different Ag + doping (,,, 3, nd mmol) re nmed s,,, nd. Friction of luminescent films. The films were prepred y spin-coting method through dropping the lcoholic suspensions of onto the pre-clened sustrte which ws fixed on Lurell spin-coter. The spin-coting speed nd time ws kept t rpm for 3 s. The spin-coting process ws repeted severl times, nd then the film ws dried t room temperture. Vpor sensing. The fricted luminescent films were used for vpor sensing experiments. For ech experiment, the luminescent spectr of the films were mesured efore exposure to vrious solvent vpors. The film ws then crefully plced into seled continer (~ ml glss ottle) which contins ~ ml of given solvent for h t C, s shown elow. Susequently the film ws tken out of the continer, nd its emission spectrum ws quickly tken gin. Digrm of gs-sensing mesurements for solvent vpors
c Figure S. Structure of : () tetrhedrl cge; () octhedrl cge; nd (c) pcking of the two types of cges. V ds (STP) / cm 3 g - 3...... P/P Figure S. N dsorption-desorption isotherms of smples.
Asornce 7 7 Figure S3. FT-IR spectr of compound nd. 3 3 Wvenumer / cm - Zr Ag Eu Figure S. EDX mppings of the Zr, Ag, nd Eu elements in. Tle S. The detiled ICP-MS studies of smples. Mterils Zr + Eu 3+ Ag + Zr + Eu 3+ Ag + Zr : Eu : Ag (ppm) (ppm) (ppm) (mm) (mm) (mm) 9..7...97:: 7..7...3..3::.. 3.33..3..9.::.7. 3....37.79.9::3.3.9. 7.37.9.9..97::. 3
Reltive EX em = 3 nm EM ex = 3 nm Reltive EX em = 7 nm EM ex = 37 nm 3 3 7 37 7 7 7 Figure S. The excittion (lck line) nd emission (red line) spectr of H tec () nd compound (). The inset in () shows the corresponding photogrph under 3 nm UV-light irrdition. 3 7 3 = 7. Figure S. () The emission spectr of (λ ex = 33 nm), inset shows the enlrged spectr of in the rnge of -7 nm; () the luminescence intensities of Eu 3+ t 3 nm (red r) nd the lignd t 9 nm (cyn r) in. 3... I L
) ) Figure S7. ) The CIE chromticity coordintes of clculted from the emission spectr shown in Figure S, which shows the luminescent color chnges with the increse of Ag + -doping; ) The CIE chromticity coordintes nd the photogrphs of efore nd fter treted y. 3 C (mg/ml) Figure S. The intensity rtios ( ) of treted films fricted y different concentrtions of ethnol suspensions.
NH 3 OX Und Ben Tol BA EB 7 7 EB BA Tol Ben Und OX NH 3 Figu re S9.The luminescence spectr () nd the intensities (, I L, nd ) () of films fter treted y vrious indoor polluted gses. 7 7 NH 3 OX Und Ben Tol BA EB Figu re S. The emission spectr () nd the intensities (, I L, nd ) () of films fter treted y vrious indoor polluted gses. 3 s s s 3 s s 3. 3.... I L I L EB BA Tol Ben Und OX NH 3 7. Time / min Figure S. () The emission spectr of the film upon exposed to gs t vrious time intervls (λ ex = 33 nm) nd () the intensity ( ) s function of exposure time.
7 3 Ag + 7 c 7 Figure S. The emission spectr of, nd treted. As... 9 nm Reltive ex = 33 nm. 3 3 3 3 3 3 Figure S3. () UV-vis sorption spectrum of the lignd in nd () the phosphorescence spectrum of Ag + /Gd 3+ - nlogous to t 77 K. Becuse the P 7/ S 7/ Gd 3+ trnsition occurs t high energy (c. 3 cm - ), which presents the lignd-to-metl energy trnsfer, the oserved pek is scried to triplet lignd emission. Eu 3d Asornce c Reltive 3 3 3 3 3 3 3 3 Binding Energy / ev Wvenumer / cm - 7 Figure S. The Eu 3d XPS () nd FT-IR () spectr for Eu 3+ -doped efore nd fter exposure to ; (c) The emission spectr of efore nd fter exposure to (λ ex = 37 nm). 7
treted with Ag 3d / 37.9 ev Reltive *. Ag 3d 3/ 37 ev 3 3 Thet / degree 3 37 37 37 Binding Energy / ev Figure S. PXRD ptterns of efore nd fter treted y ; () The Ag 3d XPS for fter tretment with vpors. Figure S. TEM imge () nd HR-TEM imge () of fter treted with.