Cu-BTC Functional Microdevices as Smart Tools for Capture and Preconcentration of Nerve Agents

1 Cu-BTC unc ional mic ode ices as sma ools o 1 cap u e and p econcen a ion o ne e agen s 2 F. Almazán, 1 M.A. U biz ondo,1, 2 P. Se a-C espo,3 B. Seoane,4 J. Gascon,4, 5 J. San ama ía,1, 6, 3 7 M.P. Pina1, 6, 7 4 1 Nanoscience Ins i u e o A agon (INA), Uni . Za agoza, Depa men o Chemical & 5 En i onmen al Enginee ing, Campus Rio Eb o, C/Ma iano Esquillo s/n, 50018 Za agoza, Spain 6 2 Cen o Uni e si a io de la De ensa de Za agoza, Ca e e a Huesca s/n, 50090 Za agoza, Spain 7 3 Applied Radia ion and Iso opes, Depa men o Radia ion Science and Technology, Facul y o 8 Applied Sciences, Technical Uni e si y Del , Mekelweg 15, 2629 JB, Del , he Ne he lands 9 4 Ca alysis Enginee ing, Depa men o Chemical Enginee ing, Del Uni e si y o Technology, 10 Van de Maasweg 9, 2629 HZ Del , The Ne he lands 11 5 Ad anced Ca aly ic Ma e ials, KAUST Ca alysis Cen e , King Abdullah Uni e si y o Science 12 and Technology, Thuwal 23955, Saudi A abia 13 6 Ne wo king Resea ch Cen e on Bioenginee ing, Bioma e ials and Nanomedicine, CIBER- 14 BBN, 28029 Mad id, Spain 15 7 Uni Za agoza, CSIC, Ins i u o de Ciencia de Ma e iales de A agón (ICMA), C/Ped o Ce buna 16 12, 50009 Za agoza, Spain 17 2 KEYWORDS: mic o ab ica ion, coppe modi ied glass subs a es, h eshold cu en densi y, 18 in eg a ion o me al o ganic amewo k ilms, co-adso bed wa e apo , ne e agen s cap u e 19 20 ABSTRACT: Cu-based Me al O ganic F amewo ks (MOF) mic ode ices a e applied in 21 sampling and p econcen a ion o ne e agen s (NAs) dilu ed in gaseous s eams. An in-si u 22 elec ochemical assis ed syn hesis o Cu-BTC hick ilm is ca ied ou o unc ionalize a Cu 23 modi ied glass subs a e. This simple, apid, ep oducible and easy o in eg a e MOF syn hesis 24 app oach, enables he mic o ab ica ion o unc ional mic op enconcen a o s wi h la ge BET 25 su ace a ea (abo e 2000 cm2) and ac i e po e olume (abo e 90 nanoli e s) o he e icien 26 adso p ion o ne e agen molecules along he mic o luidic channel 2.5 cm in leng h. Equilib ium 27 adso p ion capaci y o he bulk ma e ial has been cha ac e ized h ough he mog a ime ic 28 analysis a e exposu e o con olled a mosphe es o a sa in gas su oga e, dime hyl 29 me hylphosphona e (DMMP), in bo h d y and humid condi ions (30% RH a 293 K). 30 B eak h ough es s a ppm le el (162 mg/m3) e eal equilib ium adso p ion capaci ies up o 691 31 mg/g. The p econcen a ion pe o mance o such µ-de ices when dealing wi h highly dilu ed 32 su oga e a mosphe e, i.e. 520 ppbV (2.6 mg/m3) a 298 K, leads o p econcen a ion coe icien s 33 up o 171 o sample olume up o 600 STP cm3. We demons a e he po en iali ies o Cu-BTC 34 mic op econcen a o s as sma i s esponde ools o  d de ec ion o ne e agen s in 35 gas phase a ele an condi ions. 36 37 3 INTRODUCTION 38 Vulne abili y o c i ical indoo in as uc u es o in en ional ne e agen s elease poses a 39 signi ican poin o conce n o au ho i ies esponsible o inciden p epa edness and p e en ion. 40 Such chemical compounds a e odo less, colo less, highly pe sis en , ola ile and le hal e en a 41 low concen a ion.1 Pa icula ly, he o ganophosphona es-based ne e agen s (NAs), whe e he 42 well-known sa in and soman gases belong o, ha e been used agains ci ilian popula ion in 43 shocking e o is a acks. In amously known a e he e o is a ack in he subway o Tokyo in 44 1991 and he ecen ones agains ci ilians in Sy ia.2 A ew s udies a e a ailable o sa in apo 45 exposu es on human olun ee s in o de o di ec ly de i e acu e exposu e guideline le els. 46 Resul s indica e ha he h eshold o miosis and o he minimal oxic e ec s alls in he ange o 47 0.05  0.5 mg/m3 (9  87 ppbV) o 30 - 10 min exposu es, espec i ely.3 48 Due o he po en ial h ea ha NAs cons i u e agains he popula ion, many e o s ha e been 49 dedica ed o i s ea ly de ec ion. To imp o e he limi o de ec ion o he a ailable equipmen , a 50 common solu ion is o implemen a apping-p econcen a ion uni ups eam he de ec o . This 51 app oach has been success ully applied in many ields whe e he iden i ica ion o compounds a 52 e y low concen a ion (sub ppmV) is equi ed; such as wo kplace heal h and sa e y4 o o non- 53 in asi e, diagnos ic ools based on he de ec ion o exhaled ola ile bioma ke s5. En ichmen 54 ac o s up o 300 ha e been epo ed o a oma ic VOCs using ca bon nano ubes-based µ- 55 p econcen a o s o 100 ppbV eed concen a ion and sample olume up o 400 STP cm3.6 56 MOFs a e hyb id ma e ials composed o coo dina i ely linked me al ions o clus e s ia 57 o ganic ligands o o m po ous c ys alline amewo ks wi h p o en mic opo osi y. Compa ed o 58 mic opo ous zeoli es o mesopo ous silica, MOFs exhibi highe chemical e sa ili y. 59 Rema kable adso p ion capaci ies ha e been epo ed owa ds o ganophosphona e compounds. 60 4 The iso e icula IRMOF-1 Zn4O(dmcapz)3, dmcapz s ands o 4-ca boxy-3,5- 61 dime hylpy azola e, exhibi s an adso p ion capaci y up o 950 mg DMMP/g IRMOF-1 o 62 sa u a ed a mosphe e o dime hyl me hylphosphona e (DMMP) a 50 ºC 7; as well as mild 63 adso p ion hea alues (-Had = 44.8 J/  da (DIFP) a 64 empe a u es anging om 383 o 513 K 8). Newly de eloped Z -based MOFs, such as NU-1000, 65 UiO-66 o MOF-808, ha e a ac ed in e es in NAs decon amina ion no only due o hei 66 so p ion p ope ies (713 mgDMMP/gNU-1000 and 152 mgDMMP/gUiO-66 o 507 mg/m3 67 DMMP a 298K 9) bu also due o hei ca aly ic p ope ies owa ds o ganophospho us 68 deg ada ion by hyd olysis.10 69 Cu-based MOFs, such as Cu-BTC (HKUST-1), ha e also been widely epo ed as adequa e 70 adso ben s o o ganophospho ous apo s due he high a ini y ha hose compounds exhibi 71 owa ds Cu clus e s and he s abili y o he esul ing me al complexes. Fou ie - ans o ma ion 72 in a ed (FTIR) spec oscopy analysis on su ace acous ic wa e ype senso s unc ionalized ia 73 sel -assembled monolaye wi h (CO2)2Cu as e minal g oup and exposed o diisop opyl 74 me hylphosphona e (DIMP) in gas phase e eal he o ma ion o CuDIMP complexes (P=O- 75 Cu). 11 The a ini y o o ganophospho ous compounds o coppe ions s ill p e ails in HKUST-1 76 as demons a ed by he expe imen ally measu ed adso p ion hea alue o 77 diisop opyl luo ophospha e (DIFP), -Hads = 48.4 kJ/mol, which is highe han ha obse ed o 78 comme cial Ca boxen, -Hads = 38.3 kJ/mol.12 Finally, heo e ical compu a ional models13 using 79 densi y unc ional heo y (DFT) poin ou ha he mos a o able MOFs, among he 1544 MOFs 80 es ed, o Sa in gas adso p ion a e hose wi h po e sizes in he ange o 6-8 Å. Smalle po es 81 canno accommoda e Sa in molecules and on la ge po es he molecula in e ac ions wi h he 82 amewo k become weake . Acco dingly, Cu-BTC eme ges as po en ial adso ben o 83 5 o ganophosphona es compounds hanks o i s po e size dis ibu ion14 and he chemical a ini y o 84 he Cu nodes. Thus, well-in e g ow h laye s o Cu-BTC on mic o luidic de ices a e he ein 85 explo ed o cap u e and p econcen a e DMMP, a Sa in su oga e, om highly dilu ed gas 86 s eams. 87 The syn hesis o MOF ilms has been pa icula ly o in e es in he ield o chemical senso s15 88 and gas memb anes o selec i e sepa a ions16. No el app oaches such as mic o luidic pen 89 li hog aphy17 o inkje p in ing echnology a e gaining impo ance due o hei po en ial o la ge 90 scale manu ac u ing o unc ional mic ode ices. Recen ly, UiO-66 has been syn hesized in si u 91 by inkje p in ing on esonan Si mic ocan ile e s wi h piezo esis i e de ec ion, which ha e been 92 applied o DMMP sensing wi h heo e ical limi o de ec ion down o 0.025 mg/m3 (5 ppbV).18 93 In his wo k, in si u elec ochemical g ow h o Cu-BTC, a well-known MOF ma e ial ha has 94 been ex ensi ely in es iga ed bo h expe imen ally and heo e ically, on a glass modi ied 95 subs a e is ca ied ou o unc ionalize µ-p econcen a o s o NAs19,20 in o de o demons a e 96 he po en iali ies o cap u e and p econcen a ion applica ions. The mic opa e ned Cu elec ode 97 is exposed o he elec oly e solu ion and used as me al sou ce o he in si u elec ochemical 98 syn hesis o Cu-BTC ilms ollowing a simila app oach o ou p e ious publica ions21. The wo k 99 is di ided in wo pa s. The i s pa is de o ed o s udy he in luence o he cu en densi y and 100 numbe o elec osyn hesis cycles on he he e ogeneous MOF c ys alliza ion a e, c ys al 101 mo phology and su ace co e age o he glass subs a e. Special a en ion is paid o he na u e o 102 he Cu adhesion p omo e s (Au-C s. Ti). As a esul , an op imum po en iome ic p ocedu e is 103 de ined o he ab ica ion o unc ional mic ode ices based on Cu-BTC ilms. The second pa 104 is ocused on he adso p ion pe o mance o he unc ional µ-p econcen a o s owa ds DMMP. 105 Equilib ium up ake alues, dynamic adso p ion p ope ies om b eak h ough es s a ppmV le el 106 6 and p econcen a ion coe icien s a e e alua ed and compa ed wi h published da a. Fu he mo e, 107 he molecula in e ac ions o DMMP wi h Cu-BTC and Cu/Cu2O su aces in d y and humid 108 condi ions a e compu a ionally s udied o gain insigh in o he expe imen al esul s. Thus, his 109 wo k cons i u es one o he s ill e y sca ce epo s on MOF based unc ional mic ode ices. To 110 he bes o ou knowledge, con inuous Cu-BTC ilms and Si based mic o luidic de ices a e 111 combined o he i s ime o be employed e icien ly in sampling and p econcen a ion 112 applica ions o oxic compounds. 113 EXPERIMENTAL SECTION 114 µ-p econcen a o ab ica ion 115 The µ-p econcen a o de ice is composed o wo pa s: 1) a mic o luidic channel on a Si 116 subs a e and 2) a glass subs a e whe e he adso ben is syn hesized. The mic o luidic channel, 117 2.5cm leng h and 20 µm dep h, on un-doped <100>-o ien ed, polyc ys alline 500 ± 20 µm Si 118 wa e is ab ica ed as p e iously desc ibed.22 Channel dep h has been con i med by p o ilome y. 119 Each 4-inch Si wa e con ains 8 di e en mic ode ices subs a es, which a e diced apa a e he 120 p ocess is inished (see Sec ion 1 o he Suppo ing In o ma ion). 121 The elec ochemical syn hesis o he Cu-BTC was pe o med on he mic opa e ned coppe on 122 he Bo o loa subs a e as elec odes (Sige Wa e , 500 ± 20 µm hickness, su ace oughness < 123 1.2 nm). In pa icula , wo di e en Cu modi ied glass subs a es ha e been in es iga ed (Figu e 124 1) o analyze he in luence o he me al adhesion laye : i) 200 nm o Cu o e an adhesion laye o 125 10 nm C and 50 nm Au deno ed as Cu-C /Au subs a e (0.52 cm2 me allized su ace) and ii) 500 126 nm Cu o e an adhesion laye o 40 nm Ti deno ed as Cu-Ti subs a e (0.69 cm2 me allized 127 su ace). The inished Bo o loa wa e is also diced in 8 di e en subs a es and p ocessed 128 indi idually. 129 7 A e he Cu-BTC MOF syn hesis, he Bo o loa subs a e is bonded o i s Si coun e pa by 130 anodic bonding and luidic po s we e inse ed o connec o ans e lines. Compu e modelling 131 in COMSOL Mul iphysics o he mic o luidic de ice was pe o med in ad ance o ensu e 132 dac cac   adc bd a. T, ca P a  244 ba 133 o 10 STP cm3/min was calcula ed. I is no ewo hy o unde line ha ca i y dep hs a ying om 134 20 µm o 120 µm we e sc u inized by CFD simula ions. In addi ion, p elimina y b eak h ough 135 es s, no shown he e, e ealed he exis ence o an op imal ade-o a 20 m channel dep h 136 which ensu es e icien so ba e-so ben con ac a a o dable p essu e d op alues o he 137 wo king condi ions he ein s udied ( low a e and DMMP concen a ion). 138 139 Figu e 1. Main s eps o he mic ode ice ab ica ion. a) Bo o loa subs a e. b) Cu based 140 deposi ion on Bo o loa subs a es (used as e e ence: Cu  C /Au and Cu  Ti subs a es. c) 141 elec ochemical syn hesis o he Cu-BTC on Bo o loa subs a e. d) anodic bonding wi h Si 142 coun e pa . 143 8 Syn hesis and cha ac e iza ion o Cu-BTC ilms on Bo o loa subs a es 144 The elec osyn hesis o Cu-BTC was ca ied ou as p e iously epo ed (see Sec ion 2 o he 145 Suppo ing In o ma ion).21 Using an Au olab po en ios a PGSTAT302N, cyclic pulses o 146 di e en cu en ( anging om 1 o 15 mA) we e applied be ween he Cu modi ied glass 147 subs a e used as wo king elec ode and he coun e -elec ode. In his wo k, di e en 148 elec osyn hesis pa ame e s we e explo ed (Table 1) in o de o maximize he e ogeneous Cu- 149 BTC c ys alliza ion, su ace co e age and homogenei y. Ve y p elimina y esul s, no shown 150 he e, pe o med wi h he same elec ochemical cell e ealed he exis ence o a minimum cu en 151 densi y alue, i.e. 1.5 mA/cm2, o he e ogeneous syn hesis on Cu-C /Au modi ied glass 152 subs a es. Abo e his cu en densi y, an adequa e concen a ion o Cu2+ ions, as ne mass 153 balance esul ing om he gene a ion e m by Cu elec ode oxida ion and he consump ion e m 154 by Cu-BTC o ma ion, emains in he elec oly e solu ion o he success ul nuclea ion and 155 g ow h on he wo king elec ode. Cu en du y cycle, i.e. on/o swi ching o applied cu en , was 156 kep cons an h ough all o he expe imen s ( cycle = 20 s, du y cycle = 0.75, i.e. on = 15 s, o = 157 5s). 158 Cu-BTC coa ings we e i s ly cha ac e ized by op ical inspec ion suppo ed by he u quoise 159 (wa e coo dina ed s a e) colo ha Cu-BTC exhibi s. SEM-EDX analyses (INSPECT-F50) we e 160 pe o med o de e mine he composi ion and mo phology o he ilms. Pu i y and c ys allini y o 161 he Cu-BTC coa ings we e e alua ed by su ace X- ay di ac ion (B uke D8 Ad ance High 162 Resolu ion Di ac ome e ) and XPS (K a os Axis X- ay spec ome e ). 163 164 Table 1. Elec osyn hesis condi ions s udied in his wo k. 165 Subs a e Sample Isyn hesis Jsyn hesis (mA/cm2) Ncycles 9 (mA) Cu-C /Au #1_12 1.0 1.6 12 #2_12 #2_15 #2_20 9.0 17.3 12 15 20 #3_12 15.0 28.8 12 Cu-Ti #4_15* 6.0 8.7 15 #5_7 #5_15 12.0 17.4 7 15 * Condi ions selec ed o he ab ica ion and es ing o he unc ional mic ode ices s udied in 166 his wo k. 167 Adso p ion p ope ies o Cu-BTC 168 The ex u al p ope ies o Cu-BTC ilms we e assessed om A physiso p ion analysis, ca ied 169 ou on comme cial Cu-BTC in powde o m, Basoli e C300, pu chased om Sigma Ald ich. The 170 as ecei ed bulk ma e ial was also used o quan i y he adso p ion p ope ies owa ds DMMP 171 when exposed o 3748 mg/m3 o DMMP a 293 K (in d y ai and a 30 % RH a 293K). Simila 172 expe imen s we e pe o med on p e iously ac i a ed samples (degassed o e nigh in an o en a 173 423 K and a mosphe ic p essu e) o analyze he in luence o wa e con en on DMMP adso p ion 174 p ope ies. An aliquo o he exposed MOF as well as o he ac i a ed ma e ial we e aken and 175 analyzed by he mog a ime y on a TA Ins umen s TGA-Q5000 (using N2 up o 873 K a 10 176 K/min as hea ing a e). Quan i ica ion was pe o med using CuO as basis o calcula ion. 177 Theo e ical adso p ion iso he ms ha e been calcula ed by combina ion o Mon e Ca lo (MC) 178 simula ions, in pa icula , by using he Me opolisHas ings algo i hm and molecula dynamics 179 calcula ions based on UFF23 as a o ce ield. 180 16 gi es ise o he su ace Cu2+/Cu+/0 M a io o 1.017. Simila ly, he Cu 2p1/2 peak is de- 286 con olu ed in wo componen s a 952.7 and 954.5 eV. 287 In addi ion, he e a e h ee shake up sa elli e peaks, which a e ypical Cu2+ in cup ic 288 compounds. These sa elli e peaks, on he high binding ene gy side o he co e le el Cu 2p XPS 289 da a a 939.8, 944.1 and 963.1 eV, o igina e om mul iple exci a ions in coppe oxides and hey 290 a e known o be cha ac e is ics o CuO phase.33 The e o e, he p esence o he in ense shake-up 291 sa elli e s uc u es obse ed in he Cu 2p XPS spec a o D3 sample, accoun ing o ci ca 35% o 292 o al coppe con en on he su ace, was an indica ion o he simul aneous o ma ion o Cu-BTC 293 and CuO phases, aon he su ace o he elec osyn hesized ilms. 294 The s a ing Cu/Ti elec ode was also examined. Peaks a 932.8 eV (Cu 2p3/2) and 952 eV (Cu 295 2p1/2) and he absence o sa elli es shake-up lines cha ac e is ic o Cu2+ gi e clea e idence ha 296 Cu is p esen in he+1 oxida ion s a e, in ag eemen wi h he XRD spec a show in Figu e 4.c. 297 17 298 Figu e 4. Elec ochemical syn hesis o Cu-BTC on Cu-Ti subs a es: sample #4 (Jsyn hesis = 8.6 299 mA/cm2, Ncycles =15). a) Op ical image, below SEM mic og aph o a ep esen a i e a ea o he 300 coa ing. b) SEM-EDS esul s on he clamping egion highligh ed in a), showing he o e lapping 301 o Cu (g een) and C (whi e) signals. c) XRDs o he Cu-BTC ilm (blue), p is ine Cu-Ti subs a e 302 ( ed) and comme cial Cu-BTC powde (black). C ys allog aphic pa e ns om.14 d) Co e le el 303 Cu2p XPS spec a o he Cu-BTC ilm (blue) and p is ine Cu-Ti subs a e ( ed). 304 18 Figu e 5 shows he ch onopo en iome ic measu emen s wi h ime on s eam. This analysis is 305 e ealed as a eliable cha ac e iza ion ool o he assessmen on he he e ogeneous Cu-BTC 306 c ys alliza ion p ocess. A smoo h inc ease o he elec ic po en ial di e ence ac oss he wo king 307 and coun e elec odes would be expec ed wi h elec o syn hesis ime and numbe o cycles. 308 A ca  c ad  c-cd ,   c 309 would be explained by he e ol ing wo king elec ode, which becomes mo e insula o wi h 310 syn hesis ime due o he lesse conduc i i y o Cu-BTC ilms (Cu-BTC < 3 x 10-9 S/m s. Cu = 311 5.96 x 107 S/m).34 O e lapped ol age signals a e egis e ed o #4_15 (1) and #4_15 (2) 312 samples, espec i ely; bo h p epa ed unde iden ical condi ions (Jsyn hesis = 8.6 mA/cm2, Ncycles = 313 15). Mo e speci ically, he applied o e po en ial sligh ly inc eases om 4.1 V o he 1s cycle o 314 4.7 V in he 15 h cycle in ag eemen wi h he con olled o ma ion o homogeneous Cu-BTC 315 ilms. Acco dingly, hese condi ions ha e been selec ed o he ab ica ion o he unc ional 316 mic ode ices o sampling and p econcen a ion o ne e agen s (NAs) dilu ed in gaseous 317 s eams. 318 319 19 Figu e 5. Ch onopo en iome ic analyses along he Cu-BTC elec osyn hesis o e Cu-Ti 320 subs a es: #4_15 (1) in blue, #4_15 (2) in yellow, #5_7 (1) in pu ple, #5_7 (2) in ed, #5_15(1) 321 in g een and #5_15(2) in o ange. 322 On he con a y, on samples #5_7 and #5_15, bo h a Jsyn hesis = 17.4 mA/cm2; he o e po en ial 323 e olu ion a e wi h ime on s eam is subs an ially highe om he 4 h cycle and pa icula ly 324 no iceable on 9 h cycle. We a ibu e his obse a ion o he de achmen o he Cu-BTC laye 325 om he wo king elec ode due o he exhaus o he Cu laye and he educ ion o he 326 elec oac i e su ace a ea. 327 Wa e and DMMP adso p ion p ope ies o Cu-BTC powde 328 Figu e 6.a shows he cha ac e is ic Type I A iso he m a 87.3 K o comme cial Cu-BTC. The 329 BET su ace a ea is 1812 m2/g (co ela ion coe icien o 0.9999). Mic opo e size dis ibu ion 330 has been modeled using nonlocal densi y unc ional heo y (NLDFT) and conside ing cylinde 331 shape po e. The po e ne wo k o Cu-BTC has a simple cubic symme y. I consis s on a 3 332 dimensional channel sys em wi h main po es o ca. 9 Å and e ahed al side pocke s o ca. 5 Å.35 333 Such po e size dis ibu ion is illus a ed in Figu e 6.b wi h a o al po e olume o 0.81 cm3/g. 334 Cu-BTC is ex emely sensi i e o wa e con en due o he e y s ong in e ac ion be ween 335 open Cu(II) si es and wa e molecules.27 TGA o he as ecei ed Cu-BTC is shown in Figu e 6.c. 336 The i s weigh -loss up o 373 K accoun s o 1216 mg/gCuO and i is mainly associa ed wi h 337 wa e con en due o he ela i ely hyd ophilic la ge po es. On he con a y, he wa e con en o 338 ac i a ed samples is no ably educed, i.e. 150-175 mg/gCuO (Table 2). This obse a ion highligh s 339 he impo ance o he he mal ac i a ion o emp y he amewo k e icien ly.36 The sample does 340 no show any signi icance weigh change up o ci ca 523 K, onse empe a u e o he o ganic 341 linke deg ada ion. 342 20 343 Figu e 6. Tex u al cha ac e iza ion and TGA o comme cial Cu-BTC (Basoli e C300) a) A 344 adso p ion iso he m (blue) and NLDFT model i ed cu e ( ed). Inse : de ail o low-p essu e 345 egion (0.0 < P/P0 < 0.1) o A adso p ion iso he m (blue) and NLDFT i ed cu e in 346 loga i hmic scale. b) Po e olume dis ibu ion (blue) and cumula i e po e olume ( ed) 347 acco ding o NLDFT model assuming cylinde shape po e. (c) TGA (con inuous line) and DTA 348 (discon inuous line) o as ecei ed sample. d) The mal s abili y o as ecei ed sample a 523 K in 349 N2 a mosphe e o 36 h. Inse : de ail o he i s 5 h exposu e ime. 350 An aliquo o as ecei ed Cu-BTC sample was exposed o he ab ica ion p ocess condi ions o 351 assess he amewo k he mal s abili y du ing he anodic bonding, i.e. 523 K o 36 h (see Figu e 352 21 6.d). A simila wa e weigh loss is egis e ed du ing he i s hea ing amp up o 523 K. Du ing 353 he nex 5 h a 523 K, no app eciable weigh loss is eco ded. A e wa ds, he slope inc eases 354 g adually wi h ime on s eam. A e 36 h exposu e a 523 K, he weigh loss due o he pa ial 355 deg ada ion o he o ganic linke accoun s o 11 %. Acco dingly, he anodic bonding condi ions, 356 523 K @ 1 kV, we e kep o 5 h o p ese e he Cu-BTC amewo k. 357 Table 2. DMMP adso p ion on Cu-BTC a 293 K es ima ed by TGA 358 Ac i a ed Cu-BTC As ecei ed Cu-BTC ∆m < 373 K (mg/gCuO) ∆m > 373 K (mg/gCuO) ∆m < 373 K (mg/gCuO) ∆m > 373 K (mg/gCuO) Con ol* 150  1216  DMMP (3748 mg/m3) 175 771   DMMP + Wa e (3748 mg/m3 + 7362 mg/m3) 238 297 323 267 *analyses on aw samples, wi hou being exposed o DMMP o DMMP + wa e a mosphe es 359 360 Table 2 compa a i ely shows he wa e and DMMP up ake alues o ac i a ed Cu-BTC 361 samples o single DMMP (DMMP@3748 mg/m3) and bina y DMMP + wa e mix u e 362 (DMMP@3748 mg/m3 + wa e @7362 mg/m3) in N2, espec i ely. The i s weigh -loss up o 363 373 K is a ibu ed o wa e deso p ion, whe eas hose shown a empe a u es abo e 373 K a e 364 due o DMMP elease. Acco ding o abula ed da a, DMMP up ake is shown o be dependen on 365 he wa e con en o he gas s eam wi h a maximum DMMP so p ion capaci y o 771 mg/gCuO a 366 d y condi ions. Fo single DMMP adso p ion on ac i a ed samples, he di e en ial he mog am 367 e eals he exis ence o h ee di e en so p ion si es wi h di e en in e ac ion ene gies (Figu e 368 22 7.a). I is also ound ha mos o he weigh loss o DMMP d cc a 433 K, DMMP 369 = 473.0 mg/gCuO, s. 112 mg/gCuO @ 500 K and 186 mg/gCuO @ 543 K. Fo he bina y mix u e 370 (Figu e 7.b), he DMMP up ake o ac i a ed sample is no ably educed o less han hal , i.e. 297 371 mg/gCuO; and he iple peak ha was seen be o e, no longe appea s. This alue is only sligh ly 372 supe io o he quan i ied o co-adso bed wa e apo , i.e. 238 mg/gCuO. 373 374 Figu e 7. a) DTA o ac i a ed Cu-BTC be o e (black) and a e exposu e o 3748 mg/m3 DMMP 375 in d y condi ions (blue). Slashed blue lines depic de-con olu ed peaks o exposed Cu-BTC. b) 376 DTA o ac i a ed Cu-BTC ( ed) and as ecei ed Cu-BTC (g een) a e co-exposu e o DMMP 377 (3748 mg/m3) and wa e (7362 mg/m3). Slashed ed and g een lines depic de-con olu ed peaks 378 o ac i a ed Cu-BTC ( ed) and as ecei ed Cu-BTC (g een). 379 I a cd C-BTC, he s a ing amoun o p e-adso bed wa e apo s (1216 mg/gCuO) 380 has almos no in luence on he inal DMMP up ake in compa ison wi h he ac i a ed sample: 267 381 mg/gCuO e sus 297 mg/gCuO. In bo h samples, a b oad peak cen e ed a 473 K associa ed o 382 DMMP deso p ion is obse ed in he di e en ial he mog ams. In o he wo ds, he binding 383 ene gy o DMMP- uncoo dina ed Cu(II) si es is lowe in p esence o co-adso bed wa e apo . 384 23 We a ibu e his e ec o he o ma ion o a DMMP-complex on he Cu(II) paddlewheels, whe e 385 he s ong in e ac ion o non-b idging phospho yl oxygen a om in DMNP wi h uncoo dina ed 386 Cu(II) si es is a enua ed due o p oximi y o wa e Cu(II) coo dina ed si es. Thus, he o ma ion 387 o weake hyd ogen bonds be ween he hyd oxyl g oups p esen on he wa e Cu(II) coo dina ed 388 si es C and he P=O unc ion o DMMP is so ening he ene gy ba ie o DMMP deso p ion. In 389 addi ion, he acili a ed di usion o deso bed DMMP molecules om he hyd a ed po es o Cu- 390 BTC is posi i ely con ibu ing due o he hyd ophilic cha ac e o he su oga e. 37 391 Mo eo e , wa e adso p ion o as ecei ed Cu-BTC sample is educed o almos a qua e in 392 p esence o DMMP, i.e. 1216 mg/gCuO in non-compe i i e wa e adso p ion scena io s. 323 393 mg/gCuO o he bina y mix u e. Thus, he p esence o DMMP in a compe i i e so p ion scena io 394 is able o dehyd a e he Cu-BTC sample and o alloca e on ac i e si es p e iously occupied by 395 wa e molecules. 396 The ole o wa e inclusion in he physicochemical in e ac ions o DMMP so p ion wi hin he 397 po ous s uc u e o Cu-BTC has been compu a ionally s udied o co obo a e ou hypo hesis. 398 Low ene gy adso p ion on su ace si es o DMMP and wa e molecules on pe iodic Cu-BTC slab 399 buil on di e en c ys al o ien a ions ha e been iden i ied h ough Mon e Ca lo (MC) 400 simula ions. In o de o ind minimal ene gy o he sys em, he empe a u e was modi ied 401 ex e nally o simula e he annealing o he sys em om 100 K o 105 K o 20 cycles wi h 20000 402 o s eps pe cycle. The molecula in e ac ions ha e been simula ed by using UFF o ce ield and 403 Ewald me hod as summa ion me hod. A simila s udy was pe o med on coppe /coppe oxides o 404 quan i y he e ec o he elec ode and c ys alline impu i ies. 405 Figu e 8 shows he adso p ion ene gies o DMMP in absence o co-adso bed wa e apo . 406 C ys al o ien a ion o he simula ed Cu-BTC slab plays an impo an ole in DMMP su ace 407 24 adso p ion. Mo phologies o he s uc u es a e also in es iga ed (see Sec ion 5 o Suppo ing 408 In o ma ion). The (110), (101), (011) and (111) o ien a ions o Cu-BTC slabs show simila 409 appea ance: o al-shape holes (13.2 Å x 18.6 Å). The (010) and (001) o ien a ions p esen a 410 c oss-shape ench o 6.5 Å, and he in e sec ion o hese enches p o ides holes o 16.2 Å in 411 diame e . The (110), (101), (011) and p e e en ial (111) c ys allog aphic planes exhibi simila 412 adso p ion ene gies, ca. -55 kcal/mol. On he con a y, he (010) and (001) o ien a ions possess 413 wo ene gy dis ibu ion p obabili ies cen e ed a -51 kcal/mol and -73 kcal/mol, espec i ely. 414 Addi ionally, he a e age o adso p ion ene gy o DMMP molecules adso bed inside he Cu- 415 BTC mic opo es is lowe han -30 kcal/mol. Such di e ences in he binding ene gies a e 416 suppo ing he di e en ial DMMP deso p ion p o ile shown in Figu e 7.a. Thus, he b oad peak 417 cen e ed a 433 K would be a ibu ed o he elease o DMMP molecules om he Cu-BTC 418 mic opo es. The elease o DMMP adso bed on he su ace seems o occu a highe empe a u e 419 due o s eng h o he in e ac ions. The dis ibu ion o DMMP molecules on he a ailable 420 so p ion si es would explain he h ee deso p ion bands obse ed in he di e en ial he mog ams. 421 25 422 Figu e 8. Mon eca lo simula ions o DMMP in e ac ions o e Cu-BTC and Cu2O/CuO su aces 423 wi hou and wi h co-adso bed wa e apo molecules. 424 Simila ly, Figu e 8 illus a es how he p esence o co-adso bed wa e apo shi s he DMMP 425 ene gy dis ibu ion p obabili y o lowe and mo e dispe sed alues. These simula ions sugges 426 ha DMMP in e ac ions wi h Cu-BTC su ace become weake in p esence o co-adso bed wa e 427 apo , suppo ing ou hypo hesis on he hyd ogen bonding ype in e ac ions be ween he 428 phospho yl oxygen a om in DMMP and he hyd oxyl g oups p esen on he wa e Cu(II) 429 coo dina ed si es. 430 -80 -60 -40 -20 0.0 0.2 0.4 0.6 0.8 1.0 HKUST (101)=(110)=(011)+H2O HKUST (111)+H2O HKUST (010) = (001) + H2O HKUST (101)=(110)=(011) HKUST (111) HKUST (010)=(001) P(E) Eads (kcal/mol) Cu2O (111) CuO (111) 32 *Email: mapina@uniza .es (M.P.P.) 548 ORCID 549 Fe nando Almazan: 0000-0001-5063-2987 550 Miguel A. U biz ondo: 0000-0002-4931-1358 551 Pablo Se a-C espo: 0000-0002-5106-0527 552 Bea iz Seoane: 0000-0002-9100-4773 553 Jo ge Gascon: 0000-0001-7558-7123 554 Jesus San ama ia: 0000-0002-8701-9745 555 M. Pila Pina: 0000-0001-9897-6527 556 Au ho Con ibu ions 557 The manusc ip was w i en h ough con ibu ions o all au ho s. All au ho s ha e gi en app o al 558 o he inal e sion o he manusc ip . 559 Funding Sou ces 560 Au ho s a e g a e ul o inancial suppo om MICINN ia CTQ2013-49068-C2-1-R 561 (AEI/FEDER, UE) and CTQ2016-79419-R (AEI/FEDER, UE) g an s; H2020 Ma ie 562 Sda-Cu ie Ac ions (g an MSCA-RISE-GA 823895) and Gobie no de A agon (T57- 563 17R). 564 No es 565 The au ho s decla e no compe ing inancial in e es s. 566 33 ACKNOWLEDGEMENTS 567 Au ho s a e g a e ul o inancial suppo MICINN (CTQ2013-49068-C2-1-R AEI/FEDER, 568 UE, CTQ2016-79419-R AEI/FEDER, UE), H2020 (MSCA-RISE-GA 823895) and Gobie no de 569 A agón (T57-17R). 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A.; Mallada, R.; Pina, M. P.; 718 San ama ía, J. Highly Sensi i e SERS Quan i ica ion o O ganophospho ous Chemical 719 Wa a e Agen s: A Majo S ep owa ds he Real Time Sensing in he Gas Phase. Senso s 720 Ac ua o s B Chem. 2018, 267, 457466. 721 h ps://doi.o g/h ps://doi.o g/10.1016/j.snb.2018.04.058. 722 (44) La uen e, M.; Almazan, F.; Be nad, E.; U biz ondo, M. A.; San ama ia, J.; Mallada, R.; 723 Pina, M. P. SERS De ec ion o Neu o oxic Agen s in Gas Phase Using Mic o luidic Chips 724 Con aining Gold-Mesopo ous Silica as Plasmonic-So ben . In 2019 20 h In e na ional 725 Con e ence on Solid-S a e Senso s, Ac ua o s and Mic osys ems and Eu osenso s XXXIII, 726 TRANSDUCERS 2019 and EUROSENSORS XXXIII; 2019. 727 h ps://doi.o g/10.1109/TRANSDUCERS.2019.8808289. 728 729 730 731 732 733 734 735 41 Fo Table o Con en s Only 736 737 7 Sec ion 3. B eak h ough Tes ing o unc ional mic op econcen a o s So p ion dynamics o he unc ional µ-p econcen a o s we e e alua ed by analysis o he moni o ed b eak h ough cu e. A ypical b eak h ough cu e, as depic ed on Figu e S6, ollows he e olu ion in ime o olume (o ci cula ed gas) o he elu ed analy e concen a ion downs eam o he so p ion uni . Mos ly, he elu ed concen a ion Cx is no malized by he eeding concen a ion C0, so i anges om 0 o 1. Fo his wo k, b eak h ough poin is conside ed as he momen whe e Cx/C0 = 0.05, which implies ha he adso ben is becoming sa u a ed and begins o be unable o ap all he analy e molecules ca ied by he eeding gas. The momen a which b eak h ough akes place is deno ed as b eak h ough ime ( b). Simila ly, he olume ha has been ed o he bed is de ined as b eak h ough olume (Vb = b * Q eed, being Q eed: eed olume ic low). The a io o up ake so ba e ( a ge analy e) mass up o b eak h ough poin (mb) o he so ben mass is de ined as dynamic so p ion capaci y (Wd). Analogously, he poin whe e he adso ben is exhaus ed is deno ed as sa u a ion poin ; and in his wo k is assumed i akes places when Cx/C0 = 0.95, his poin de e mines he equilib ium so p ion capaci y when wo king in dynamic condi ions (We). The Figu e S6. Typical b eak h ough cu e whe e he no malized concen a ion is plo ed as a unc ion o he olume ha has been ci cula ed inside he so p ion uni . 0.05 8 maximum mass o so ba e can be calcula ed by in eg a ed he a ea abo e o he b eak h ough cu e (up o Cx/C0 = 0.95). A con en ional b eak h ough es comp ises he ollowing s eps (see Figu e S7) depic s he schema ics o he se up ins alled a he Uni e si y o Za agoza): 1. Adso ben p e- ea men : be o e he adso p ion expe imen , he adso ben is egene a ed he mally by placing he mic ode ice on a ho pla e a 200 ºC while ine N2 sweeps he ca i y and degas he so p i e laye . Ideally his s ep is pe o med un il no undesi able specie was de ec ed. 2. Analy e baseline: analy e was ed di ec ly in o he de ec o o ob ain he baseline signal ha is used o calib a ion. To a oid con amina ion on he adso ben ma e ial, d y N2 is ci cula ed h ough he mic ode ice while his s ep akes place. a) b) c) d) Figu e S7. Scheme o low a angemen in he expe imen al se -up o b eak h ough es ing: a) adso ben p e- ea men , b) analy e baseline, c) analy e adso p ion and d) analy e deso p ion. 9 3. Analy e adso p ion: analy e is ed o he mic ode ice un il so ben sa u a ion, which is assessed by p e ious calib a ion (Cexi = C0). 4. Analy e deso p ion: he analy e was deso bed unde he same condi ions as s ep 1. 10 Sec ion 4. Expe imen al Se -up o P econcen a ion Fac o De e mina ion P econcen a ion expe imen s we e pe o med wi h a mosphe es o 2.65 mg/m3 (520 ppbV) o DMMP in d y N2. Al hough his concen a ion is 8- old highe han epo ed le hal alue o sa in gas o exposu e imes up o 10 min (AEGL-3 = 0.38 mg/m3, 64 ppbV), i is ai ly easonable alue o accu a ely cha ac e ize he µ-de ice pe o mance a a ep oducible concen a ion wi hou he need o use addi ionally dilu ion s eams. The syn he ic DMMP/N2 mix u e was gene a ed by ci cula ing 10 STP cm3/min o d y N2 h ough a calib a ed pe mea ion ube o DMMP (VALCO, pe mea ion a e o 148.41 ng/min ± 3.07 a 90 ºC) and ed o he µ-de ice. The moni o ing o he deso p ion peak was pe o med wi h a gas ch oma og aph coupled wi h a mass spec ome y de ec o (GCMS, Shimadzu GCMS QP2010) downs eam he µ-de ice. The cha ac e is ic DMMP mass signals we e ollowed (m/z = 79, 94, 109, 124) as well as he p incipal uma signals o he main decomposi ion p oduc s: me hanol (m/z = 31), dime hyl e he (m/z = 45), CO2 (m/z = 44) and o maldehyde (m/z = 29). The µ-de ice is connec ed o he GCMS 6-po al e h ough capilla y ubing (320 µm inne diame e ) hough high empe a u e sep um glued o he Bo o loa side o he de ice. In o de o a oid adso p ion o he DMMP in he aces o he sep a, an in e media e laye o Kap on has been placed be ween he Bo o loa side and he sep um. This app oach elies on he apid he mal deso p ion o DMMP and he adequa e ca ie low a e o push ou he bolus in a plug- low ashion, wi hou he need o a ocusing s age. Thus, he expe imen al p o ocol is educed o he sampling o DMMP a oom empe a u e and 10 cm3/min o ce ain ime, he lushing ou o he DMMP molecules in gas phase wi h GCMS ca ie o 5 min, a e which, he adso ben is apidly hea ed a 523 K, eleasing he DMMP and being pushed ou o he de ec o by he GCMS ca ie (see Figu e S8). 11 The p econcen a ion pe o mance o he µ-de ice as sampling uni is e alua ed om i s p econcen a ion coe icien , deno ed as K. Acco ding o IUPAC guidelines, his alue is de ined as he a io o he gas sample collec ed olume o he olume in which ha same mass is eleased acco ding o he quan i ica ion a he poin o de ec ion, assuming no ans e mass losses ake place. Acco dingly, he K es ima ion is ca ied ou unde expe imen al condi ions ha gua an ee he absence o a ge molecules in he ou le s eam, i.e. no b eak h ough condi ions. Thus, gi en a deso p ion peak (see Figu e S9), he p econcen a ion coe icien K is calcula ed as ollows: whe e Qsampling is he eeding low a e, sampling is he sampling ime, Qdeso p ion is he low a e a which he eleased sample is being lushing ou and FWHM is he ull wid h a hal maximum o he deso p ion peak egis e ed by he de ec o . a) b) Figu e S8. Dynamic p econcen a ion se -up. a) sampling o he DMMP/N2 mix u e. b) The mal deso p ion and concen a ion o he DMMP adso bed. Be ween a) and b) akes place a lushing s age (no depic ed in he igu e). G een line depic s DMMP/N2 low pa h whe eas o ange line depic s He low pa h. K  𝑉  𝑉  𝑄 ∗ 𝑡 𝑄 ∗ 𝐹𝑊𝐻𝑀 12 Figu e S9. G aphical ep esen a ion o a ypical deso p ion peak. On he g aph a e shown he mos impo an desc ip i e pa ame e s: peak heigh Imax, ull wid h a hal maximum (FWHM) and he asyme ic ac o AS. 13 Sec ion 5. Mo phologies o he s uc u es used o Mon eca lo Simula ions Figu e S10. A omis ic ep esen a ion o Cu2O and Cu-BTC (HKUST) acuum slabs wi h di e en su ace o ien a ions. 14 Figu e S11. A omis ic ep esen a ion o he ene gy minimized s uc u es o adso p ion o DMMP molecules o e Cu- BTC (HKUST) acuum slabs a di e en c ys al o ien a ions. 15 Figu e S12. Adso p ion Si es o wa e (g een colo ) and DMMP ( ed colo ) molecules on o Cu-BTC s uc u e. 16 Sec ion 6. Du abili y and S abili y o Cu-BTC unc ional mic ode ices The du abili y and s abili y o he Cu-BTC unc ionalized µ-de ices we e con i med by assessmen o he so p ion p ope ies upon exposu e o se e al so p ion-deso p ion cycles o DMMP. The b eak h ough cu es ob ained wi h a #4_15 ype unc ional de ice, along 1 mon h es ing and being unin e up edly exposed o ambien ai , a e shown below. The da a analyses e eal an a e age alue o 67.6 ± 1.5 mg/g and 664.4 ± 47.0 mg/g o dynamic and equilib ium adso p ion capaci ies, espec i ely. These esul s con i m he s abili y o he Cu-BTC so p ion capaci y, and he eusabili y o he unc ional mic ode ices. Figu e S13. Pe o mance o unc ional Cu-BTC µ-p econcen a o exposed o sequen ial adso p ion-deso p ion cycle. Run 1 co esponds o he i s b eak h ough cu e. Run 2 shows he b eak h ough cu e a e 1 mon h es ing, i.e. abo e 20 so p ion/deso p ion cycles. Expe imen al condi ions: Adso p ion 162 mg/m3 (32 ppmV) o DMMP 10 STP cm3 /min d y N2; Deso p ion 12 h a 473 K 10 STP cm3 /min d y N2.