1
Cu-BTC unc ional mic ode ices as sma ools o
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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,
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7 M.P. Pina1, 6, 7
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1 Nanoscience Ins i u e o A agon (INA), Uni . Za agoza, Depa men o Chemical &
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En i onmen al Enginee ing, Campus Rio Eb o, C/Ma iano Esquillo s/n, 50018 Za agoza, Spain
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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
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3 Applied Radia ion and Iso opes, Depa men o Radia ion Science and Technology, Facul y o
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Applied Sciences, Technical Uni e si y Del , Mekelweg 15, 2629 JB, Del , he Ne he lands
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4 Ca alysis Enginee ing, Depa men o Chemical Enginee ing, Del Uni e si y o Technology,
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Van de Maasweg 9, 2629 HZ Del , The Ne he lands
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5 Ad anced Ca aly ic Ma e ials, KAUST Ca alysis Cen e , King Abdullah Uni e si y o Science
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and Technology, Thuwal 23955, Saudi A abia
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6 Ne wo king Resea ch Cen e on Bioenginee ing, Bioma e ials and Nanomedicine, CIBER-
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BBN, 28029 Mad id, Spain
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7 Uni Za agoza, CSIC, Ins i u o de Ciencia de Ma e iales de A agón (ICMA), C/Ped o Ce buna
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12, 50009 Za agoza, Spain
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2
KEYWORDS: mic o ab ica ion, coppe modi ied glass subs a es, h eshold cu en densi y,
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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
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ABSTRACT: Cu-based Me al O ganic F amewo ks (MOF) mic ode ices a e applied in
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sampling and p econcen a ion o ne e agen s (NAs) dilu ed in gaseous s eams. An in-si u
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elec ochemical assis ed syn hesis o Cu-BTC hick ilm is ca ied ou o unc ionalize a Cu
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modi ied glass subs a e. This simple, apid, ep oducible and easy o in eg a e MOF syn hesis
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app oach, enables he mic o ab ica ion o unc ional mic op enconcen a o s wi h la ge BET
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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
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adso p ion o ne e agen molecules along he mic o luidic channel 2.5 cm in leng h. Equilib ium
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adso p ion capaci y o he bulk ma e ial has been cha ac e ized h ough he mog a ime ic
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analysis a e exposu e o con olled a mosphe es o a sa in gas su oga e, dime hyl
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me hylphosphona e (DMMP), in bo h d y and humid condi ions (30% RH a 293 K).
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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
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mg/g. The p econcen a ion pe o mance o such µ-de ices when dealing wi h highly dilu ed
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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
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up o 171 o sample olume up o 600 STP cm3. We demons a e he po en iali ies o Cu-BTC
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mic op econcen a o s as sma i s esponde ools o  d de ec ion o ne e agen s in
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gas phase a ele an condi ions.
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3
INTRODUCTION
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Vulne abili y o c i ical indoo in as uc u es o in en ional ne e agen s elease poses a
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signi ican poin o conce n o au ho i ies esponsible o inciden p epa edness and p e en ion.
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Such chemical compounds a e odo less, colo less, highly pe sis en , ola ile and le hal e en a
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low concen a ion.1 Pa icula ly, he o ganophosphona es-based ne e agen s (NAs), whe e he
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well-known sa in and soman gases belong o, ha e been used agains ci ilian popula ion in
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shocking e o is a acks. In amously known a e he e o is a ack in he subway o Tokyo in
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1991 and he ecen ones agains ci ilians in Sy ia.2 A ew s udies a e a ailable o sa in apo
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exposu es on human olun ee s in o de o di ec ly de i e acu e exposu e guideline le els.
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Resul s indica e ha he h eshold o miosis and o he minimal oxic e ec s alls in he ange o
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0.05  0.5 mg/m3 (9  87 ppbV) o 30 - 10 min exposu es, espec i ely.3
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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
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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
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common solu ion is o implemen a apping-p econcen a ion uni ups eam he de ec o . This
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app oach has been success ully applied in many ields whe e he iden i ica ion o compounds a
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e y low concen a ion (sub ppmV) is equi ed; such as wo kplace heal h and sa e y4 o o non-
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in asi e, diagnos ic ools based on he de ec ion o exhaled ola ile bioma ke s5. En ichmen
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ac o s up o 300 ha e been epo ed o a oma ic VOCs using ca bon nano ubes-based µ-
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p econcen a o s o 100 ppbV eed concen a ion and sample olume up o 400 STP cm3.6
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MOFs a e hyb id ma e ials composed o coo dina i ely linked me al ions o clus e s ia
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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
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mic opo ous zeoli es o mesopo ous silica, MOFs exhibi highe chemical e sa ili y.
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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-
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dime hylpy azola e, exhibi s an adso p ion capaci y up o 950 mg DMMP/g IRMOF-1 o
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sa u a ed a mosphe e o dime hyl me hylphosphona e (DMMP) a 50 ºC 7; as well as mild
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adso p ion hea alues (-Had = 44.8 J/  da (DIFP) a
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empe a u es anging om 383 o 513 K 8). Newly de eloped Z -based MOFs, such as NU-1000,
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UiO-66 o MOF-808, ha e a ac ed in e es in NAs decon amina ion no only due o hei
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so p ion p ope ies (713 mgDMMP/gNU-1000 and 152 mgDMMP/gUiO-66 o 507 mg/m3
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DMMP a 298K 9) bu also due o hei ca aly ic p ope ies owa ds o ganophospho us
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deg ada ion by hyd olysis.10
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Cu-based MOFs, such as Cu-BTC (HKUST-1), ha e also been widely epo ed as adequa e
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adso ben s o o ganophospho ous apo s due he high a ini y ha hose compounds exhibi
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owa ds Cu clus e s and he s abili y o he esul ing me al complexes. Fou ie - ans o ma ion
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in a ed (FTIR) spec oscopy analysis on su ace acous ic wa e ype senso s unc ionalized ia
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sel -assembled monolaye wi h (CO2)2Cu as e minal g oup and exposed o diisop opyl
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me hylphosphona e (DIMP) in gas phase e eal he o ma ion o CuDIMP complexes (P=O-
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Cu). 11 The a ini y o o ganophospho ous compounds o coppe ions s ill p e ails in HKUST-1
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as demons a ed by he expe imen ally measu ed adso p ion hea alue o
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diisop opyl luo ophospha e (DIFP), -Hads = 48.4 kJ/mol, which is highe han ha obse ed o
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comme cial Ca boxen, -Hads = 38.3 kJ/mol.12 Finally, heo e ical compu a ional models13 using
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densi y unc ional heo y (DFT) poin ou ha he mos a o able MOFs, among he 1544 MOFs
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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
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canno accommoda e Sa in molecules and on la ge po es he molecula in e ac ions wi h he
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amewo k become weake . Acco dingly, Cu-BTC eme ges as po en ial adso ben o
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5
o ganophosphona es compounds hanks o i s po e size dis ibu ion14 and he chemical a ini y o
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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
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explo ed o cap u e and p econcen a e DMMP, a Sa in su oga e, om highly dilu ed gas
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s eams.
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The syn hesis o MOF ilms has been pa icula ly o in e es in he ield o chemical senso s15
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and gas memb anes o selec i e sepa a ions16. No el app oaches such as mic o luidic pen
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li hog aphy17 o inkje p in ing echnology a e gaining impo ance due o hei po en ial o la ge
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scale manu ac u ing o unc ional mic ode ices. Recen ly, UiO-66 has been syn hesized in si u
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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
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applied o DMMP sensing wi h heo e ical limi o de ec ion down o 0.025 mg/m3 (5 ppbV).18
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In his wo k, in si u elec ochemical g ow h o Cu-BTC, a well-known MOF ma e ial ha has
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been ex ensi ely in es iga ed bo h expe imen ally and heo e ically, on a glass modi ied
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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
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he po en iali ies o cap u e and p econcen a ion applica ions. The mic opa e ned Cu elec ode
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is exposed o he elec oly e solu ion and used as me al sou ce o he in si u elec ochemical
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syn hesis o Cu-BTC ilms ollowing a simila app oach o ou p e ious publica ions21. The wo k
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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
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numbe o elec osyn hesis cycles on he he e ogeneous MOF c ys alliza ion a e, c ys al
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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
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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
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de ined o he ab ica ion o unc ional mic ode ices based on Cu-BTC ilms. The second pa
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is ocused on he adso p ion pe o mance o he unc ional µ-p econcen a o s owa ds DMMP.
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Equilib ium up ake alues, dynamic adso p ion p ope ies om b eak h ough es s a ppmV le el
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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,
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he molecula in e ac ions o DMMP wi h Cu-BTC and Cu/Cu2O su aces in d y and humid
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condi ions a e compu a ionally s udied o gain insigh in o he expe imen al esul s. Thus, his
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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
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he bes o ou knowledge, con inuous Cu-BTC ilms and Si based mic o luidic de ices a e
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combined o he i s ime o be employed e icien ly in sampling and p econcen a ion
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applica ions o oxic compounds.
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EXPERIMENTAL SECTION
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µ-p econcen a o ab ica ion
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The µ-p econcen a o de ice is composed o wo pa s: 1) a mic o luidic channel on a Si
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subs a e and 2) a glass subs a e whe e he adso ben is syn hesized. The mic o luidic channel,
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2.5cm leng h and 20 µm dep h, on un-doped <100>-o ien ed, polyc ys alline 500 ± 20 µm Si
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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.
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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
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p ocess is inished (see Sec ion 1 o he Suppo ing In o ma ion).
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The elec ochemical syn hesis o he Cu-BTC was pe o med on he mic opa e ned coppe on
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he Bo o loa subs a e as elec odes (Sige Wa e , 500 ± 20 µm hickness, su ace oughness <
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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
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1) o analyze he in luence o he me al adhesion laye : i) 200 nm o Cu o e an adhesion laye o
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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
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nm Cu o e an adhesion laye o 40 nm Ti deno ed as Cu-Ti subs a e (0.69 cm2 me allized
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su ace). The inished Bo o loa wa e is also diced in 8 di e en subs a es and p ocessed
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indi idually.
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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
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anodic bonding and luidic po s we e inse ed o connec o ans e lines. Compu e modelling
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in COMSOL Mul iphysics o he mic o luidic de ice was pe o med in ad ance o ensu e
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dac cac   adc bd a. T, ca P a  244 ba
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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
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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
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which ensu es e icien so ba e-so ben con ac a a o dable p essu e d op alues o he
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wo king condi ions he ein s udied ( low a e and DMMP concen a ion).
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Figu e 1. Main s eps o he mic ode ice ab ica ion. a) Bo o loa subs a e. b) Cu based
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deposi ion on Bo o loa subs a es (used as e e ence: Cu  C /Au and Cu  Ti subs a es. c)
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elec ochemical syn hesis o he Cu-BTC on Bo o loa subs a e. d) anodic bonding wi h Si
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coun e pa .
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Syn hesis and cha ac e iza ion o Cu-BTC ilms on Bo o loa subs a es
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The elec osyn hesis o Cu-BTC was ca ied ou as p e iously epo ed (see Sec ion 2 o he
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Suppo ing In o ma ion).21 Using an Au olab po en ios a PGSTAT302N, cyclic pulses o
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di e en cu en ( anging om 1 o 15 mA) we e applied be ween he Cu modi ied glass
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subs a e used as wo king elec ode and he coun e -elec ode. In his wo k, di e en
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elec osyn hesis pa ame e s we e explo ed (Table 1) in o de o maximize he e ogeneous Cu-
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BTC c ys alliza ion, su ace co e age and homogenei y. Ve y p elimina y esul s, no shown
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he e, pe o med wi h he same elec ochemical cell e ealed he exis ence o a minimum cu en
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densi y alue, i.e. 1.5 mA/cm2, o he e ogeneous syn hesis on Cu-C /Au modi ied glass
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subs a es. Abo e his cu en densi y, an adequa e concen a ion o Cu2+ ions, as ne mass
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balance esul ing om he gene a ion e m by Cu elec ode oxida ion and he consump ion e m
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by Cu-BTC o ma ion, emains in he elec oly e solu ion o he success ul nuclea ion and
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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
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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).
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Cu-BTC coa ings we e i s ly cha ac e ized by op ical inspec ion suppo ed by he u quoise
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(wa e coo dina ed s a e) colo ha Cu-BTC exhibi s. SEM-EDX analyses (INSPECT-F50) we e
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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
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he Cu-BTC coa ings we e e alua ed by su ace X- ay di ac ion (B uke D8 Ad ance High
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Resolu ion Di ac ome e ) and XPS (K a os Axis X- ay spec ome e ).
163
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Table 1. Elec osyn hesis condi ions s udied in his wo k.
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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
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his wo k.
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Adso p ion p ope ies o Cu-BTC
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The ex u al p ope ies o Cu-BTC ilms we e assessed om A physiso p ion analysis, ca ied
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ou on comme cial Cu-BTC in powde o m, Basoli e C300, pu chased om Sigma Ald ich. The
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as ecei ed bulk ma e ial was also used o quan i y he adso p ion p ope ies owa ds DMMP
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when exposed o 3748 mg/m3 o DMMP a 293 K (in d y ai and a 30 % RH a 293K). Simila
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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
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423 K and a mosphe ic p essu e) o analyze he in luence o wa e con en on DMMP adso p ion
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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
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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)
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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
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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). The mic oscopy images ha e been eco ded in he Labo a o io de
570
Mic oscopias A anzadas a Ins i u o de Nanociencia de A agon-Uni e sidad de Za agoza.
571
Au ho s acknowledge he LMA-INA o o e ing access o hei ins umen s and expe ise.
572
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573
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729
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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.