Solar energy for liquid wastewater treatment with novel TiO2 supported catalysts

A ailable online a www.sciencedi ec .com ScienceDi ec Ene gy Repo s 8 (2022) 489–494 www.else ie .com/loca e/egy The 8 h In e na ional Con e ence on Ene gy and En i onmen Resea ch ICEER 2021, 13–17 Sep embe Sola ene gy o liquid was ewa e ea men wi h no el TiO2 suppo ed ca alys s Rui C. Ma insa, Ângelo Sac asa, Sanja Jo ano ica,b, Pa ícia Al esa, Paula Fe ei aa,c, João Gomesa,∗ aUni e si y o Coimb a, CIEPQPF, Depa men o Chemical Enginee ing, Facul y o Sciences and Technology, Rua Síl io Lima, Polo II, 3030-790 Coimb a, Po ugal bDepa men o Chemical Enginee ing, Facul y o Technology and Me allu gy, Uni e si y o Belg ade, Se bia cDepa men o Chemical and Biological Enginee ing, ISEC, Rua Ped o Nunes, 3030-199 Coimb a, Po ugal Recei ed 13 Janua y 2022; accep ed 27 Janua y 2022 A ailable online xxxx Abs ac Pho oca aly ic oxida ion is p omising echnology o emo al o ecalci an pollu an s om wa e . Sola ene gy can be an in e es ing adia ion sou ce since he ope a ing cos s can be lowe . Howe e , he use o powde pho oca alys is a majo d awback o he echnology since sui able sepa a ion echnologies a e equi ed and ca alys s eco e y is di icul . This wo k aims o es he sui abili y o using polyme ic suppo s o immobilize TiO2in he eac o and apply i o pa abens emo al om wa e by sola pho oca aly ic oxida ion. Polyu e hanes (PU) and polydime hylsiloxane (PDMS) memb anes we e p epa ed and modi ied wi h TiO2. While PU ma e ials a e only able o adso b (35% in 1 h) pa abens whiche e he modi ica ion applied, modi ied PDMS was able o p omo e pa abens pho oca aly ic oxida ion emo ing 20% in 1 h unde sola ene gy. Plasma/UV modi ica ion was able o ac i e PDMS memb anes (16% o me hyl pa aben (MP) emo al) and u he en apmen o TiO2in he polyme ic ma ix did no imp o e he p ocess (18% o MP emo al). Thus, only he supe icial TiO2was ac i e. Resul s show ha PDMS is sui able ma e ial o suppo TiO2aiming pho oca aly ic was ewa e ea men p ocess using he Sun as a clean and enewable ene gy sou ce. ©2022TheAu ho (s).PublishedbyElse ie L d. This isanopenaccessa icleunde heCCBY-NC-NDlicense (h p://c ea i ecommons.o g/licenses/by-nc-nd/4.0/). Pee - e iew unde esponsibili y o he scien i ic commi ee o he 8 h In e na ional Con e ence on Ene gy and En i onmen Resea ch, ICEER, 2021. Keywo ds: Sola ene gy; Con aminan s o eme ging conce n; Pa abens; Polyme ic suppo s; Sola pho oca aly ic oxida ion; Suppo ed TiO2 1. In oduc ion Public heal h and ecological conce ns ega ding he p esence o con aminan s o eme ging conce n such as pha maceu icals and pe sonal ca e p oduc s (PPCPs) in wa e a e g owing. These compounds a e no e icien ly ∗Co esponding au ho . E-mail add ess: [email p o ec ed] (J. Gomes). h ps://doi.o g/10.1016/j.egy .2022.01.196 2352-4847/© 2022 The Au ho (s). Published by Else ie L d. This is an open access a icle unde he CC BY-NC-ND license (h p: //c ea i ecommons.o g/licenses/by-nc-nd/4.0/). Pee - e iew unde esponsibili y o he scien i ic commi ee o he 8 h In e na ional Con e ence on Ene gy and En i onmen Resea ch, ICEER, 2021. R.C. Ma ins, ˆ A. Sac as, S. Jo ano ic e al. Ene gy Repo s 8 (2022) 489–494 emo ed by he con en ional was ewa e ea men due o hei e ac o y cha ac e is ics. Thus, a e discha ged un ea ed o na u al wa e cou ses and a e being de ec ed in wa e sou ces and hei po en ial impac is no well known [1]. Among hose subs ances’ pa abens a e used as p ese a i e and an imic obial agen s in many PPCPs [2]. Pa abens cons i u e an impo an g oup o conce n also due o hei addi i e es ogenic cha ac e . Thus, he seek o sui able e ia y ea men p ocesses is a scien i ic challenge and di e en app oaches can be ound in he li e a u e o he aba emen o hese con aminan s. Ad anced oxida ion p ocesses such as pho oca aly ic oxida ion, pho oca aly ic ozona ion using sola ene gy as adia ion sou ce appea as sui able al e na i es o hei emo al [3–5]. Pho oca aly ic oxida ion can be pe o med a ambien p essu e and empe a u e condi ions using a ca alys wi h semiconduc o cha ac e is ics. This me hodology gains mo e po en ial specially i sola ene gy can be used as a cos less and clean adia ion sou ce. TiO2is he mos usual pho oca alys in his app oach since i can p oduce hyd oxyl adicals in he p esence o sui able adia ion. Typically, his ca alys is used as powde o minimize he mass ans e esis ances as well as maximizing he ca aly ic a ea exposed o adia ion ene gy [6] Howe e , when applied in suspension in he liquid bulk i b ings p oblems o he ca alys eco e y and euse. Al e na i ely, o allow he ca alys euse, powde can be immobilized on o a suppo , ha can ha e di e en sou ces. In his s udy will be ocus polyme ic suppo s, such as PU and silicones. A a e al. [7] immobilized N-TiO2on o he polys y ene (PS) su ace o pho oca aly ic oxida ion o me hylene blue and compa ed i s pe o mance wi h N-TiO2powde . The high amoun o N-TiO2on o PS su ace has simila esul s wi h he powde which means low di usional esis ances. The e o e, he immobiliza ion o TiO2in a sui able suppo has se e al ad an ages o e i s use in aqueous medium suspension. One o hem is he ac ha no expensi e pos - ea men is necessa y o he eco e y o ca alys pa icles a e oxida ion om he pu i ied wa e enabling a con inuous ope a ion o he eac o [8]. Howe e , immobiliza ion o TiO2on a suppo may also b ing some disad an ages ha may comp omise oxida ion e iciency. As an example, in e ac ion be ween sunligh pho ons as well as eac an s wi h he ca alys ’s su ace may be educed. Addi ionally, pho oca aly ic eac ion is limi ed by he a e o mass ans e o eac an s be ween he bulk luid and he ca aly ic su ace [9]. Finally, by inc easing he hickness o he ca alys ilm, he in e nal mass ans e migh play a dominan ole while limi ing he pho oca alysis a he suppo su ace. The e o e, a possible s a egy o maximize TiO2/pho ons/ eac an s in e ac ions is by p omo ing an e ec i e immobiliza ion o he ca alys in he su ace o he suppo . This may be achie ed by se e al echniques and a plasma su ace ea men is one he mos e ec i e, pa icula ly when he o iginal su aces ha e no chemically eac i e g oups [10]. In his wo k, h ee di e en ma e ials (one PDMS and wo PU) we e used o p epa e ilms. These ma e ials p esen se e al cha ac e is ics which p esen hemsel es as highly ad an ageous o he pu pose o his wo k, namely hei anspa ency and lexibili y as well as he abili y o adhe e o glass. The no el y o his wo k was ocused on he assessmen o he oxida ion e iciency o pa abens when using hese polyme ic ma e ials as suppo ma ices o he pho oca alys TiO2. Fo his pu pose, TiO2was immobilized in he polyme ic ilms ei he by en apmen (achie ed du ing ilms p epa a ion) o supe icially (achie ed by plasma ollowed by UV i adia ion). The oxida ion e iciency o TiO2was hen e alua ed o bo h immobiliza ion echniques by using a pa abens mix u e (me hyl-MP, e hyl-EP and p opyl-PP pa aben). The use o low-cos , clean and enewable ene gy om he Sun o p omo e oxida ion is an impo an ad an age o such p ocess when compa ed wi h o he ene gy sou ces such as UV lamps ha will inc ease he was ewa e ea men ene ge ic cos . 2. Ma e ials and me hods 2.1. Chemicals MP, EP and PP we e pu chased om Sigma-Ald ich. TiO2(Ae oxide Degussa P25) was pu chased o E onik Indus ies. Desmopan®481 (481) and Desmopan®3330 (3330) we e ob ained om Baye Ma e ial Science AG and Sylga d®184 (PDMS), a ki con aining wo pa s, a liquid silicon ubbe base and a cu ing agen , was pu chased om DOW-Co ning. Dime hyl o mamide >95% (DMF) was acqui ed om Fishe Chemical. 2.2. Films p epa a ion and immobiliza ion o TiO2 Desmopan®based PU ilms we e p epa ed by cas ing (sol en e apo a ion). Desmopan®was dissol ed in DMF o a 10% (w/ ) PU solu ion. This solu ion was pou ed in o glass Pe i pla es. Then, he Pe i dishes we e s o ed in 490 R.C. Ma ins, ˆ A. Sac as, S. Jo ano ic e al. Ene gy Repo s 8 (2022) 489–494 an o en, a 60 ◦C o 24 h and a e wa ds 1 mm ilms we e ob ained and emo ed om he dishes. Sylga d®184 PDMS p e-polyme and c oss-linking agen we e mixed a he a io o 10:1 (w /w ) and degassed unde acuum. Films wi h 2 mm hickness we e ob ained by cu ing a 65 ◦C du ing 4 h. Se e al app oaches we e ollowed o immobilize TiO2in o he polyme ic memb anes. The i s me hod was he en apmen o he pho oca alys in he polyme ic ma ix (E). Du ing his me hodology, 1.27 mg o TiO2/g o polyme we e homogeneously mixed in he liquid polyme and once cu ing occu ed, a uni o m dis ibu ion o he agen was ob ained. The o he app oach in ol ed he linkage o TiO2 o he su ace o he ilms, which was achie ed by c ea ing adicals on he polyme ’s su ace by a gon plasma i adia ion (P). Fo ha pu pose, a labo a o y and small-scale p oduc ion plasma sys em FEMTO (low p essu e plasma), manu ac u ed by Diene Elec onics, wi h a s ainless-s eel plasma chambe o 100 mm diame e and 270 mm leng h, was used o he plasma su ace modi ica ion expe imen s. The PU memb anes we e placed 80 mm om he elec ode. The memb anes we e plasma ea ed wi h A gon, a chambe p essu e o 0.6 mba , o 2 min and ene gy powe o plasma o 100 W [11]. Then, wo me hodologies we e e alua ed: a) a hin laye o TiO2solu ion (70 mg/L) was pou ed on o he plasma- ea ed su ace and u he plasma i adia ed (Plasma); b) he plasma- ea ed memb anes we e dipped in o a (70 mg/L) TiO2 aqueous solu ion and UV ene gy i adia ed in an UV chambe (D . G obel UV-Elek onik GmbH, Model BS-02) o 30 min (plasma/UV). A e wa ds, all he ilms we e washed abundan ly wi h wa e and d ied un il cons an weigh . Finally, a combina ion o bo h echniques was applied. The e o e, ilms wi h en apped TiO2we e p epa ed and u he ea ed wi h plasma/UV ollowing he p e iously desc ibed me hodology (E+P). 2.3. Sola pho oca aly ic oxida ion expe imen s The pho oca aly ic ac i i y o he p epa ed ma e ials was e alua ed unde sunligh condi ions and a da k condi ions. Expe imen s we e ca ied ou a he Depa men o Chemical Enginee ing o he Uni e si y o Coimb a (40.186622◦,−8.4182372◦). A mix u e o 3 pa abens: MP, EP and PP was p epa ed (1 mg/L o each in ul apu e wa e ). A ci cula memb ane co e ing he glass eac o (50 mL) bo om we e placed and he liquid s i ing was p omo ed by bubbling ai . The eac o is exposu e o he sunligh adia ion di ec ly wi hou any concen a o . The a e age sola adia ion powe was a ound 700 ±150 W/m2du ing he expe imen s. The concen a ion o pa abens du ing he expe imen s was measu ed by he high-pe o mance liquid ch oma og- aphy (HPLC) equipped wi h a diode a ay de ec o (DAD) (UFLC, Shimadzu). The mobile phase is composed by a a io o 50:50 o me hanol and ul apu e wa e acidi ied wi h 0.1% o phospho ic acid. The low a e o his phase h ough he column C18 (SiliaCh om) a 40 ◦C was 0.5 mL/min. The de ec ion o pa abens was pe o med a a wa eleng h o 255 nm. 3. Resul s and discussion 3.1. TiO2immobiliza ion me hodology e ec The TiO2 immobiliza ion me hodology is a pa ame e ha may in luence he pho oca aly ic e ec o TiO2 o e he pa aben’s mix u e deg ada ion. In a p ima y assessmen o he immobiliza ion me hodology e ec he 3 main s a egies we e e alua ed: en apmen (E), plasma/UV ea men (P) and en apmen + plasma/UV ea men (E+P). Fig. 1 shows pa abens emo al by pho oca aly ic oxida ion a e 1 h o sunligh ene gy (700 ±150 W/m2) exposu e using as ca alys he ma e ials e e ed. The pa abens emo al is no a unc ion o TiO2 immobiliza ion me hod when he suppo is PU (ei he 481 o 3330). S ill, he use o plasma/UV seems o sligh ly inc ease MP emo al when compa ed o he case whe e he memb anes we e no subjec ed o plasma ea men , p obably due o he inc ease in hei hyd ophilici y [10]. Di e en esul s a e ound o PDMS memb anes. While deg ada ion was e y low (below han 5%) when memb anes wi h en apped TiO2(E) we e used, emo als o abou 30% o PP we e ob ained when PDMS was modi ied using plasma/UV and TiO2was added o he su ace. Mo eo e , no u he imp o emen was achie ed when TiO2was added by bo h me hods (E+P). Thus, one may conclude ha only supe icial TiO2is a ailable o he deg ada ion eac ions since i is exposed o bo h pollu an s and ligh ene gy. Ligh has u he di icul y on eaching TiO2in he polyme ic ma ix. Besides, di usional esis ances di icul pollu an s o ge hose ac i e si es. 491 R.C. Ma ins, ˆ A. Sac as, S. Jo ano ic e al. Ene gy Repo s 8 (2022) 489–494 Fig. 1. TiO2 immobiliza ion me hodology o e pa abens emo al o (a) Desmopan 481; (b) Desmopan 3330; (c) PDMS suppo s. 3.2. Selec ion o su ace modi ica ion me hodology When wo king wi h hyd ophobic ma e ials, en apmen o he ca alys in he polyme ic ma ix may no be a sui able app oach since no con ac o he wa e wi h he pho oca aly ic agen will occu . In such cases, and as al eady con i med in Sec ion 3.1, polyme s’ su ace modi ica ion wi h immobiliza ion o he ca alys showed o be a mo e con enien me hod, by p omo ing con ac be ween con aminan s and TiO2and leading o he p oduc ion o hyd oxyl adicals. The deg ada ion o pa abens mix u e was used as e alua ion c i e ia o he selec ion o he be e su ace immobiliza ion solu ion o TiO2(Plasma o Plasma/UV). This was pe o med using sunligh adia ion (700 ±150 W/m2) along 1 h o exposu e (Fig. 2). The inco po a ion me hod o TiO2will ep esen an impo an ole o he pa aben’s deg ada ion pe o mance. Fig. 2. Su ace modi ica ion me hod o immobiliza ion o TiO2, (a) Desmopan 481; (b) Desmopan 3330; (c) PDMS suppo s. The PUs (Desmopan 481 and Desmopan 3330) do no p esen signi ican di e ences in e ms o deg ada ion o bo h inco po a ion me hods (Plasma and Plasma/UV). The esul s a e qui e simila bu sligh ly highe when UV adia ion was used. Howe e , o PDMS his di e ence was mo e e iden which p o ed he bene icial e ec o UV adia ion on TiO2inco po a ion. The applica ion o UV adia ion leads o a mo e hyd ophilic PDMS [12] which has g ea ele ance o TiO2ac i i y since wa e wi h ca alys will p omo e he p oduc ion o hyd oxyl adicals. In ac , wa e p esen s an impo an ole o he e iciency o mic ocon aminan s emo al and hyd ophilic memb ane imp o es he pa abens deg ada ion (Fig. 2). Ano he ea u e ele an o his modi ica ion me hodology could be ela ed wi h di usional esis ances. This modi ica ion could make he memb ane mo e pe meable allowing wa e and con aminan s di usion o each ac i e si es o ca alys [12]. 492 R.C. Ma ins, ˆ A. Sac as, S. Jo ano ic e al. Ene gy Repo s 8 (2022) 489–494 3.3. Suppo s adso p ion e ec Rega ding o he p e ious esul s he bes pe o mance (Fig. 1) seems o be o PU memb anes. Meanwhile, i is impo an o con i m i pa abens emo al is due o deg ada ion h ough he ca alys in e ac ion wi h sola ene gy o i we e jus adso bed o he memb ane’s su ace. This analysis was made compa ing he pollu an s emo al a da k condi ions esul s wi h hose ob ained by sola pho oca aly ic oxida ion o memb anes p epa ed by plasma/UV. Also, he adso p ion capaci y a da k condi ions o he memb anes wi hou modi ica ion was assessed. In ac , he mic ocon aminan s can be easily adso bed on o he polyme ic su ace, due o hei pola i y. I is also expec ed ha he inc ease o chain leng h dec eases he pola i y which makes PP mo e nonpola han EP and e en mo e han MP. Fig. 3 compa es he esul s using he modi ied memb anes a da k and sola condi ions. Fo compa a i e pu poses, sola expe imen s we e also pe o med using non-modi ied memb anes. Fig. 3. Compa ison o adso p ion and sola adia ion wi h and wi hou TiO2 o (a) Desmopan 481; (b) Desmopan 3330; (c) PDMS suppo s. Fo PUs (481 and 3330), he deg ada ion o pa abens was almos negligible, which indica es hei adso p ion on he memb ane su ace as he main mechanism behind hei emo al om wa e using hese ma e ials (Fig. 3a,b). Besides, e en using he non-modi ied PU (Blank Sola expe imen s) i was possible o achie e a pa abens emo al pe cen age simila o he one ob ained when he memb anes we e modi ied wi h TiO2(481 Sola and 3330 Sola ). This highligh s ha only pollu an s adso p ion on he polyme ic memb ane is occu ing when PU ma e ials a e used. Thus, he p esence o TiO2is no impo an o he p ocess no he in e ac ion wi h he sola ene gy. Mo eo e , i is possible o see he e ec o pa abens pola i y. The a e o adso p ion o each pa aben inc eased wi h he dec ease o pola i y since PP p esen ed he highes emo al compa ing o he o he pa abens. On he o he hand, i is possible o see pe o mance di e ences o he PDMS memb anes subjec ed o di e en condi ions. Fo he da k condi ions and he memb ane wi hou TiO2 he pa abens deg ada ion was almos null. Unde he sunligh ene gy (700 ±150 W/m2) wi h he TiO2inco po a ed on o he PDMS memb ane was possible o achie e abou 15% o emo al o MP and EP while achie ing abou 30% o PP emo al. The e o e, i is possible o conclude ha wi h he modi ied PDMS memb anes subjec ed o ligh ene gy, hyd oxyl adicals we e p oduced leading o pa abens deg ada ion and he con aminan s emo al was no only due o adso p ion. The a es o hyd oxyl adical ega ding o pa abens inc eases wi h he chain leng h [4]. Besides, he p esence o TiO2is c ucial o he pho oca aly ic ac i i y since negligible pa abens emo al occu ed when PDMS memb ane wi hou TiO2was used unde sunligh condi ions. 4. Conclusions PU ma e ials we e only able o emo e pa abens om wa e by adso p ion and no ca aly ic oxida ion was p omo ed. Con a ily, when PDMS memb anes we e es ed, pa abens adso p ion was negligible. Thus, pa abens emo al by TiO2modi ied PDMS memb anes unde sola ene gy was achie ed by hyd oxyl adical’s p oduc ion ollowed by o ganic con aminan s oxida ion. When compa ing he pe o mance o memb anes modi ied by di e en 493 R.C. Ma ins, ˆ A. Sac as, S. Jo ano ic e al. Ene gy Repo s 8 (2022) 489–494 p ocesses i was concluded ha TiO2en apped in he polyme ic ma ix was no ac i e. Di e en ly, TiO2added o PDMS su ace by Plasma/UV was he main esponsible o he pho oca aly ic ac i i y. This s udy p o ed o PDMS suppo 30% o PP emo al in 1 h o eac ion. These esul s show ha PDMS is an in e es ing ma e ial o suppo TiO2in pho oca aly ic was ewa e ea men s o e coming he d awback associa ed o he use o powde ca alys s. Thus, his may p omo e he applica ion o pho oca aly ic oxida ion using clean and cheap sola ene gy o wa e ea men and euse, gi ing a con ibu ion o ensu e access o a o dable, eliable, sus ainable and mode n ene gy o all (SDG7). CRediT au ho ship con ibu ion s a emen Rui C. Ma ins: Concep ualiza ion, Fo mal analysis, W i ing – o iginal d a , W i ing – e iew & edi ing, Funding acquisi ion. ˆ Angelo Sac as: Da a cu a ion, In es iga ion, Fo mal analysis. Sanja Jo ano ic: Da a cu a ion, In es iga ion, Fo mal analysis. Pa ´ ıcia Al es: W i ing – e iew & edi ing. Paula Fe ei a: Concep ualiza ion, W i ing – e iew & edi ing. Jo˜ ao Gomes: Concep ualiza ion, Supe ision, W i ing – o iginal d a , W i ing – e iew & edi ing, Funding acquisi ion. Decla a ion o compe ing in e es The au ho s decla e ha hey ha e no known compe ing inancial in e es s o pe sonal ela ionships ha could ha e appea ed o in luence he wo k epo ed in his pape . Acknowledgmen s This wo k was inanced by Eu opean S uc u al and In es men Funds h ough Po ugal2020 by he p ojec Pho oSupCa al – De elopmen o suppo ed ca aly ic sys ems o was ewa e ea men by pho o-assis ed p ocesses (POCI-01-0247-FEDER-047545). The au ho s acknowledges Founda ion o Science and Technology – FCT (Po ugal) by he inancial suppo s CEECIND/01207/2018 and UIDB/00102/2020. The au ho S.J. acknowledges he g an BTI 08/2019 o he IAESTE in e nship, Po ugal unde he p o ocol be ween APIET and FCT. Re e ences [1] N.H. T an, M. Reinha d, K.Y-H. Gin, Occu ence and a e o eme ging con aminan s in municipal was ewa e ea men plan s om di e en geog aphical egions-a e iew, Wa e Res 133 (2018) 182–217. [2] M. Bosio, B. Souza-Cha es, J. Gomes, M. Gmu ek, R. Ma ins, E. Saggio o, M. Dezo i, J.P. Bassin, M.E. Quin a-Fe ei a, R.M. Quin a-Fe ei a, Elec ochemical oxida ion o pa aben compounds and he e ec s o byp oduc s on neu onal ac i i y, Ene gy Rep 6 (2020) 903–908. [3] T. Veleg aki, E. 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