Photocatalytic Degradation of Deoxynivalenol Using Cerium

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Photocatalytic Degradation of Deoxynivalenol Using Cerium

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toxins

Article
Photocatalytic Degradation of Deoxynivalenol Using Cerium Doped Titanium Dioxide under Ultraviolet Light Irradiation
Pengzhen He 1,2,†, Zhiyong Zhao 2,†, Yanglan Tan 3, Hengchao E 2, Minghui Zuo 1, Jianhua Wang 2, Junhua Yang 2, Shuxin Cui 1,* and Xianli Yang 2,*

1 College of Chemistry and Chemical Engineering, Mu Danjiang Normal University, Mu Danjiang 157012, China; [email protected] (P.H.); [email protected] (M.Z.)
2 Institute for Agro-food Standards and Testing Technology, Shanghai Academy of Agricultural Sciences, Shanghai 201403, China; [email protected] (Z.Z.); [email protected] (H.E.); [email protected] (J.W.); [email protected] (J.Y.)
3 CAS Key Laboratory of Nutrition, Metabolism and Food Safety, Shanghai Institute of Nutrition and Health, Chinese Academy of Sciences, Shanghai 200031, China; [email protected]
* Correspondence: [email protected] (S.C.); [email protected] (X.Y.) † Both P.H. and Z.Z. rank as the first authors.

Citation: He, P.; Zhao, Z.; Tan, Y.; E, H.; Zuo, M.; Wang, J.; Yang, J.; Cui, S.; Yang, X. Photocatalytic Degradation of Deoxynivalenol Using Cerium Doped Titanium Dioxide under Ultraviolet Light Irradiation. Toxins 2021, 13, 481. https://doi.org/ 10.3390/toxins13070481
Received: 6 May 2021 Accepted: 9 July 2021 Published: 11 July 2021

Abstract: Deoxynivalenol (DON) is a major mycotoxin with high toxicity that often contaminates grains, foods and feeds. The traditional approaches for DON removal are difficult to meet industry and agriculture demands due to the high stability of the DON molecule. Therefore, there is an urgent need to develop green and effective strategies for DON degradation. In this study, a batch of photocatalytic nanomaterials of cerium (Ce) doped titanium dioxide (TiO2) were successfully prepared by sol-gel method. The catalysts were systematically characterized by XRD, HRTEM, FT-IR, UV-Vis and XPS. The catalyst 0.5Ce-TiO2 showed superior photocatalytic activity for DON degradation in aqueous solution under ultraviolet light irradiation, better than that of traditional photocatalyst pure TiO2, and 96% DON with initial concentration of 5.0 mg/L could be degraded in 4 h. In addition, the two possible degradation intermediate products C5H8O3 and C17H18O6 were identified, the photocatalytic degradation mechanism and degradation pathway were studied. The results indicate that Ce doped TiO2 photocatalyst can be used to reduce DON effectively.
Keywords: deoxynivalenol; photocatalytic degradation; cerium doped titanium dioxide; mechanism; pathway
Key Contribution: 0.5Ce-TiO2 showed superior photocatalytic activity for DON removal in aqueous solution under ultraviolet light irradiation.

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1. Introduction
Deoxynivalenol (DON), a high-toxicity secondary metabolite produced by Fusarium graminearum, is one of the most common mycotoxins in grains [1], foods and feeds [2]. This mycotoxin poses a serious threat to human health and animals [3,4].
Some technologies have been employed to eliminate DON. Physical methods such as washing and grinding can reduce the content of DON in contaminated grains, but DON is transferred to some other by-products. Heat treatment for DON removal is very limited, due to the strong thermal stability of DON molecule [5]. Bretz et al. reported that the DON molecule could be decomposed under alkaline conditions and then neutralized by chemical agents [6]. Biological detoxification methods could efficiently reduce the toxicity of DON under mild conditions [7]. Yin et al. found a strain A16 isolated from wheat fields, and identified as Devosia sp., which could survive and degrade DON in several conditions [8]. Although biological methods have good detoxification effects, the disadvantage is relatively long treatment time, which limits its further application. Therefore, developing a safe and

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efficient strategy for DON degradation is the trend in food and other related industries and agricultures.
In recent years, more and more researchers have paid increasing attention in the field of photocatalytic technology with high efficiency, low energy consumption and mild reaction conditions for DON degradation [9]. Oxide semiconductor modified doping materials can effectively degrade DON under light conditions, such as ZnO, TiO2, etc. Wang et al. prepared photocatalytic materials dendritic-like α-Fe2O3, which could reduce 90.3% DON with initial concentration of 4.0 µg/mL in an aqueous solution [10]. Bai et al. found the photocatalyst graphene/ZnO hybrids GZ0.3 prepared by a simple one-step hydrothermal method showed good ability to degrade DON in an aqueous suspension under ultraviolet light (UV) light irradiation. Zhou et al. reported a nanoparticles photocatalyst [email protected] composite ([email protected]), which was employed to reduce DON under the simulated sunlight [11]. Additionally, Wu et al. utilized upconversion [email protected] composites [email protected] to degrade DON in wheat.
Compared to other oxide semiconductor photocatalysts, TiO2 as a non-toxic and environmentally friendly nanomaterial with good catalytic degradation of harmful substances has received extensive attention [12]. However, the wide band gap energy of TiO2 with about 3.2 eV reduces the efficiency of light utilization and weakens its photocatalytic degradation ability [13]. Metal doping is one of the effective control strategies to enhance the photocatalytic activity by reducing the band gap energy of TiO2 [14], which also could inhibit rapid recombination of photogenerated electron-hole pairs and broaden light absorption range redshift due to doping ions in TiO2, making it possible to form complexes with Lewis bases such as organic acids or alcohols [15]. Cerium (Ce), as a rare earth element, is relatively nontoxic and cheaper than other rare earth metals. It was doped with TiO2 to form a new composite catalysts and can effectively reduce the band gap energy of materials and have better catalytic degradation performance [16].
In this study, we successfully synthesized photocatalytic nanomaterials Ce doped TiO2 by sol-gel method. The obtained 0.5Ce-TiO2 showed superior photocatalytic activity for DON removal under ultraviolet light irradiation (λ = 254 nm) in an aqueous solution compared with traditional photocatalyst pure TiO2. In addition, the possible degradation intermediate products were identified, and the photocatalytic degradation mechanism and degradation pathway were studied.
2. Results and Discussion 2.1. Structural Characterizations 2.1.1. Morphology Analyses and Crystal Phase
HRTEM Images and XRD Analysis In order to study the microstructure and crystal phase composition of Ce doped TiO2 catalytic materials, High Resolution Transmission Electron Microscope (HRTEM) were used to characterize the prepared catalytic materials. X-ray diffraction (XRD) was conducted to determine the phases and crystal structures of pure TiO2, xCe-TiO2(x = 0.5, 1, 5, 10, 20, 40) and CeO2. The results are shown in Figure 1. Figure 1a shows the morphology of the pristine TiO2 particles with tiny spherical shapes. Ce doped TiO2 shapes appearance becomes uniform and regular with doping Ce, shown in Figure 1b–h. Figure 1j displays the clear lattice fringes of 0.5Ce-TiO2 with the particle size of approximately 24 nm. The interplanar distance of approximately 0.35 nm corresponds to the (101) crystal plane of anatase TiO2, and the lattice fringe spacing is about 0.19 nm, corresponding to the (220) crystal plane of anatase TiO2. Then, the particle size of TiO2 doped with 0.5% Ce is about 24 nm, as seen in Figure 1i. Figure 1i shows the morphology of the pristine CeO2 particles. Figure 1i shows that the distinct diffraction peaks at 25.4, 37.9, 48.5, 55.1, 62.8, 68.8, 75 and 82.5◦ correspond to the (101), (004), (200), (211), (204), (116), (215) and (224) crystal planes of anatase TiO2, while the diffraction peaks at 47.4 respond to the (220) planes of the cubic CeO2. For the different Ce doping, the XRD patterns demonstrate a similar pattern

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dominated by anatase, and no other phases can be observed, which is consistent with
the HRTEM images. The results are different from previous reports, which showed the
formation of the cerium titanate Ce2Ti2O7 phase with Ce:Ti = 50% in molar ratio [17]. Most of the Ce ions cannot enter the TiO2 lattice because the radius of Ce4+ is larger than that of Ti4, and Ce dopant have been well dispersed on the surface of TiO2 as the form of cerium oxide [18], which may be the reason why CeO2 phases cannot be observed. In addition, the Ce doping expands the TiO2 lattice, causing a large lattice distortion and strain energy. In order to compensate the lattice stress, the oxygen atoms on the TiO2 surface escape the lattice to form oxygen vacancy, playing a role of trapping holes. The effect may contribute
to reduce the probability of recombination of holes and electrons in TiO2 and to increase the photocatalytic activity. The main peak (101) broadens with the increase of Ce content, Toxins 2021, 13, x FOR PEER REVIEWand even disappears, suggests Ce doping inhibits the crystal growth and decrease3softh13e
crystallinity of the synthesized materials.

FFiigguurree11..HHRRTTEEMMiimmaaggeessooffccaattaallyyssttpprreeppaarreeddbbyyssooll--ggeellmmeetthhoodd:: ((aa)) TTiiOO22,, ((bb,,cc,,jj)) 00..55CCee--TTiiOO22,, ((dd)) 11CCee--TTiiOO22,,((ee))55CCee--TTiiOO22, , ((ff))1100CCee--TTiOiO22,,((gg))2200CCee--TTiiOO22,, ((hh)) 4400CCee--TTiiOO22,, ((ii)) CCeeOO22 aanndd((kk))XXRRDDppaatttteerrnnssooffaass--pprreeppaarreeddnnaannooccoommppoossiitteessCCeeddooppeeddTTiiOO22, , TTiOiO22 aanndd CCeeOO22..
Figure 1(n) shows that the distinct diffraction peaks at 25.4, 37.9, 48.5, 55.1, 62.8, 68.8, 75 and 82.5° correspond to the (101), (004), (200), (211), (204), (116), (215) and (224) crystal planes of anatase TiO2, while the diffraction peaks at 47.4 respond to the (220) planes of the cubic CeO2. For the different Ce doping, the XRD patterns demonstrate a similar pat-

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XPS Analysis

The high resolution XPS spectra were performed to analyze and determine the chemi-

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cal state of the synthesized Ce-doped TiO2 photocatalyst. All the obtained spectra were

calibrated to the C 1s electron peak at 284.6 eV. The results are shown in Figure 2.

FFiigguurree 22.. XXPPSSssppeeccttrraaooff00..55CCee--TTiiOO22ssaammpplleess::((aa))tthheewwiiddeessccaannssppeeccttrraa,,((bb))TTii22pp,,((cc))OO11ssaanndd ((dd)) CCee 33dd..
2.1.2.FFiTg-uIRrea2naddUeVm-oVnistDraRteSsAthnealfyuslilsrange survey XPS spectrum of 0.5Ce-TiO2 sample. It coFnutanicntsioOn,alTigaronudpCs oenlemtheenstus,rfwacitehosfhtahrepTpiOho2,toCeeleOc2traonndpCeea-kTsiOap2 pcaeatarliynsgt awt ebriendaninagleynzeerdgbieysFoofu5r3ie1r (TOra1nss)f,or4m58In(Tfria2rped) aSnpdec2tr8o5meeVter(C(F1Ts-)I.R)O. TahnedUTVi-vairseddifefruisveedrefflreocmtanthcee sspyenctthraesoizf ethdepmhaotteorciaatlsaliynstth, ewrhainlegeCof1s20i0s–d8e0r0ivnemd wfreorme rtehceoradnehdy. dTrhoeurseseuthltasnaorlessohlovwennt iandFdiegdurdeu3r.ing the synthesis process, which fails to volatilize completely during drying and calciWnaeticoannasnede rfermomainFsigounreth3e(as)utrhfaactethoef tthhereseammpailne. cHhaorwacetveerri,stiitcaalsbososrhpotwiosnthpaetaksisnocef TthiOer2eairseloatw4d90o,p1in63g4Caencdon34te2n5t,cmth−e1,crheasrpaecctetirvizeelyd, paenadktohfetthhereCeecehleamraecntetriisstviceraybwsoerapkti.on peaksFcigourrreesp2bonsdhotowtshtehsetrheitgchhirnegsovliubtriaotnioXnPoSf sthpeecTtir-aOo-fTTi ib2opndfoirntthhee sTyinOt2h, easnidzetdhesabmenpdlei0n.g5Cveib-TraiOtio2nananddpsutrreetcThiOin2g. vTihbreaTtiioOn2oefxthhiebOits-Htwboonpdeainksthaet wbiantdeirnm4g+oelneceurgleiessp4re5s8e.5n8t oenV t(hTei s2upr3f/ac2e) a[2n6d–2496]4..C28omeVpa(Triin2gpt1h/e2i)n, fcroanrefidrmabinsogrTpitimonaicnulryviens tohfeTTiOi 2 dcohpemedicwalitshtaCtee,[t1h9e]. TCiOom2 cphaarreadcwteirtihstpicuarbesToirOp2t,iothneptewaoksbiinndthinegceonmeprgoiseisteosfdToi p2pedafwteirthdCopeianrgeCaellsphroewsenats,laignhdt shift for both the two spin orbitals Ti 2p3/2 (458.68 eV) and Ti 2p1/2 (464.48 eV), which tihnedaicbastoerspatisotnrosntgreinngtethraoctfiothneopf eTaikasnadtC3e42s5peccmie−s1 i[s20e]n. hTahnecereds.uTlthsesuregsguelstst tahree cchoannsgisetsenint wthitehTtihoexpidreavtiioonusstraetpeosr(tfsro[2m9]T. iM4+otroeoTvi3e+r), ainndthceoinnfifrramretdhaabt sthorepCtieonelceumrevnetoifstshuecCcees-sTfiuOll2y, tdhoepcehdariancttoertihsteicTaiObs2orsptrtuiocntupreea. kFcigourrreesp2ocnsdhionwgstoththeeOTi1Os2haitg4h90recsmol−u1 itsiosnhisftpeedc,taran.dTthhee pcohsairtaiocnteorifsttihceppeeaakkaatp5p29e.a8r8s eaVt aibnopuutr5e1T3iOcm2 −i1s. aTshsiisgnmeadytobethbeeccaryussteaCl leatetnicteerosxtyhgeelnatOti2c−e. oTfhTeiOm2ation fOor1ms pTei-aOk-Cpoesbitoinondsf,ocra0u.s5iCnge-TefifOec2tisonslitghhetslytresthcihftiendg tvoiblorawtieornboinf dthinegoeringeinrgayl Tair-oOu-nTdi b53o0n.d08. FerVo.mThtehreefaisgounrefo, rwpeecaaknshailfstos isneeOth1satanthderTei 2ispacnanabbseoerxpptiloaninepdeabkyatrhoeufnacdt 2t3h4a5t tcrman−1scfeorrrriensgpoenledcitnrogntsofCroOm2. OTh1escahnadraTcite2rpisotircbaitbaslosrtpotiCoen4pfeoarkbiintadlsiccaateussethsactheatnhgaenoinl dthide nchotarcgoemdpelnetseitlyievs oolfatthileizOe daunrdinTgi athtoemsysn[t2h1e]s. is of the material, and the remaining small amouFnitgoufrein2odrgshaonwicsctahrebohnigwh aressooxluidtiioznedXPtoSCspOe2cdtruurminogfdCrey3indgf.or the synthesized sample 0.5Ce-TiO2. The spin orbitals coupling states of 3d5/2 and 3d3/2 are labelled with v and u, respectively. The XPS spectrum of the Ce 3d is relatively complex, mainly due to the

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hybridization of O 2p and Ce 4f orbital electrons and the partial occupation of the 4f [21]. Hence, the spectrum is categorized into ten constituents. The binding energies of Ce 3d5/2 at 880.06, 881.67, 882.58, 885.66 and 899.39 eV are labelled with v0, v, v , v and v , while Ce 3d3/2 at 901.22, 903.62, 908.08, 904.12 and 913.74 eV are labelled with u0, u, u , u and u [22]. The peaks at v0, v , u0 and u are characteristic binding energies of Ce3+ configurations between the O 2p level and Ce 4f level. v /u is related to the Ce(3d94f2) (O 2p5) final state, and v0/u0 is assigned to the Ce(3d94f1) (O 2p6) final state [23]. The peaks at v, v , v , u, u and u” are attributed to Ce4+. v /u is related to the primary photoemission from Ce(3d94f0) (O 2p6) final state, and v/u is related to the Ce(3d94f1) (O 2p5) final state [24]. The v /u is from the transfer of two electrons from the O 2p orbital to an empty Ce 4f orbital with the Ce(3d94f1) (O 2p5) final state [25]. It is deduced that the surface of 0.5Ce-TiO2 is not fully oxidized due to the presence of Ce4+/Ce3+, and the Ce–O–Ti bond may be formed at the interstitial sites or interfaces between CeO2 and Ce2O3, though their contents are too small to be detected by XRD [25].
2.1.2. FT-IR and UV-Vis DRS Analysis
Functional groups on the surface of the TiO2, CeO2 and Ce-TiO2 catalyst were analyzed Toxins 2021, 13, x FOR PEER REVIEWby Fourier Transform Infrared Spectrometer (FT-IR). The UV-vis diffuse reflectance sp6eocftr1a3
of the materials in the range of 200–800 nm were recorded. The results are shown in Figure 3.

Figure 3. (a) FT-IR ssppeeccttrraa ooffTTiiOO22,, CCeeOO22 and Ce-TiiOO22 samples. (b) UV-Viiss aabbssoorrppttiioonn ssppeeccttrraaooffTTiiOO22,, CCeeOO22 and CCee-TiiOO22 with different Ce iioonn ddooppiinngg ccoonncceennttrraattiioonn.. (c) TThhee ccoorrrreessppoonnddiinngg bbaanndd ggaappss ooff 00..55CCee--TTiiOO22..
AWcecocardnisnege tforotmheFsigpuercetr3aa, TthiOat2tmheatihnrlyeeambsaoinrbcshualrtarcatveiroisletitc(aUbVso)rlpigtihotn, paneadkistsofmTaiOxi2maruemat w49a0v,e1l6e3n4gtahnids 3349235ncmm.−T1h, eremspaexcitmivuemly,aabnsdortphteiothnrweeacvhealernacgttehriosftiaclal bthseorCpeti-oTniOp2ecaaktsacloyrsrtesapmonpdletsoisthsehisftreedtcthoitnhge vibsirbalteiornanogfethoef 4T0i0-O–6-T00i bnomn,dwihnictheeTxpiOan2,dasntdhethraenbgeenodfinitgs avbibsroartpiotinonansdpescttrreutcmh.inMgovrieborvaetiro, nwoitfhththeeOin-HcrbeaosnedoifnCtheecownatteenrt,mthoelerceudlesshpifrteosefntht eoncatthaelsyusrtfsaacme [p2l6e–s2i9s]m. Coroemopbavriionugs.tAhemionnfrgaraeldl Caeb-sToirOp2ticoantaclyusrtvseasmopf lTeisO, t2hdeorpededshwifitthofCdeo,ptehde mTieOt2alcChaercaocnteterinsttiics athbesolarprgtieosnt wpehaeknstihnetchoenctoemntpoofsCiteesisd4o0p%e.dTwheithabCsoerabraenaclel porfepsuenret,TainOd2 itshefraobmsotrhpetieolnecsttrroenngtrtahnosfittihoenpfreoamks Oat 23p42t5ocTmi −31dissteanteh.aTnhceedr.eTdhsehrifetsuolftsCaer-edocponedsisTteiOnt2 mwiatyh btheecparuesveidoubsyretpheorftosr[m29a]t.ioMnoareonvewer, einlecthtreoinnifcrasrteadtea, bwshoricphtiorendcuucrevsetohfethdeisCtaen-TceiOo2f, cthhearcgheartraacntesrfiesrtibceatbwsoeerpnt4iofnelpeecatrkocnosrorefsCpeoniodninsgantodtthheeTcioOn2dautc4t9io0ncmor−v1ailsenshcieftbeadn, danind tthhee TpioOsi2tiboannodfgtahpe,peenakhaanpcpineagrsthaet apbhooutto5c1a3taclmyt−ic1.aTchtiivsitmya[y3b0]e. bLeicaeutsealC. eheanvteerasstchreibleadttictoe Cofe4T+/iCOe23+toiofnosrmasTeil-eOct-rCoen bscoanvdesn, gcearusstiongtreafpfetchteoenletchterosntrseotcfhTiinOg2 vainbdratthieonCeof4tfhleevoerligasinaanl iTnit-eOr-fTaciibaol nchda.rFgreotmranthsfeerfiganudree, lwimeincaantioanlsoofseeleectthraotnt-hheorlee risecaonmabbisnoartpiotnio[n24p]e.ak around 2345Ccmom−1pacorirnregswpoitnhdainllgctaotaClyOs2t.sTamhepclhesarianctthereisUtiVc arbegsoiorpntoiofn20p0e–a4k0i0ndnmica,tietsisthfoatuentdhathnaotl tdhieddnoopticnogmopflCeteeclyanvoimlaptirliozveedtuhreinabgstohrebsaynnctehoefsTisiOof2,thanedmtahteeraibasl,oarnbdantcheeorfemTiaOin2 iinngcrsemasaelsl wamithoutnhteoinf icnreoargseanoifctchaerbdoonpiwnagsaomxioduiznetdoftoCCe.OB2adnudrignagpds reysitnimg.ated from Tauc transformatioAncscoofrdthinegabtosothrbeasnpceectsrpae, cTtirOa2amreasihnolywanbsinorFbisguulrtera3v(cio).leTth(eUbVa)nldigghat,pa(nEdg)itiss cmaalcxuimlautemd mwaaivnellyenbgytthhiesf3o9ll3onwmin.gTfhoermmualxaim[3u1]m: absorption wavelength of all the Ce-TiO2 catalyst samples is shifted to the visible range of 400–600 nm, which expands the range of its absorption spectrum. Moreover, with t(hαehνin)1c/2re=aKse(hoνf-CEeg)content, the red shift of the cataly(1s)t
where hν represents photon energy, α represents absorption coefficient, Eg represents band gap energy and K is a constant. It can be seen from Figure 3(c) that the band gap width of the synthesized 0.5Ce-TiO2 sample is 2.9 eV, less than that of TiO2 (Eg = 3.2 eV). The results indicate that doping Ce in TiO2 significantly reduces the band gap energy and

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samples is more obvious. Among all Ce-TiO2 catalyst samples, the red shift of doped metal Ce content is the largest when the content of Ce is 40%. The absorbance of pure TiO2 is from the electron transition from O 2p to Ti 3d state. The red shift of Ce-doped TiO2 may be caused by the formation a new electronic state, which reduces the distance of charge transfer between 4f electrons of Ce ions and the conduction or valence band in the TiO2 bandgap, enhancing the photocatalytic activity [30]. Li et al. have ascribed to Ce4+/Ce3+ ions as electron scavengers to trap the electrons of TiO2 and the Ce 4f level as an interfacial charge transfer and elimination of electron-hole recombination [24].
Comparing with all catalyst samples in the UV region of 200–400 nm, it is found that the doping of Ce can improve the absorbance of TiO2, and the absorbance of TiO2 increases with the increase of the doping amount of Ce. Band gaps estimated from Tauc transformations of the absorbance spectra are shown in Figure 3c. The band gap (Eg) is calculated mainly by the following formula [31]:

(αhν)1/2 = K(hν − Eg)

(1)

where hν represents photon energy, α represents absorption coefficient, Eg represents band Toxins 2021, 13, x FOR PEER REVIEWgap energy and K is a constant. It can be seen from Figure 3c that the band gap wid7 tohf 1o3f
the synthesized 0.5Ce-TiO2 sample is 2.9 eV, less than that of TiO2 (Eg = 3.2 eV). The results indicate that doping Ce in TiO2 significantly reduces the band gap energy and effectively binyhCibeitdsothpeinrgecpolmaybaincaot-iocantaolfyptihcoetfofegcetnoenraDteOdNeledcetgrorands-ahtioolnes. .The removal effects of 5Ce-
TiO2 and 10Ce-TiO2 are equivalent to pure TiO2. However, the degradation rate of 10CeT2.i2O. 2Pahnodto4ca0tCaley-tTiciOD2eagrreadloawtioenr othf aDneothxyant iovfaTleinOo2l. The main reason may be that excessive Ce d2.e2s.t1r.oEyvtahleuaTtiiOon2 loatfttihcee sEtrffueccttuivreenaensds dofecDreOaNseDtheegrpahdoattoioacntivity of the nanomaterials, alt-
hougThhteheeffleicgthivteanbesosropftCioen-TriOan2gpehoretodcsahtiafltysti[c3d2e].gTrahdeatrieosnuDltsOiNnduincdateer UthVatli0g.h5tC(λe-=Ti2O524hnams) saunpdetrhioertopthaoltoorcgaatanliyctcicarabcotinvi(tTyOfoCr)DchOaNngreinmgotvreanl duns ddeurrUinVg tlihgehrte(aλc=tio2n54onfmp)hiorrtoacdaiatatiloynti,c wdehgircahdiasteiovnenDbOeNtteirnthaqanuetohuats osfoltuhteiotrnaduistiinogna0l.5pCheo-tToicOa2taalyrestsThoiOw2n. in Figure 4.

FFiigguurree44..((aa))HHPPLLCCcchhrroommaatotoggrraammooffDDOONNpphhoototoddegergardadataitoinonusuisnigng0.05.C5eC-eT-iTOi2O. 2(.b()bT) OTOCCrermemovoavlainl iDn ODNONaqauqeuoeuosussolsuotliuo-n otifodnifofefrdeinftfeirneintitalinciotinaclecnotnracetinotnra. t(ico)nT.h(ce)dTehgeraddeagtrioadnartaiotenorfadteifofefrdeniftfeprhenottopchaotatolycsattsaluynsdtserunUdVerliUghVt ilrigrahdt iiartriaodniaftoironDOfoNr rDemOoNvraelmafotevral24a0ftemri2n4.0 min.
ITnhtehreacpoiudrpsehootfotchaetadleygtircaddaetgiorand, athtieonmeoafsDuOreNmeonvteorf0T.5OCCe-iTsiaOn2 inmapnoormtaanttereimalbsowdai-s mcleeanrtloyfsteheenmbiyneursailnizgatHioinghrePaecrtifoonrmanadnctheeLmiqiuniedraClihzraotimonatdoeggrraepeh. Dy O(HNPaLqCu)e,oausssshooluwtnioinn wFiigtuhrieni4tiaa.l cTohneceHnPtrLaCtiocnhsroofm1amtogg/rLamansdsh5omwg/dLecwreeraesisnegleDctOedNhepreea.kIst caatnrebteensetieonnfrtoimme F2.i7g4umrei(nb)wthitahtptrhoeloTnOgCingvairlruaedsiaatrieongrtaimdue.alTlyhedFeicgruearesi4ncgswhoitwhspthroelodnifgfeinregntthpehpothooctaotcaalytati-c ldyetgicraredaacttiioonn,ewffehcitcsh omf eCaen-sTtihOa2t wthiethmdinifefrearleinzat tCioendraotpeinogf tchoenDteOnNt aanqduepouurse sToilOu2ti.onThise ionpctriemasuimngdwopitihngthaemroeaucntitoonf tCime eis i0n.c5r%eaisninogu. rTshteudrey.suTlthseidnedgicraatdeathioant mraotereofanthde mDoOrNe DaqOuNeomusolseocluulteios naraetf5urmthge/rLoxcaidnizredactho 9H62%O uansidngCO0.25Ccoem-TpiOle2teulyn.dTehreUTVOlCig/ThOt iCrr0ardatiaiotiofn 5afmtegr/2L4i0s mleisns.thTahnetphhaot toofc1atmalgy/tLicredseuglrteadaftrioomn emffoercet misohleigchuelerstihnavnol8v5e%d iunntdheerdthegersaadma-e tcioonndrietaiocntiso.n TinhteherehsiuglhtscoinndceicnattreattihoantotfhtehesmDOalNl CaeqOue2opuasrstoiclluetsiopnr.oduced on the TiO2 particles caused by Ce doping play a co-catalytic effect on DON degradation. The removal 2ef.2fe.2c.tsFroefe5RCaed-TiciOal2Tarnadpp1i0nCgeE-TxipOe2riamreenetqsuaivnadlePnhtottoocpautraelyTtiOc D2.eHgroawdeavtieorn, tMheecdheagnraisdmation
To explore the main active substances in the process of DON degradation, the active
material capture experiments were carried out. We choose EDTA-2Na as hole (h+) scaven-
ger [33], tert-butanol as the hydroxyl radical (•OH) [34] and nitrogen (N2) bubbling was
used to superoxide radicals (•O2-) trapping agents. The results are shown in Figure 5(a).

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rate of 10Ce-TiO2 and 40Ce-TiO2 are lower than that of TiO2. The main reason may be that excessive Ce destroy the TiO2 lattice structure and decrease the photoactivity of the nanomaterials, although the light absorption range redshifts [32]. The results indicate that 0.5Ce-TiO2 has superior photocatalytic activity for DON removal under UV light (λ = 254 nm) irradiation, which is even better than that of the traditional photocatalyst TiO2.
In the course of the degradation, the measurement of TOC is an important embodiment of the mineralization reaction and the mineralization degree. DON aqueous solution with initial concentrations of 1 mg/L and 5 mg/L were selected here. It can be seen from Figure 4b that the TOC values are gradually decreasing with prolonging the photocatalytic reaction, which means that the mineralization rate of the DON aqueous solution is increasing with the reaction time increasing. The results indicate that more and more DON molecules are further oxidized to H2O and CO2 completely. The TOC/TOC0 ratio of 5 mg/L is less than that of 1 mg/L resulted from more molecules involved in the degradation reaction in the high concentration of the DON aqueous solution.

2.2.2. Free Radical Trapping Experiments and Photocatalytic Degradation Mechanism

To explore the main active substances in the process of DON degradation, the active

material capture experiments were carried out. We choose EDTA-2Na as hole (h+) scav-

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enger [33], tert-butanol as the hydroxyl radical (•OH) [34] and nitrogen (N2) bubbling was

used to superoxide radicals (•O2−) trapping agents. The results are shown in Figure 5a.

FFiigguurree 5. (a) The various scavengers’’ effects on the photocatalytic degradation of DON using 0.5Ce-TiO22.. ((bb)) Schemmaattiicc

iilllluussttration for the cchhaarrggeesseeppaarraattioionnaannddtrtarannsfsefrerofofCCe-eT-iTOiO2 i2ninthteheprporcoecsessosfoDf ODNONdedgeragdradtiaotniounnudenrdUerVUliVghlitgihrrtaidrriatdioian-. tion.

From Figure 5a, the photocatalytic activity of 0.5Ce-TiO2 decreases largely by the

addiTtihoenpohfohtoolceatsaclayvteicngdergr(aEdDaTtiAo-n2Nmae)c,hwanhiislme nfoorsiDgnOifiNcarenmt doevcarleuaseinwg aCseo-TbisOer2vneadnboy-

mthaeteardiadlistisoynntohfe•sOizHedsicnatvheinsgeexrpse, riinmdeicnattfinorgDthOaNt •aOreHsharoewnnoitnthFeigmuraein5(obx)i.dTahteiveelescpterociness

ianfftehcetinvgalceantcaelybtaicnde(gVraBd) aotfiotnh.eTChea-tTiisO, t2hseahmoplelepalareyseaxcmitoedretkoetyhreocleoninduthcetipohnobtoancadta(lCyBti)c

udnedgerar dthaetioirnrardeaiacttiioonn othf aUnV•OligHhti.nTthe nUuVmlbigehrtoifrrhaodlieastioonnV[3B5]i.sItnheadsdamitieonas, tthheedneugmrabdear-

otfioenleecftfirocniesnocny CofBD. UOnNdeursignegne0r.5aCl ceo-TnidOit2ioisnso,bpvhioutosglyenrerdautecdedelwecithrotnhse-haonloexciacrsrioelrustiaorne,

eiansdiliycaitninclgintehdattoOr2eicsoamnboitnhee,rremsuorlteinimg ipnoortnalnytarosmleailnl pthaertpohfothtoedeelgecrtardoantsioinvroelavcetdioinntthhaet cpartoadlyuticcesdemgorareda•tOio2n−,pwrohciecshs i[s37c]o.nTshisetebnatnwdipthosthiteiopnreovf idooupsesdtusdaym[p3l6e]s. iBsamseadinolny acalllcthue-

lraetseudltbsyatbhoevfeo,lwloewcinang cfornmcluuldaes t[h38a]t:the photooxidation mechanism occurring on the sur-

face

of

0.5Ce-TiO2

may

involve

in

the direct EVB = χ -

oxidizing Ee + 0.5Eg

reaction

of

DON

with

•O2−

a(n2d)

holes. The photocatalytic degradation mechanism of the 0.5Ce-TiO2 sample may involve

the oxidation process of holes and •OE2C−B.= χ - Ee - 0.5Eg

(3)

The photocatalytic degradation mechanism for DON removal using Ce-TiO2 nano-

wmhaetreeriEaVlsB,sEyCnBt,hχesainzdedthine Ethg iasreextpheerVimBeendtgfeorpDotOenNtiaalr,eCsBhoewdgneinpoFtiegnutriael5, bSa. nTdheeresolencterloenc-s

tirnontheegavtaivleitnyceanbdantdhe(VbaBn)dofgtahpe oCfet-hTeiOp2hsoatomcpatlealayrsetse.xTchiteedvatloutehoefcχonfodruTctiiOon2 ibsa5n.8d1(eCVB,)

aunnddEere rtheperiersreandtisattihoenforfeeUeVlelcigtrhotn. TenheernguymonbetrhoefhhyodlreosgoennVscBailse,thweitshama evaalsutehoefn4u.5mebVe.r

AofcceolerdctirnognstootnhCe Ba.bUovnedfeorrgmeunlear,atlhceonEdCBitoiofnCse, -pThioOt2oigse-n0e.1ra4teedV ealnecdtrtohnesE-hVBolies c2a.7rr6ieerVs.aIrne

tehaissimlyaitnecrliianle, dCetodroepcaonmtsbiinneto, rtehseuTltiiOng2 lianttoicnelyinatrsomdaulclepnaertwofimthpeuerlietyctlreovneslsin(vemolpvetydCine t4hfe)

with a smaller band gap close to the Ti 3d conduction band of TiO2 [32]. Under light illu-

mination, the distance of the excited charge carrier transfer from Ti 3d of TiO2 to Ce 4f

level is narrowed [39], which can reduce the charge carrier’s recombination rate [40]. In

addition, the photogenerated electrons on the conduction band react with O2 to form •O2-

, and holes in VB react with DON to form CO2 and H2O. The reaction formula is:

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catalytic degradation process [37]. The band position of doped samples is mainly calculated by the following formulas [38]:

EVB = χ − Ee + 0.5Eg

(2)

ECB = χ − Ee − 0.5Eg

(3)

where EVB, ECB, χ and the Eg are the VB edge potential, CB edge potential, Sanderson electronegativity and the band gap of the photocatalysts. The value of χ for TiO2 is 5.81 eV, and Ee represents the free electron energy on the hydrogen scale, with a value of 4.5 eV. According to the above formula, the ECB of Ce-TiO2 is −0.14 eV and the EVB is 2.76 eV. In this material, Ce dopants into the TiO2 lattice introduce new impurity levels (empty Ce 4f) with a smaller band gap close to the Ti 3d conduction band of TiO2 [32]. Under light illumination, the distance of the excited charge carrier transfer from Ti 3d of TiO2 to Ce 4f level is narrowed [39], which can reduce the charge carrier’s recombination rate [40].
In addition, the photogenerated electrons on the conduction band react with O2 to form •O2−, and holes in VB react with DON to form CO2 and H2O. The reaction formula is:

e− + O2 → •O2−

(4)

h+ + -OH → •OH

(5)

DON + h+ → CO2 + H2O

(6)

DON + •O2− → CO2 + H2O

(7)

2.2.3. Intermediate Products of Don Degradation and Possible Photodegradation Pathway
The intermediate products of DON photocatalytic degradation were analyzed using by Ultra Performance Liquid Chromatography coupled with Quadrupole Time-of-flight Mass Spectrometry (UPLC-QTOF/MS) (ESI+ mode).
As shown in Figure 6a, Extracted Ion Chromatogram (XIC) shows the two intermediate products’ peaks. The two intermediates chemical structures P1 C5H8O3 (m/z theoretical 117.06, experimental 117.07) and P2 C17H18O6 (m/z theoretical 319.12, experimental 319.12) are identified by comparing with the DON (m/z theoretical 297.00) molecule, as shown Figure 6b. We speculate that P1 and P2 structures are from a possible unstable intermediates (IP1) six-membered ring compound via opening loop with C1-C2 bond fractures and by removing the five-membered ring. The five-membered ring with a 12,13-epoxy group is one of the main toxic functional groups in DON [41]. The reaction can eliminate the toxicity of DON. However, we did not find that the carbonyl-containing intermediate product ion (m/z 303.09) formed by the epoxy ring group destroyed, which is different from the previous study [42] due to the strong oxidizing ability. Then, IP1 dehydrates to form the relatively stable compound IP2. Two possible reaction pathways may exist. One is that IP2 continue to be oxidized to form P1. The other one is that the two IP2 molecules are coupled to form P2. The intensity changing trends of the molecular ion peak of [DON+H]+, [P1+H]+ and [P2+H]+ with the reaction time are shown in Figure 6c. Because TOC content gradually decreases with the reaction time increasing, DON is further oxidized and mineralized to CO2 and H2O completely. The possible pathway that intermediate products P1 and P2 generated from DON molecular break, continued to react and finally disappeared with the photocatalytic degradation reaction is speculated and shown in Figure 6d.

Toxins 2021, 13, 481

molecules are coupled to form P2. The intensity changing trends of the molecular ion peak of [DON+H]+, [P1+H]+ and [P2+H]+ with the reaction time are shown in Figure 6(c). Because TOC content gradually decreases with the reaction time increasing, DON is further oxidized and mineralized to CO2 and H2O completely. The possible pathway that intermediate products P1 and P2 generated from DON molecular break, continued to reac9toafn1d3 finally disappeared with the photocatalytic degradation reaction is speculated and shown in Figure 6(d).

FFiigguurree66.. (a) Extracctteedd IIoonn CChhrroommaattooggrraamm((XXIICC))ooffiinntteerrmmeeddiaiatteepprroodduucctstsPP11aannddPP22. .((bb))MMSS//MS spectruumm ooff inntteerrmmeeddiiaattee pprroodduuccttssPP11aannddPP22. .(c(c))TThheeinintetennsistiytychchaannggininggtrternednds sofotfhtehemmoloelceuclualrairoinonpepaekaokfo[fD[ODNO+NH+H]+],+[,P[1P+1H+H]+]+aanndd[P[P22++HH]+]+ wwiitthh tthhee rreeaaccttiioonn ttiimmee.. ((dd)) TThhee ppaatthhwwaayy ooff DDOONN ddeeggrraaddaattiioonn..
3. Conclusions
In conclusion, TiO2 photocatalytic nanomaterials doped with Ce were successfully prepared by the sol-gel method. In these synthesized materials, 0.5Ce-TiO2 shows superior photocatalytic activity for DON removal in aqueous solution under UV light irradiation (λ = 254 nm). The free radical trapping experiments indicate that the photogenerated h+ and •O2− are the two main active substances for DON photocatalytic degradation. The two possible degradation intermediate products C5H8O3 (m/z 117.07) and C17H18O6 (m/z 319.12) were identified, which indicates that the main toxic groups in the DON molecule were destroyed. This work provides an efficient and mild method to reduce DON contamination. In order to further evaluate the feasibility of this method, the study on toxicity of DON degradation products is ongoing.
4. Materials and Methods 4.1. Materials
Tertbutyl titanate (TBOT), cerium nitrate hexahydrate (Ce(NO3)3•6H2O, 99%), tertbutyl alcohol (TBA), EDTA-2Na and acetic acid were purchased from Shanghai Titan Technology Co., Ltd. Water used in the experiment was ultrapure water prepared from the

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Milli-Q system (Millipore, Billerica, MA, USA). Acetonitrile and methanol (mass spectrum grade) were purchased from Fisher Chemical.

4.2. Synthesis of Ce-TiO2, TiO2 and CeO2
Ce-dropped TiO2 (Ce-TiO2) based catalysts were prepared using the sol-gel method. In the study, tertbutyl titanate (TBOT) and cerium nitrate hexahydrate (Ce(NO3)3•6H2O) were used as the reaction precursors. The typical synthetic procedure was as follows: first, 15 mL TBOT and little amounts of acetic acid were dissolved in 30 mL absolute ethanol to make the solution A. The solution B was cerium nitrate hexahydrate aqueous solution. Solution B was dropped into solution A slowly with vigorous stirring. The mixed solution continued to stir, and the solution became sol and gel. The gel stood for 12 h, and then was dried at 120 ◦C in an oven; finally, it was calcined at 550 ◦C for 3 h. The product was Ce-TiO2. Using the same synthesis procedure, the product with different proportion was obtained by only changing the content of cerium nitrate (the Ce contents were varied as Ce: Ti = 0.5, 1, 5, 10, 20 and 40% in molar ratio) and was marked as 0.5Ce-TiO2, 1CeTiO2, 5Ce-TiO2, 10Ce-TiO2, 20Ce-TiO2 and 40Ce-TiO2, respectively. In addition, pure TiO2 nanomaterials were synthesized without adding cerium nitrate as a control. The CeO2 catalyst was also prepared by sol-gel method [43].

4.3. Characterization of Catalysts
The crystal structure of the sample was determined by X-ray diffraction (Bruker D8 ADVANCE, Germany), with Cu Kα radiation as the X-ray source, and operated at 40 kV and 40 mA. The 2θ scan range was 20–85◦ with a step size of 0.02◦. Morphology and structure of catalysts were observed using high-resolution transmission electron microscopy instruments (JEM-2100F, Japan). X-ray photoelectron spectroscopy (XPS) studies were performed with a Escalab 250Xi spectrometer (ThermoFisher, MA, USA), using a monochromatic Al Kα source. The infrared spectra were recorded on the Nicolet iS5 FT-IR Spectrometer (Thermo Scientific, WI, USA). The UV-Vis diffuse reflectance spectra of 200–800 nm were recorded on the Shimadzu UV 3600plus (Shimadzu, Japan).

4.4. DON Photocatalytic Tests
Photocatalytic tests were carried out in photochemical reaction apparatus, and the tests were performed using a UV lamp (254 nm). The initial concentration of DON solution was 5 mg/L. Before the light irradiation, 2.5 mg catalyst was added to 20 mL of DON solution and kept in the dark for 30 min to reach the adsorption-desorption equilibrium. After different irradiation times (30 min, 60 min, 90 min, 120 min, 180 min and 240 min), 1 mL of suspension was collected and centrifuged at high speed. The upper liquid was filtered through a 0.22 µm filter membrane and was analyzed. The concentration of DON was determined by Acquity Ultra Performance LC (Waters, Milford, MA, USA) equipped with a Waters Acquity BEH C18 column (1.7 µm, 2.1 × 100 nm) and with an isocratic mobile phase composed of methanol-water (20:80) at a flow rate of 0.25 mL/min. The DON degradation rate was calculated by the following formula.

η(%) = (C0 − Ct)/C0 × 100

(8)

where C0 represents the initial concentration of DON, and Ct represents the concentration of DON after photocatalytic degradation.
Seven DON aqueous solutions of 20 mL with the same initial concentration 1 mg/L and 5 mg/L were, respectively, irradiated at different irradiation times (0 min, 30 min, 60 min, 90 min, 120 min, 180 min and 240 min) and directly submitted to TOC analysis. The TOC content was determined by Total Organic Carbon Analyzer TOC-L CPH Basic System (Shimadzu Co. Ltd., Kyoto, Japan).
To investigate the photocatalytic mechanism of DON degradation, the active species trapping experiment was performed with three different active substance capture agents
SolutionDegradationPhotocatalytic ActivityPhotocatalytic DegradationRemoval