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Titanium dioxide (TiO ) nanoparticles were functionalized with maleic anhydride (MA). The extension of adsorbed MA on the TiO was evaluated by ultrasonic and magnetic stirring. Total Organic Carbon and Thermogravimetric Analysis confirmed the presence of surface MA even after the washing process. The Fourier Transform Infrared and UV-Vis Diffuse Reflectance spectra clearly showed the chemical anchored maleic anhydride on the TiO surface as bidentate bridging adsorption. The surface modification of TiO extended its light absorption range to the visible light region reducing its bandgap energy from 3.05 to 2.55 eV. X-Ray Diffraction patterns showed that the TiO functionalized presented a mixture of anatase and rutile phases without any crystalline phase transformation after MA chemisorption process. The functionalization percentage and the reaction efficiency for the TiO with 5 wt% MA sample were 3.6 and 69%, respectively, as shown by Differential Thermal Analysis and Thermogravimetric Analysis. The performance of pure and functionalized TiO samples were evaluated in the photocatalytic degradation of the Methyl Orange dye under ultraviolet light. TiO with 5 wt% MA produced a maximum degradation of 97% after 90 min, 3% higher than the commercial TiO . Keywords: Functionalization, Titanium dioxide nanoparticles, Photocatalysis, Maleic anhydride, Nanostructures 1 Introduction (UV) light absorption range [6, 7]. Chen et al. [8] investi- The study of metal oxides has been of great interest in gated the photocatalytic activity of Fe O /TiO function- 2 3 2 developing hybrid materials, catalysis, and solar cells. alized biochar in Fenton processes; the percentages For example, titanium dioxide (TiO ) is the most popu- degradation of Methyl Blue, Rhodamine B, and Methyl lar photocatalyst because of its excellent physical and Orange (MO), were 78, 67, and 83%, respectively. Chala- chemical characteristics. However, it only absorbs 4% of sani and Vasudevan [9] observed that even after 10 cy- sunlight [1]. The light absorption range of TiO can be cles, the efficiency of the Fe O @TiO functionalized 2 3 4 2 shifted to the visible region by modifying its structure or with carboxymethyl-β-cyclodextrin for the photocatalytic surface. There are some methods to improve the phys- degradation of Bisphenol A remains at high level, main- ical and chemical properties of TiO , such as etching, taining 90% efficiency as compared to the first use effi- photo-deposition of metals, organic compounds anchor- ciency. Also, Sun et al. [10] reported the surface ing, and metal ions doping [2–5]. modification of TiO with polydopamine in the removal Previous studies have been focused on increasing the of Rhodamine B, showing a percentage degradation of ability of TiO to capture photons outside the ultraviolet 99% under UV light radiation. In addition, Galoppini [11] considered it necessary to know the physicochemi- cal properties of the solid surfaces to obtain a good sta- * Correspondence: pavel.hernandez@ipicyt.edu.mx bility between the organic and inorganic phases. Advanced Materials Department, The Institute for Scientific and Technological of San Luis Potosi, 78216 San Luis Potosi, Mexico Full list of author information is available at the end of the article © The Author(s). 2022 Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article's Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article's Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/. Del Castillo et al. Sustainable Environment Research (2022) 32:7 Page 2 of 9 Commonly, the maleic anhydride (MA) has been used points for ET at 70 °C, TO at 105 °C. It was maintained as a coupling agent in the functionalization of nanoparti- at constant reflux for 4.5 h. Finally, the solvent was sepa- cles because it serves as a “seed molecule” capable of an- rated by centrifugation and decanting to recover the choring organic compounds [12–14]. However, there are functionalized nanoparticles. The TiO nanoparticles a few investigations about surface modification of metal were prepared with different concentrations of MA: 2 oxides with MA. This compound has two functional wt% (1TiMA) and 5 wt% (2TiMA). groups: carboxyls and alkenes. The carboxyl group inter- acts chemically on the TiO surface. The sensitization of 2.3 Washing methodology inorganic nanoparticles surface with MA induces the Functionalized TiO nanoparticles were washed using transfer of electrons from the bonds of the organic com- 500 mL of deionized water. First, 100 mL were used to pound to the conduction band of TiO by photonic exci- wash under ultrasonic stirring for 30 min. Next, 400 mL tation. The visible light absorption in the solid is were used to wash by magnetic stirring for 240 min. Fi- increased when the amount of anchored carboxylate nally, the nanoparticles were filtered and dried at 120 °C groups is higher. This condition gives it the ability to to get the powered functionalized materials. have more photon receptor sites [15, 16]. The decom- position of MA on the surfaces (1 0 1), (1 0 0), and (0 0 2.4 Synthesis of modified TiO by physical methods 1) of TiO single crystal (anatase) indicates the presence A comparative study with other two synthesis ap- of two types of oxygen on the plane (0 0 1), which are proaches was carried out to determine the effectiveness found by X-ray photoelectron spectroscopy. This obser- of the functionalization method. The first method, vation explains the bidentate adsorption geometry known as a physical mixture, consisted of a simple com- formed by a ring-opening reaction of MA on the planes bination of MA with TiO powders at room (1 0 1) and (0 0 1). Also, four oxygen equivalents on the temperature. The second one, the impregnation method, TiO surface indicate a similar behavior of MA for car- was done under similar conditions as in the functionali- boxylic acid [12]. Wilson et al. [14] found similar results zation method but at room temperature to get dried about the adsorption of MA on the plane (0 0 1) of sin- powered materials. gle rutile crystals. Dissociative adsorption was suggested to be the most stable configuration of the TiO /MA sys- 2.5 Quantification of chemically adsorbed MA on the TiO 2 2 4+ tem. The MA is adsorbed by the Ti species on the surface 5C TiO surface, interacting with the oxygen atoms [17– The initial weights of MA in the synthesis of the samples 20]. Others have mentioned the procedures to anchor 1TiMA-ET and 2TiMA-ET were 0.0061 and 0.0158 g, MA on the solids [21–23]; however, such procedures respectively. At the end of the reaction and the post- imply using highly specialized methodologies such as functionalization treatments (washing and drying), the ultra-high vacuum systems. Therefore, this work de- final weights of MA obtained by Thermogravimetric velops an easy and efficient method of functionalizing Analysis (TGA) were 0.0046 and 0.0108 g. From this TiO nanoparticles with MA. data, the actual amount of chemically adsorbed MA on the TiO surface can be quantified. 2 Materials and methods 2.1 Materials 2.6 Photocatalytic procedure -1 The MA (C H O , MW = 98.06 g mol , ≥ 99.0% pure) A kinetic study evaluated the photocatalytic activity of 4 2 3 was supplied by Sigma-Aldrich. The solvents used as re- the functionalized samples to degrade the dye under UV action media, toluene (TO) and ethanol (ET), were pur- radiation using 40 mg of catalyst and 40 mL of MO so- -5 chased from CTR Scientific. TiO nanoparticles were lution (4 × 10 M), maintaining room temperature purchased from Degussa P-25 with a mean particle size using a cooling system. Adsorption tests were performed 2 -1 of ~21 nm, a surface area of 50 m g , and a mixture of on the catalysts in a MO solution using magnetic stirring anatase (~80%) and rutile (~20%). The dye used in the without UV light for 60 minutes. After that, the solution photocatalytic tests was MO (C H N NaO S, MW = was irradiated by 4 UV lamps Vilber-Lourmat T-15L (15 14 14 3 3 -1 327.3 g mol ) from Sigma-Aldrich. W, λ = 365 nm) for 90 min, and its absorbance was ana- lyzed every 10 min by UV-Vis. Previously, the solid- 2.2 Synthesis of functionalized TiO liquid phases were separated by centrifugation. 0.3 g of TiO were dispersed in 190 mL of ET or TO. The mixture was stirred and heated to 50 or 80 °C de- 2.7 Characterization of the samples pending on the solvent used. Then, MA was dissolved in The thermal behavior of the modified TiO was deter- 10 mL of solvent while adding slowly. After that, the re- mined by TGA and Differential Thermal Analysis (DTA) action was brought to a temperature below the boiling on an SDT Q600 of TA. The heating rate was 10 °C Del Castillo et al. Sustainable Environment Research (2022) 32:7 Page 3 of 9 -1 min from 25 to 600 °C. The Fourier Transform Infra- required for the total desorption of unreacted MA and red (FTIR) spectra were recorded using a Nicolet 670 residual solvent was 500 mL. -1 spectrometer from 400 to 4000 cm . The samples were TGA curves show a noticeable decrease in the per- mixed with spectroscopic grade KBr, measured with 32 centage of weight loss of the washed samples in the -1 scans with a resolution of 4 cm . Diffuse Reflectance temperature range from 200 to 600 °C, due to the de- Spectra (DRS) were collected by S2000 UV-Vis spectro- composition and desorption of chemically adsorbed MA photometer from Ocean Optics using Ca SO as a blank. on the TiO surface shown in Fig. 2. In addition, sample 2 4 2 The crystal structure of the samples was determined by 2TiMA-ET had a more significant weight loss than sam- X-Ray Diffraction (XRD, GBC-Difftech MMA model) ple 1TiMA-ET due to the increased anchored MA on using Cu Kα irradiation at λ =1.54 A° in a range from the TiO surface. This observation showed the outstand- -1 10 to 80° of 2θ, a speed recording of 2° min and an ing contribution of washings in eliminating physically interval of 0.02°. The absorption spectra of the MO were adsorbed organic compounds from the functionalized obtained by S2000 UV-Vis spectrophotometer using an TiO surface. Before the characterization, these trials integration time of 100 ms and 5 scans. In addition, the were very important to perform the exclusive quantifica- residual water used in the washings was analyzed by tion of chemically adsorbed MA on the TiO surface. Total Organic Carbon (TOC, VCPH-CPN, Shimadzu) to determine the TOC concentration. 3.2 Crystal structure The XRD patterns were indexed with the crystallo- graphic planes corresponding for each phase according 3 Results and discussion to the JCPDS 21-1272 (anatase) and JCPDS 03-1122 (ru- 3.1 Chemical stability tile) cards. Figure 3 shows the XRD patterns of the The physical adsorption between the organic com- surface-modified TiO samples by physical mixture, im- pounds and the TiO surface has a lower cohesion than pregnation, and functionalization methods. All the pat- the chemical adsorption. Therefore, these attraction terns, corresponding to the pristine sample and the forces can be eliminated by washing with ultrasonic and modified samples, showed similar crystalline phases (an- magnetic stirring. These processes removed the un- atase and rutile), indicating that the surface MA functio- reacted MA from the functionalized TiO surface be- nalization of the TiO has no effect in its crystalline cause of its high solubility in water. The washing effect- structure. However, there is a slight shift to the left in iveness was confirmed by the decrease in the TOC the diffraction pattern of the sample 2TiMA-ET synthe- concentration of the wastewater collected after washings. sized by functionalization (chemical method). While the Figure 1 shows the progressive decrease of the TOC XRD patterns obtained of the samples synthesized by concentration when the volume of water is increased. physical mixture and impregnation methods did not The concentrations of the last three washes were lowest show any shift because its surface modification is by and very similar, which confirms the loss of organic ma- simple physical interaction. The shift in the diffraction terial. As a result, the minimum volume of water angle is observed due to the transparency effect Fig. 1 TOC analysis of residual water used in washings of the Fig. 2 TGA curves of the functionalized samples before and after sample 2TiMA-ET washing process Del Castillo et al. Sustainable Environment Research (2022) 32:7 Page 4 of 9 according to a similar procedure for an XPS spectrum [25, 26]. The most precise fit presented for the band -1 centered at 1700 cm resulted in two components. The deconvolution showed two peaks around 1714 and 1696 -1 cm which were considered asymmetric vibrations of - -1 COO . The band centered at 1570 cm was fitted into three components. The deconvolution revealed the con- tribution of three different bands. Two at 1546 and 1514 -1 cm are assigned to different symmetric vibrations of - -1 COO , and the last one at 1584 cm corresponding to the stretching vibration of C=C, which has a shift of 10 -1 cm compared with the absorption band on the FTIR spectra of the pure MA [27–29]. Mirone and Chiorboli -1 [27] observed a similar absorption band at 1587 cm , when the maleic acid was used. This slight shift is justi- fied because there is no direct interaction between the C=C bond and the solid surface. Vibration bands of C-O Fig. 3 XRD patterns of the samples: pristine TiO , 2TiMA-M, 2TiMA-I, -1 were observed at 1160 and 1096 cm . Another well- and 2TiMA-ET -1 defined band at 1220 cm was assigned to a bending vi- bration in the plane of the C-H bond [28, 29]. presented when the X-ray beam interacts with the chem- Thedifferencebetween theasymmetric andthe symmet- ically anchored MA on the TiO surface [24]. ric stretch vibrations of the carboxylic acids (Δγ ) defines 2 as-s the adsorption geometry of the MA molecule on the solid 3.3 FTIR spectroscopy surface. Commonly, the ranges for monodentate adsorption -1 Fig. 4 shows the FTIR spectra of the functionalized sam- are 350-500 cm , bidentate bridging are 150-180, and 60- -1 ples 1TiMA-ET and 2TiMA-ET, previously washed and 100 cm for bidentate chelating. In our case, there is a -1 -1 dried. The asymmetric (1869 cm ) and symmetric (1783 Δγ of 150 cm , approximately. Therefore, the adsorp- as-s -1 cm ) C=O vibrations of the MA molecule were not ob- tion form of the MA on the TiO surface corresponds to -1 served. However, two bands at 1714 cm and another at bidentate bridging, as shown in Fig. 6C. Furthermore, the -1 -1 -1 1696 cm were found on the band centered at 1700 cm . vibration band at 1160 cm assigned to the C-O bond sup- -1 The band centered at 1570 cm of the spectrum of the ports the assumption of bidentate bridging adsorption. sample 2TiMA-TO is composed of COO symmetric vi- Others authors observed a stretching vibration of the C-O -1 brations and stretching vibrations of the C=C bond. bond near 1140 cm [30, 31], which confirms the bidentate These assumptions were confirmed by deconvolutions geometry of the propoxy species on the TiO surface. of the FTIR spectra, as shown in Fig. 5. The fit was done The TiO nanoparticles used in our study consist in two and three components using Lorentzian functions mainly of anatase. The (1 0 1) plane is the most com- mon surface for this phase. Therefore, it favors the bidentate bridging adsorption, which involves the ring- opening of the MA molecule [32, 33]. Kim and Barteau [34] observed an identical behavior in the carboxylic acids and other analogous organic molecules. 3.4 TG and DT analyses The thermal behavior of the sample 2TiMA-ET had two main weight losses, as shown in Fig. 7. The first one was about 1.2% in a temperature range from 25 to 200 °C, at- tributed to the elimination of water, residual solvent, and possible remnants of unreacted MA [35]. Feist et al. [36] observed the same endothermic peak as the typical behavior of a desorption process. The second weight loss was 4.1%, which coincided with a strong exothermal ef- fect in the range from 200 to 580 °C on the thermal Fig. 4 FTIR spectra of TiO , 1TiMA-ET, and 2TiMA-ET in the range curve, attributed to the decomposition and desorption of -1 from 4000 to 1000 cm anchored MA. Nikumbh et al. [35] observed exothermic Del Castillo et al. Sustainable Environment Research (2022) 32:7 Page 5 of 9 -1 Fig. 5 FTIR spectra of TiO , 1TiMA-ET, 2TiMA-ET, and 2TiMA-TO in the range from 2000 to 1100 cm peaks related to the decomposition of maleates com- Functionalization degreeðÞ % pounds between 250 and 450 °C. Decomposition- anchored MAðÞ g ¼ 100 ðÞ 1 desorption of MA on the TiO mainly occurred between TiO usedðÞ g 280 and 470 °C. Desorption of carbonates due to the de- composition of MA was observed at 470 °C, the desorp- Experimental result Reaction efficiencyðÞ % ¼ 100 tion of acetylene and CO occurred at 500 °C [5, 21]. 2 Theoretical result The functionalization degree and the reaction effi- ciency of the samples 1TiMA-ET and 2TiMA-ET (as shown in Table 1) were calculated from the experimen- The functionalization process suggests there is a low tal conditions of the reaction and TGA results, using the concentration of anchored MA molecules on the TiO Eqs. (1) and (2): surface due to steric hindrance when occupying surface Fig. 6 Possible adsorption modes of the MA molecule on the TiO surface: A and A’) monodentate, B) bidentate chelating, and C) bidentate bridging Del Castillo et al. Sustainable Environment Research (2022) 32:7 Page 6 of 9 Fig. 7 TG-DTA curves of the sample 2TiMA-ET from 25 to 600 °C Fig. 8 UV-Vis diffuse reflectance spectra of the samples: pristine TiO , 2TiMA-M, 2TiMA-I, 2TiMA-TO, and 2TiMA-ET area in the TiO nanoparticles. Therefore, the TiO sur- 2 2 face is partially functionalized and has a limited amount light penetrates through molecular chains of anchored of anchored reactant on all the reaction sites located on MA to interact with the TiO surface. the TiO surface. As a result, a decrease in the reaction Figure 9 shows a decrease in the bandgap energy of efficiency of the sample 2TiMA-ET for the sample TiO from 3.05 to 2.55 eV that extended to visible re- 1TiMA-ET was observed. gion for the functionalized sample 2TiMA-ET due to the anchored MA on the TiO surface. The samples 2TiMA-ET and 2TiMA-TO synthesized by the chemical 3.5 UV-Vis DRS method showed a significant decrease in its bandgap en- The UV-Vis spectra of modified TiO samples synthe- ergy compared with the samples 2TiMA-physical mix- sized by physical and chemical methods are shown in ture and 2TiMA-impregnation method obtained by Fig. 8. The functionalized samples exhibited a noticeable physical methods, which showed similar behavior in the increase in visible light absorption and decreased band- visible light absorption to commercial TiO . The band- gap energy. For example, the area under the curve of the gap energy values of the functionalized samples were 2TiMA-ET absorption spectrum, integrated from 400 to similar to the results of other authors with the dye- 700 nm, increased 36 units compared with that of pris- sensitized TiO surface because the dye can absorb vis- tine TiO . On the other hand, the samples performed by ible light [37]. However, our synthesis method is simpler physical methods did not show any increase in the vis- ible light region concerning pristine TiO . This observa- tion confirms the presence of anchored MA on the TiO surface and means that it can be excited with less en- ergy, thus extending its absorption range from UV light to the visible region. Also, functionalized samples were able to absorb visible light beyond 400 nm. However, the MA only absorbs at 204 nm corresponding to the UV region. Therefore, the visible light absorption observed in the UV-Vis spectra of the functionalized samples is attributed to the physical obstacle presented when the Table 1 Functionalization degree and reaction efficiency of the samples 1TiMA-ET and 2TiMA-ET a b Sample w (g) w (g) FD (%) Reaction efficiency (%) i f 1TiMA-ET 0.0061 0.0046 1.54 76 2TiMA-ET 0.0158 0.0108 3.61 69 Fig. 9 DRS spectra and bandgap energy of the samples: pristine Initial weight of MA in the reaction TiO , 2TiMA-M, 2TiMA-I, 2TiMA-ET, and 2TiMA-TO Final weight of anchored MA on the TiO surface obtained by DTA 2 Del Castillo et al. Sustainable Environment Research (2022) 32:7 Page 7 of 9 and cheaper than the other functionalization processes However, there is a faster degradation rate of the MO with complex and expensive methods [38, 39]. solution using the functionalized TiO The surface modification with MA inhibits the recombination of the 3.6 Photocatalytic tests hollow-electron pair and decreases the bandgap to 2.55 The photocatalytic analysis was carried out by degrading eV; this characteristic facilitates a more significant trans- MO under UV light radiation using pristine TiO and fer of electrons and improves photocatalytic activity. 2TiMA-ET as photocatalysts, as shown in Fig. 10. All Based on experimental studies, a schematic diagram of the UV-Vis spectra exhibit a decrease in the absorbance the band levels of the 2TiMA-ET composite and the of the band centered at 463 nm (absorption wavelength possible mechanism of the photocatalytic reaction in the attributed to -N=N- bond) due to the progressive deg- MO dye degradation are proposed and illustrated in Fig. radation of the MO solution. The catalysts were tested 11. using the same conditions to determine their capacity to The commercial and functionalized TiO were photo- adsorb dye without light. When the commercial TiO is catalytically evaluated by kinetic parameters calculated functionalized with MA, its surface adsorption is in- from the MO degradation with UV light. These parame- creased. However, thus physical ability is not significant ters were the reaction's constant rate, conversion, and because the low percentage of anchored MA cannot ad- half-life, as shown in Table 2. The conversion reaction sorb much dye. For the kinetic study, the photo- of functionalized TiO was improved by 3.2% compared degradation evaluation only is considered after the ad- with the commercial TiO , as shown in Fig. 12. The re- sorption tests. The UV-Vis absorbance spectra obtained action order is first according to the Langmuir- to degrade the MO solution using the functionalized Hinshelwood model due to its high linear correlation of sample 2TiMA-ET (Fig. 10b), and the commercial TiO values. The rate constant can be obtained through the (Fig. 10a) showed a progressive decrease of the absorp- equation Inc = -kt + Inc0 by linear regression, where (k) tion band of the MO due to its degradation. The MO is the rate constant, (c) is concentration, and (t) is the solution was degraded using both catalysts after 90 min reaction time. One of the limitations to obtain a higher of reaction time based on the absorbance curves. reaction rate is a high initial dye concentration because it can hinder the free passage of photons in the solution to be degraded [38, 39]. The constant rate and half-life of reaction also showed better results with the function- alized sample 2TiMA-ET than for the pristine TiO This result was expected because of the synergy pro- duced between the organic molecules and the TiO sur- face. These conditions favor the production of a greater amount of electron acceptor sites that retard the recom- bination of the electron-hole pair and the presence of oxidizing agents on the surface of TiO nanoparticles [40]. Figure 13 shows the reuse tests for the TiO and -5 Fig. 10 UV-Vis spectra of the degradation of MO (4 × 10 M, pH = Fig. 11 Schematic diagram of the band levels of 2TiMA-ET and the 7.0) using the catalysts: (a) pristine TiO and (b) 2TiMA-ET possible reaction mechanism of the photocatalytic procedure 2 Del Castillo et al. Sustainable Environment Research (2022) 32:7 Page 8 of 9 Table 2 Kinetic results of the photocatalytic degradation of MO -5 (4 × 10 M) under UV radiation a -1 b c Sample k (min ) C/C Conversion reaction (%) t (min) 0 1/2 TiO 0.032 0.058 94 22 2TiMA-ET 0.044 0.026 97 15.9 Reaction rate Fraction of conversion reaction Half time of reaction 2TiMA-ET samples and found that the final degradation percentage of the MO dye (after 90 min) was reduced only by 7% after using the 2TiMA-ET for 4 consecutive times while for the commercial TiO when is reused 4 times, the degradation efficiency is reduced by 13%. Thus, the 2TiMA-ET is the most stable and presents a higher photocatalytic activity in the degradation of MO Fig. 13 Reuse tests for the TiO and 2TiMA-ET photocatalysts in the than the commercial TiO . This work presented a -5 degradation of MO (4 × 10 M, pH = 7.0) greater efficiency in the photocatalytic degradation of the MO dye under UV light radiation (97% at 90 min using 2TiMA-ET) compared to other similar investiga- samples 1TiMA-ET and 2TiMA-ET were 76 and 69%, tions where MO and other types of dyes were degraded respectively. The diffraction pattern of the functionalized [8–10]. sample 2TiMA-ET did not change its crystalline phases from the pristine TiO . However, the bandgap energy of TiO decreased from 3.05 to 2.55 eV when its surface 4 Conclusions was functionalized with MA. DRS spectra show that the The MA was chemically adsorbed onto the surface of absorbance of the 2TiMA-ET sample was higher and the TiO nanoparticles showing good stability after sev- more extended in the visible range of 400-800 nm than eral washings. MA functionalization was confirmed by that for the TiO pristine due to the presence of oxygen FTIR, DRS, and XRD results. The FTIR analysis showed vacancy defects, which act as electron trapping centers vibration bands of bonds that indicate the chemical and delay the electron-hole recombination. This higher interaction between the MA molecules and the TiO absorbance is suitable because it increases the probabil- nanoparticles. The adsorption geometry of MA on the ity of photogeneration of electron-hole pairs, which are TiO surface was determined as bidentate bridging. TG- responsible for the generation of oxidizing agents that DTA quantified the chemically adsorbed MA onto the degrade the MO. As a result, the functionalized TiO TiO nanoparticles. The reaction efficiencies of the showed improvements in its photocatalytic properties, increasing 3.2% in the MO degradation rate compared with the commercial TiO . Acknowledgments The authors are grateful to Octavio Domínguez Espinos and Martha Lomelí Pacheco for carrying out the FTIR studies. Authors’ contributions Pável César Hernández-Del Castillo* carried out the experiments, discussed the results, and wrote the submitted manuscript; Saúl Robles-Manuel contrib- uted to the discussion of results, supported ideas for the project, and helped to supervise trials. Facundo Ruiz contributed to the submitted version of the manuscript, provided critical feedback, and supervised the project's perform- ance. Finally, Vicente Rodríguez-González contributed to the preparation and characterization of the samples and helped shape the research and the elab- oration of the final manuscript. All authors read and approved the final manuscript. Funding -5 The authors also appreciate the support from CONACYT (Consejo Nacional Fig. 12 The kinetics of MO (4 × 10 M, pH = 7.0) photo- de Ciencia y Tecnología) in this research and the granted postdoctoral degradation using the catalysts: pristine TiO and 2TiMA-ET fellowship. Del Castillo et al. Sustainable Environment Research (2022) 32:7 Page 9 of 9 Availability of data and materials 19. Kavathekar RS, Dev P, English NJ, MacElroy JMD. Molecular dynamics study All data generated or analyzed during this study are fully available to give of water in contact with the TiO rutile-110, 100, 101, 001 and anatase-101, certainty to the work carried out. 001 surface. Mol Phys 2011;109:1649–56. 20. Cai YQ, Bai ZQ, Chintalapati S, Zeng QF, Feng YP. Transition metal atoms 3+ pathways on rutile TiO (110) surface: distribution of Ti states and Declarations evidence of enhanced peripheral charge accumulation. J Chem Phys 2013; 138:154711. Competing interests 21. 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Sustainable Environment Research – Springer Journals
Published: Jan 21, 2022
Keywords: Functionalization; Titanium dioxide nanoparticles; Photocatalysis; Maleic anhydride; Nanostructures
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