A stable catalyst for simultaneous catalytic removal of nitrogen oxide and toluene at low temperature

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This work has compared the different behaviors of V/TiO 2 and CeV/TiO 2 in separate and simultaneous catalytic removal of NO and toluene. Both the catalysts have been detailly characterized and compared. The catalytic oxidation of toluene obviously disturbed the catalytic reduction of NO by V/TiO 2 . NO removal was decreased from 99% to 72% at 250°C. In comparison, the toluene only decreased the NO removal of CeV/TiO 2 from 95% to 85%. From the viewpoint of toluene, the NO slightly decreased the toluene removal of V/TiO 2 but hardly affected the toluene removal of CeV/TiO 2 . The more stable performance of CeV/TiO 2 was attributed to its lower adsorption energies/abilities for various pollutants and derived intermediates. Catalytic oxidation Catalytic reduction Volatile organic compounds Nitrogen oxide Titanium dioxide Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Article Highlights (1) Catalytic oxidation and reduction have a mutual interference. (2) CeV/TiO 2 is more stable than V/TiO 2 in the mutual interference. (3) The stability is attributed to lower adsorption energies for various pollutants. 1. Introduction Volatile organic compounds (VOCs) and nitrogen oxide (NOx) are two typical air pollutants [ 1 ]. Examples of VOCs are halogenated hydrocarbons, aldehydes, aromatics, alkanes, ketones, and sulfur containing compounds. High concentrations of these VOCs cause irritations, dizziness, headaches, and even cancers for both humans and animals [ 2 ]. NOx potentially cause acid rain, photochemical smog, and eutrophication. Furthermore, VOCs and NOx are both crucial precursors of ozone and PM 2.5 [ 3 ]. Some industries only discharge VOCs, such as petrochemical, pharmaceutical, paint, and leather manufacturing. However, some others discharge both VOCs and NOx, such as thermal power, incineration, glass, cement, steel sintering, and ceramics. Therefore, the simultaneous removal of VOCs and NOx is a necessary. If only VOCs are aimed to be removed, the catalytic oxidation is accepted to be the most effective and reliable technology. Theoretically, VOCs react with O 2 to form H 2 O and CO 2 with the help of the catalyst [ 4 ]. The commercial VOCs catalyst includes noble-metal (Pt, Pd, Ag) and transition-metal (Mn, Ce, Cu) catalysts [ 5 , 6 ]. If the polluted gas only contains NOx, selective catalytic reduction (SCR) is widely recognized as the most cost-effective method [ 7 ]. In brief, NOx catalytically react with the reductant, forming harmless H 2 O and N 2 [ 8 ]. The most typical reductant and catalyst are NH 3 and V/TiO 2 , respectively. In fact, V/TiO 2 is a commercial catalyst used in the real industry [ 9 ]. In recent years, other reductant is put forward to replace NH 3 , such as hydrocarbons and carbon monoxide [ 10 , 11 ]. Thus, researchers also ask themselves if VOCs can potentially be used as the reductant of SCR. The simultaneous removal thus reduces equipment construction costs and space requirement [ 12 ]. However, two difficulties exists. On one hand, one bifunctional catalyst must be developed working at a same temperature range for both these two gases [ 13 ]. This is relatively easy to solve since typical catalytic temperatures for these gases are 180–300°C. We even can find catalysts that can efficiently catalyze these gases alone. For example, MnO 2 effectively catalyze VOCs and NOx at 250°C and 100–250°C, respectively [ 14 , 15 ]. On the other hand, catalytic oxidation and catalytic reduction potentially affect each other because these two processes both utilizes surface oxygens on the catalyst [ 16 , 17 ]. Several attempts have showed that the NH 3 -SCR inhibits the toluene oxidation if a same catalyst is used [ 18 , 19 ]. The main reason is that the reactive intermediate of one catalyst is a blocking species for the other [ 19 ]. Therefore, decreasing the competitive effect seems to be more pragmatic than using VOCs as the reductant of SCR. In this work, V/TiO 2 and CeV/TiO 2 are synthesized and compared in simultaneous catalytic removal of toluene and NO. Both the catalysts and catalytic processes are detailly characterized. The adsorption energies of different gaseous molecules are calculated by the density functional theory. With these investigations, a mechanism is put forward to explain why CeV/TiO 2 is a more stable catalyst. 2. Materials and Methods 2.1. Catalyst Preparations The catalyst was synthesized by an impregnation method [ 20 ]. In detail, ammonium metavanadate and ammonium cerium nitrate were dissolved in 100 mL of deionized water at 70°C. TiO 2 (5 g) was dispersed into the above solution, and stirred for 2 h. After a well mixing, the solution was dried at 105°C before being calcined at 450°C for 2 h. The prepared catalysts were milled to 50 mesh and denoted as V/Ti and CeV/Ti. The metal contents of these catalysts were detected by which were an Inductively Coupled Plasma-Atomic Emission Spectrometry (IRIS Advantage 1000, Thermo Fisher) after the standard digestion. V/Ti resulted in a V-loading amount of 5 wt.%. In CeV/Ti, molar ratio between Ce and V was around 1:1. 2.2. Catalytic Performances Catalytic oxidation of toluene and NH 3 -SCR were carried out on a fixed-bed reactor [ 21 ], which is showed in Fig. S1 in the Supporting Information. Setup details are also provided below the figure. Removals of toluene (X T ) and NO (X NO ) are calculated according to Eqs. (1) and (2). N 2 selectivity is calculated accordingly by Eq. (3). In these equations, the subscripts “in” and “out” stands for concentrations in the inflow and outflow, respectively. 2.3. Characterizations X-ray diffraction (XRD) was carried out using a powder diffractometer (MiniFlex600, Rigaku) equipped with Cu Kα radiation. Textural properties were detected by Autosorb-IQ2. Temperature-programmed desorption of NH 3 (NH 3 -TPD) and temperature-programmed reduction of H 2 (H 2 -TPR) were carried on a VD Sorb-91i (Quzhou Vodo instrument Co. Ltd., China). Binding energies of elements were analyzed by a K-Alpha X-ray photoelectron spectroscopy (XPS, Thermo Scientific, USA). In-situ Diffuse Reflection Fourier Transform Infrared Spectrometer (DRIFTs) was carried out on Nicolet IS10 (Thermo Scientific) with an MCT detector at a resolution of 4 cm − 1 [ 22 ]. The sampling intervals are all 0, 1, 3, 5, 10, 20, and 30 min. All calculations were based on spin polarization density functional theory (DFT) such as Vienna First Principles (VASP) and projected Enhanced waves (PAW). The exchange correlation function used was a local density approximation with generalized gradient correction, called GGA-PBE [ 23 , 24 ]. The energy of the plane wave was truncated to 400 eV for all atoms, and the ion positions of all structures were relaxed until the force converges to 0.03eV·Å. 3. Results and Discussion 3.1. Simultaneous Catalytic Removal of NO and Toluene Figure S2A investigates the possibility of using toluene as the reductant of SCR process. Unfortunately, the NO removals are close to zero at the tested temperatures. If the O 2 is removed from the inflow gas, both the conversions of NO and toluene are close to zero ( Fig. S2B ). However, if the temperature is further increased to 350°C, both NO and toluene conversions are increased to about 20 − 30%. Considering this, even the toluene is feasible to be used as the reductant of SCR, the suitable temperature is too high. On one hand, if V/TiO 2 is used in the SCR, a removal of 65% is reached at 100°C (Fig. 1 A). When the temperature is increased to 200°C, the removal has been increased to 99%. In comparison, when the toluene is mixed into the inflow gas, the NO removal is obviously decreased. For example, the removal is decreased to 37% at 100°C. On the other hand, if V/TiO 2 is used in the catalytic oxidization of toluene, the ignition temperature is started between 200 and 250°C (Fig. 1 B). When the NO and NH 3 are mixed into the inflow gas, the toluene removal is also affected. For example, the removal at 300°C is decreased from 99% to 67%. When Ce is co-doped onto the TiO 2 , CeV/TiO 2 has a better resistant ability for co-existing toluene (Fig. 1 A). The removals between 100 and 200°C is hardly affected. The removal is decreased from 98% to 86% at 300°C. The difference is 12%. In comparison, the difference is 23% using V/TiO 2 . As for the side of toluene, similar phenomenon is observed (Fig. 1 B). The catalytic activity of CeV/TiO 2 is hardly affected by the co-existing NO and NH 3 . The conversion curves are almost overlapped. In addition, the co-catalysis has no influence on the N 2 selectivity either ( Fig. S2C ). After all, CeV/TiO 2 is more stable than V/TiO 2 in the simultaneous catalysis. 3.2. Basic Characterizations Table 1 Textural properties of V/TiO 2 and CeV/TiO 2 . Specific surface area (m 2 ·g –1 ) V/TiO 2 CeV/TiO 2 47.2 48.5 Pore volume (cm 3 ·g –1 ) 0.42 0.43 Pore size (nm) 38.3 38.8 O α (%) 87 86 O β (%) 8 8 O γ (%) 5 6 V 3+ (%) 26 12 V 4+ (%) 44 53 V 5+ (%) 30 35 V/TiO 2 and CeV/TiO 2 show a similar XRD pattern (Fig. 2 A). Anatase TiO 2 (PDF#84-1285) has diffractions at 25.3 ° (101), 37.8 ° (004), 48.0 ° (200), 53.9 ° (105), 55.1 ° (211), and 62.7 ° (204), while the main diffraction of rutile TiO 2 (PDF#87–0710) is detected 27.5 ° (110) [ 25 ]. Besides, both catalysts exhibits a type IV isotherm with a hysteresis loop (Fig. 2 B), which is the proof of the mesoporous structure [ 26 ]. In fact, the two catalysts have similar textural properties (Table 1 ). For example, the specific surface areas are 47.2 and 48.5 m 2 ·g –1 . Brønsted-acidic sites (100–250°C) and the Lewis-acidic sites (300–450°C) are observed in Fig. S3A . The Brønsted-acid site favors the SCR [ 27 ]. After the integration, the relative area of the Brønsted-acidic site in V/TiO 2 is 283 (a.u.), which the relative area of the Lewis-acid site is 96 (a.u.). In comparison, CeV/TiO 2 has 148 (a.u.) of Brønsted-acidic sites and 169 (a.u.) of Lewis-acid sites. This explains why V/TiO 2 has a better SCR activity than CeV/TiO 2 . H 2 -TPR stands for the reduction of both VOx and CeOx ( Fig. S3B ). The overall reductive ability is reduced after co-doping Ce in V/TiO 2 . The peak of XPS O 1s at 528–534 eV is typically made up to lattice oxygen (O α ), oxygen vacancy (O β ), and surface hydroxyl (O γ ) [ 20 ]. Figure 2 C are fitted into these components and the results are listed in Table 1 . V/TiO 2 and CeV/TiO 2 show similar amounts of these oxygen species. Their main components are O α , which occupies 86–87% of all oxygen species. Figure 2 D further compares the XPS V 2p of these two catalysts. The V 2p is usually fitted into three species, including V 5+ (517 eV), V 4+ (516 eV), and V 3+ (515 eV) [ 26 ]. Between the two catalysts, V/TiO 2 exhibits a higher proportion of low-valence V species (70%), which enhances the redox cycle on the catalyst surface [ 28 ]. This is consistent with the H 2 -TPR result. According to the above comparisons, the reason is revealed why V/TiO 2 has better catalytic performances than CeV/TiO 2 in separate removal of toluene and NO. However, the above similarity and differentia is infeasible to explain why CeV/TiO 2 has a more stable performance in simultaneous removal of toluene and NO. 3.3. Catalytic Processes When the catalytic oxidation occurs on CeV/TiO 2 at 250°C (Fig. 3 A), several obvious peaks are observed at 3029, 2930, 1644, and 1513 cm –1 . According to previous reports, clear bands at 1513and 1644 cm − 1 are associated with the vibration of aromatic rings [ 29 ]. 2931 cm − 1 is attributed to the antisymmetric peaks of CH in CH 2 , i.e., the benzyl radicals are generated [ 30 ]. 3029 cm − 1 is derived from C‒H stretching vibration in benzene ring [ 30 ]. After NH 3 flows into the reactor, the peaks are hardly affected at 1513 and 1644 cm − 1 . However, new peaks are observed at 1451 and 1173 cm − 1 , which are attributed to adsorbed NH 3 species on Brønsted and Lewis acid sites, respectively [ 31 ]. At the same time, the peaks at 3029 and 2930 cm − 1 are placed by new peaks at 3250 and 3151 cm − 1 step by step. They belongs to ascribed to N–H stretching vibration modes of NH 3 and NH 4 + , respectively [ 32 , 33 ]. This indicates that two possibilities. One is that intermediates of toluene decomposition are replaced by NH 3 -derived species. The other is that these intermediates even react with NH 3 . Whatever the possibility, NH 3 -derived species are feasible to be adsorbed onto the catalyst surface. After NO + O 2 flows into the reactor, the peaks at 1513 and 1644 cm − 1 still exists even after 30 min. On the contrary, the intensities of NH 3 -derived species are all decreased along with time. This indicates that NH 3 molecules are first adsorbed on the catalyst surface and then react with NO, which is called an Eley-Rideal (E-R) mechanism. In comparison, when V/TiO 2 is used in the catalytic oxidation of toluene (Fig. 3 B), the peak at 1400 cm − 1 represents the shorter carboxylate species (especially acetate) [ 34 ]. In addition, peaks are also observed at 3029, 2930, 1644, and 1513 cm − 1 . After NH 3 flows into the reactor, above peaks are hardly affected. Although the peaks at 3029 and 2930 cm − 1 are obviously decreased, no NH 3 -derived species are formed. After NO + O 2 flows into the reactor, the relative intensities at 1644 and 1513 cm − 1 are decreased. The peak intensity at 1400 cm − 1 is stable. Thus, the intermediate shorter carboxylate species is hard to be replaced. After all, no NO + O 2 derived species are formed. In other words, the intermediates of toluene decomposition disturb the SCR on V/TiO 2 . This is different from CeV/TiO 2 , which functions normally in SCR even with the intermediates. In Fig. 4 A, NO + O 2 flows into the reactor after the catalytic oxidation of toluene for 30 min. The peaks at 3029 and 2930 cm − 1 removed from the catalyst surface by the NO + O 2 flow. An overlapping peak at 1538 cm − 1 is formed and attributed to NO 2 on Lewis acid sides. After NH 3 flows into the reactor, these peaks are hardly affected). Besides, peaks are formed at 3250 and 3151 cm − 1 . These phenomena at least suggest that NH 3 are adsorbed. As is well-known, if NH 3 reacts with the pre-adsorbed NO + O 2 , the SCR is carried out by the Langmuir-Hinshelwood (L-H mechanism). However, it is hard to judge whether SCR is carried out by this mechanism. After NO + O 2 flows into the reactor (Fig. 4 B), the peak intensities are decreased at 1644, and 1513 cm − 1 . However, the three peaks still observed after 30 min. Although the peak intensities are also decreased at 3029 and 2930 cm − 1 , no obvious NO + O 2 -derived species are recognized. Similarly, after NH 3 flows into the reactor, no further change is observed. According to the previous reports, the V/TiO 2 -based catalyst participates in the SCR by both L-H and E-R mechanisms [ 35 , 36 ]. Considering this, the catalytic oxidation of toluene interferes the L-H mechanism by both the catalysts but only interferes the E-R mechanism by V/TiO 2 . This is the reason why CeV/TiO 2 is more stable than V/TiO 2 in the simultaneous catalysis of toluene and NO. 3.4. Catalytic Mechanism Table 2 Adsorption energies of different gases on V/TiO 2 and CeV/TiO 2 . CO 2 adsorption V/TiO 2 CeV/TiO 2 4.127 2.885 NH 3 adsorption -1.693 -1.688 NO adsorption 11.572 4.441 NO 2 adsorption -0.959 -0.841 DFT calculations are used to compare the adsorption energies of different gases (including CO 2 , NH 3 , NO, and NO 2 ) on V/TiO 2 ( Fig. S4A ) and CeV/TiO 2 ( Fig. S4B ). The detailed values are listed in Table 2 . A negative adsorption energy indicates a spontaneous adsorption on the surface. Besides, the more negative the adsorption energy, the stronger the adsorption [ 37 ]. Therefore, both NH 3 and NO 2 can be adsorbed spontaneously by both V/TiO 2 and CeV/TiO 2 . However, V/TiO 2 has a stronger adsorption than CeV/TiO 2 since its adsorption energies are more negative. On the contrary, a positive value indicates that the adsorption process is endothermic [ 38 ]. Therefore, the adsorption energy of CO 2 is significantly decreased from 4.127 eV (V/TiO 2 ) to 2.885 eV (CeV/TiO 2 ). CO 2 is an important intermediate of toluene decomposition. Its release from the catalyst surface is determining to the continuous catalysis. A lower adsorption energy indicates that the molecule is easier to be replaced by other gases. Similarly, the adsorption energy of NO is significantly decreased from 11.572 eV (V/TiO 2 ) to 4.441 eV (CeV/TiO 2 ). A more stable simultaneous catalysis of toluene and NO is attributed to lower adsorption energies on the catalyst surface after co-doping Ce. When the toluene are adsorbed by V/TiO 2 and CeV/TiO 2 . Intermediates are formed on the surfaces ( Fig. S4CI ). On one hand, NH 3 is feasible to replace these intermediates on the CeV/TiO 2 but infeasible to replace those on the V/TiO 2 ( Fig. S4CII ). As a result, NOx can react with the NH 3 -dervied species to complete the E-R mechanism on CeV/TiO 2 ( Fig. S4CIII and 3 ). On the other hand, NO is infeasible to replace the intermediates on V/TiO 2 and CeV/TiO 2 ( Fig. S4CIV ). As a result, the L-H mechanism is hindered on both these catalysts (Fig. 4 ). 4. Conclusion In this work, V/TiO 2 and CeV/TiO 2 were synthesized and compared in simultaneous SCR and catalytic oxidation of toluene. CeV/TiO 2 was more stable than V/TiO 2 in the simultaneous catalysis. The reason was revealed that CeV/TiO 2 had weaker adsorption abilities for various pollutants and derived intermediates. These species are easier to be replaced by each other on the catalyst surface. Therefore, this work put forward a successful example of designing a suitable catalyst instead of a merely active one. Declarations Acknowledgements We appreciate the help of the Instrumental Analysis & Research Center of Shanghai University in sample characterization. Funding This project was financially supported by the Natural Science Foundation of Shanghai 2021 Science and Technology Innovation Action Plan (21ZR1424000). Author Information Authors and Affiliations Yu Yan, 1 Linmin Lao, 1 Chengyan Li, 2 Yang Yue, 1,3 Guangren Qian, 3 Jia Zhang 1,3 1 SHU Center of Green Urban Mining & Industry Ecology, School of Environmental and Chemical Engineering, Shanghai University, No. 381 Nanchen Road, Shanghai 200444, P. R. China 2 Nanjing Institute of Environmental Sciences, Ministry of Ecology and Environment of the People’s Republic of China, Nanjing 210042, China 3 MGI of Shanghai University, Xiapu Town, Xiangdong District, Pingxiang City, Jiangxi, 337022, P. R. China; Contributions Yu Yan and Linmin Lao contributes to experiment design, data acquisition and analysis, and manuscript drafting. Chengyan Li and Yang Yue contribute to characterizations. Guangren Qian contributes to resources. Jia Zhang contributes to interpretation of data and critical revision of the manuscript. Corresponding Author Correspondence to Jia Zhang. Ethics Declarations Ethics Approval and Consent to Participate Not applicable. 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Rsc Adv 11:2947–2957 Salih HS, Kareem MT, Jibrael KJ (2024) Influence of electron-donating groups on the aniline oxidative coupling reaction with promethazine: a comprehensive experimental and theoretical investigation. React Kinet Mech Catal 137:3265–3296 Additional Declarations No competing interests reported. Supplementary Files SupportingInformation.docx GA.png Graphical Abstract Cite Share Download PDF Status: Posted Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-9218535","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":612234668,"identity":"cb51f4ee-5356-49b6-a966-db5aa0e9de46","order_by":0,"name":"Yu Yan","email":"","orcid":"","institution":"Shanghai University","correspondingAuthor":false,"prefix":"","firstName":"Yu","middleName":"","lastName":"Yan","suffix":""},{"id":612234669,"identity":"2b825da1-bb74-4a7a-a6a2-9e59e76bb2bd","order_by":1,"name":"Linmin Lao","email":"","orcid":"","institution":"Shanghai University","correspondingAuthor":false,"prefix":"","firstName":"Linmin","middleName":"","lastName":"Lao","suffix":""},{"id":612234672,"identity":"f789395a-003d-49bc-bf59-9a7a0f923dbb","order_by":2,"name":"Chengyan Li","email":"","orcid":"","institution":"Nanjing Institute of Environmental Sciences","correspondingAuthor":false,"prefix":"","firstName":"Chengyan","middleName":"","lastName":"Li","suffix":""},{"id":612234673,"identity":"1e83e883-f895-462b-8d01-91d0f1164469","order_by":3,"name":"Yang Yue","email":"","orcid":"","institution":"Shanghai University","correspondingAuthor":false,"prefix":"","firstName":"Yang","middleName":"","lastName":"Yue","suffix":""},{"id":612234674,"identity":"0dc1c7d0-2043-4196-bb7e-2e25671f3e92","order_by":4,"name":"Guangren Qian","email":"","orcid":"","institution":"MGI of Shanghai University","correspondingAuthor":false,"prefix":"","firstName":"Guangren","middleName":"","lastName":"Qian","suffix":""},{"id":612234675,"identity":"d1424d6b-dcb8-4004-8e71-58f2dbe43bcf","order_by":5,"name":"Jia Zhang","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAAzUlEQVRIiWNgGAWjYBACNiA2YGCwAVI8ID4z0VrSJIjXAgWHSdDCJ33GoOBnzvk6Bv6zxyQYKqwTG9jPHsDvML4cA8PebbclGCTygK47k57YwJOXgF8LD4+BAS9YC4+ZBGPb4cQGCR4DgloM/247J8HAfwao5R+RWox5tx0Aej8HqKWBKC1sBcay25Il2yRyjC0SjqUbt/Hk4Nci38O8zfDtNjt+fv4zhjc+1FjL9rOfwa8FZBFYBShOGRJgDAKA+QERikbBKBgFo2AkAwCkhDTNSDguMQAAAABJRU5ErkJggg==","orcid":"","institution":"Shanghai University","correspondingAuthor":true,"prefix":"","firstName":"Jia","middleName":"","lastName":"Zhang","suffix":""}],"badges":[],"createdAt":"2026-03-25 05:39:08","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-9218535/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-9218535/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":105752220,"identity":"d381505a-b3ad-429f-a5cc-904410809a58","added_by":"auto","created_at":"2026-03-30 15:56:02","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":51179,"visible":true,"origin":"","legend":"\u003cp\u003eNO and toluene conversions under 500-ppm toluene, 500-ppm NO, and 10% O\u003csub\u003e2\u003c/sub\u003e by V/TiO\u003csub\u003e2\u003c/sub\u003e (\u003cstrong\u003eA\u003c/strong\u003e); Influence of 500-ppm toluene (\u003cstrong\u003eB\u003c/strong\u003e) and 500-ppm NO (\u003cstrong\u003eC\u003c/strong\u003e) on SCR and toluene catalytic oxidation, respectively, by V/TiO\u003csub\u003e2\u003c/sub\u003e. NO\u003csub\u003eX\u003c/sub\u003e conversion (\u003cstrong\u003eD\u003c/strong\u003e), toluene conversion (\u003cstrong\u003eE\u003c/strong\u003e), and N\u003csub\u003e2\u003c/sub\u003e selectivity (\u003cstrong\u003eF\u003c/strong\u003e) under 500-ppm toluene, 500-ppm NO, 500-ppm NH\u003csub\u003e3\u003c/sub\u003e, and 10% O\u003csub\u003e2\u003c/sub\u003e by CeV/TiO\u003csub\u003e2\u003c/sub\u003e.\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-9218535/v1/bed676c641fa2c6c98920b5b.png"},{"id":105743660,"identity":"b5468151-af63-4709-9b8a-996775a88db2","added_by":"auto","created_at":"2026-03-30 13:46:50","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":59471,"visible":true,"origin":"","legend":"\u003cp\u003eXRD (\u003cstrong\u003eA\u003c/strong\u003e), N\u003csub\u003e2\u003c/sub\u003e adsorption–desorption isotherms (\u003cstrong\u003eB\u003c/strong\u003e), NH\u003csub\u003e3\u003c/sub\u003e-TPD (\u003cstrong\u003eC\u003c/strong\u003e), H\u003csub\u003e2\u003c/sub\u003e-TPR (\u003cstrong\u003eD\u003c/strong\u003e), XPS O 1s (\u003cstrong\u003eE\u003c/strong\u003e), and XPS V 2p (\u003cstrong\u003eF\u003c/strong\u003e) of V/TiO\u003csub\u003e2\u003c/sub\u003e and CeV/TiO\u003csub\u003e2\u003c/sub\u003e.\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-9218535/v1/3a106a0a95be021990d3f95b.png"},{"id":105752066,"identity":"7dbcbd7d-fe09-4da5-8c79-5fd1c0f84eaf","added_by":"auto","created_at":"2026-03-30 15:54:23","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":62882,"visible":true,"origin":"","legend":"\u003cp\u003eDRIFTs of toluene (\u003cstrong\u003eA\u003c/strong\u003e) — NH\u003csub\u003e3\u003c/sub\u003e (\u003cstrong\u003eB\u003c/strong\u003e) — NO+O\u003csub\u003e2\u003c/sub\u003e (\u003cstrong\u003eC\u003c/strong\u003e) adsorptions on CeV/TiO\u003csub\u003e2\u003c/sub\u003e at 250°C; DRIFTs of toluene (\u003cstrong\u003eD\u003c/strong\u003e) — NH\u003csub\u003e3\u003c/sub\u003e (\u003cstrong\u003eE\u003c/strong\u003e) — NO+O\u003csub\u003e2\u003c/sub\u003e (\u003cstrong\u003eF\u003c/strong\u003e) adsorptions on V/TiO\u003csub\u003e2\u003c/sub\u003e at 250°C.\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-9218535/v1/d02d765057ac922b1735fdad.png"},{"id":105743662,"identity":"ca943dc0-0210-4dcf-a852-7304056baacb","added_by":"auto","created_at":"2026-03-30 13:46:50","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":60294,"visible":true,"origin":"","legend":"\u003cp\u003eDRIFTs of toluene (\u003cstrong\u003eA\u003c/strong\u003e) — NO+O\u003csub\u003e2\u003c/sub\u003e (\u003cstrong\u003eB\u003c/strong\u003e) — NH\u003csub\u003e3\u003c/sub\u003e (\u003cstrong\u003eC\u003c/strong\u003e) adsorptions on CeV/TiO\u003csub\u003e2\u003c/sub\u003e at 250°C; DRIFTs of toluene (\u003cstrong\u003eD\u003c/strong\u003e) — NO+O\u003csub\u003e2\u003c/sub\u003e (\u003cstrong\u003eE\u003c/strong\u003e) — NH\u003csub\u003e3\u003c/sub\u003e (\u003cstrong\u003eF\u003c/strong\u003e) adsorptions on V/TiO\u003csub\u003e2\u003c/sub\u003e at 250°C.\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-9218535/v1/5965d48dbbe9c3588f89f24d.png"},{"id":105751987,"identity":"9f72e560-c08c-47a7-9512-c18f8d8d1a49","added_by":"auto","created_at":"2026-03-30 15:52:29","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":368345,"visible":true,"origin":"","legend":"\u003cp\u003eAdsorption energies of different gases on V/TiO\u003csub\u003e2\u003c/sub\u003e (\u003cstrong\u003eA\u003c/strong\u003e) and CeV/TiO\u003csub\u003e2\u003c/sub\u003e (\u003cstrong\u003eB\u003c/strong\u003e). Mechanism of stable simultaneous removal of toluene and NO (\u003cstrong\u003eC\u003c/strong\u003e).\u003c/p\u003e","description":"","filename":"5.png","url":"https://assets-eu.researchsquare.com/files/rs-9218535/v1/fc99d46e99be569de40fa61d.png"},{"id":107601462,"identity":"2c4dcf66-b5ac-4b36-812d-7f30cc47e9d9","added_by":"auto","created_at":"2026-04-23 06:41:14","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1000182,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-9218535/v1/f8797b68-eeb1-4aaa-b5a8-101c106fe912.pdf"},{"id":105743659,"identity":"e32d8426-0c88-4008-a79a-aa212e6ead2e","added_by":"auto","created_at":"2026-03-30 13:46:50","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":62215,"visible":true,"origin":"","legend":"","description":"","filename":"SupportingInformation.docx","url":"https://assets-eu.researchsquare.com/files/rs-9218535/v1/d2ebe419cf0b8e821ac7e408.docx"},{"id":105743667,"identity":"7305126b-82a1-455a-a2f3-feddbd81bdb3","added_by":"auto","created_at":"2026-03-30 13:46:51","extension":"png","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":70645,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eGraphical Abstract\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"GA.png","url":"https://assets-eu.researchsquare.com/files/rs-9218535/v1/3f22e4b93a47d78b77b07b00.png"}],"financialInterests":"No competing interests reported.","formattedTitle":"A stable catalyst for simultaneous catalytic removal of nitrogen oxide and toluene at low temperature","fulltext":[{"header":"Article Highlights","content":"\u003cp\u003e(1) Catalytic oxidation and reduction have a mutual interference.\u003c/p\u003e\n\u003cp\u003e(2) CeV/TiO\u003csub\u003e2\u003c/sub\u003e is more stable than V/TiO\u003csub\u003e2\u003c/sub\u003e in the mutual interference.\u003c/p\u003e\n\u003cp\u003e(3) The stability is attributed to lower adsorption energies for various pollutants.\u003c/p\u003e"},{"header":"1. Introduction","content":"\u003cp\u003eVolatile organic compounds (VOCs) and nitrogen oxide (NOx) are two typical air pollutants [\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e]. Examples of VOCs are halogenated hydrocarbons, aldehydes, aromatics, alkanes, ketones, and sulfur containing compounds. High concentrations of these VOCs cause irritations, dizziness, headaches, and even cancers for both humans and animals [\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e]. NOx potentially cause acid rain, photochemical smog, and eutrophication. Furthermore, VOCs and NOx are both crucial precursors of ozone and PM\u003csub\u003e2.5\u003c/sub\u003e [\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e]. Some industries only discharge VOCs, such as petrochemical, pharmaceutical, paint, and leather manufacturing. However, some others discharge both VOCs and NOx, such as thermal power, incineration, glass, cement, steel sintering, and ceramics. Therefore, the simultaneous removal of VOCs and NOx is a necessary.\u003c/p\u003e \u003cp\u003eIf only VOCs are aimed to be removed, the catalytic oxidation is accepted to be the most effective and reliable technology. Theoretically, VOCs react with O\u003csub\u003e2\u003c/sub\u003e to form H\u003csub\u003e2\u003c/sub\u003eO and CO\u003csub\u003e2\u003c/sub\u003e with the help of the catalyst [\u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e]. The commercial VOCs catalyst includes noble-metal (Pt, Pd, Ag) and transition-metal (Mn, Ce, Cu) catalysts [\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e, \u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e]. If the polluted gas only contains NOx, selective catalytic reduction (SCR) is widely recognized as the most cost-effective method [\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e]. In brief, NOx catalytically react with the reductant, forming harmless H\u003csub\u003e2\u003c/sub\u003eO and N\u003csub\u003e2\u003c/sub\u003e [\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e]. The most typical reductant and catalyst are NH\u003csub\u003e3\u003c/sub\u003e and V/TiO\u003csub\u003e2\u003c/sub\u003e, respectively. In fact, V/TiO\u003csub\u003e2\u003c/sub\u003e is a commercial catalyst used in the real industry [\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e]. In recent years, other reductant is put forward to replace NH\u003csub\u003e3\u003c/sub\u003e, such as hydrocarbons and carbon monoxide [\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e, \u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e]. Thus, researchers also ask themselves if VOCs can potentially be used as the reductant of SCR.\u003c/p\u003e \u003cp\u003eThe simultaneous removal thus reduces equipment construction costs and space requirement [\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e]. However, two difficulties exists. On one hand, one bifunctional catalyst must be developed working at a same temperature range for both these two gases [\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e]. This is relatively easy to solve since typical catalytic temperatures for these gases are 180\u0026ndash;300\u0026deg;C. We even can find catalysts that can efficiently catalyze these gases alone. For example, MnO\u003csub\u003e2\u003c/sub\u003e effectively catalyze VOCs and NOx at 250\u0026deg;C and 100\u0026ndash;250\u0026deg;C, respectively [\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e, \u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e]. On the other hand, catalytic oxidation and catalytic reduction potentially affect each other because these two processes both utilizes surface oxygens on the catalyst [\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e, \u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e]. Several attempts have showed that the NH\u003csub\u003e3\u003c/sub\u003e-SCR inhibits the toluene oxidation if a same catalyst is used [\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e, \u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e]. The main reason is that the reactive intermediate of one catalyst is a blocking species for the other [\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e]. Therefore, decreasing the competitive effect seems to be more pragmatic than using VOCs as the reductant of SCR.\u003c/p\u003e \u003cp\u003eIn this work, V/TiO\u003csub\u003e2\u003c/sub\u003e and CeV/TiO\u003csub\u003e2\u003c/sub\u003e are synthesized and compared in simultaneous catalytic removal of toluene and NO. Both the catalysts and catalytic processes are detailly characterized. The adsorption energies of different gaseous molecules are calculated by the density functional theory. With these investigations, a mechanism is put forward to explain why CeV/TiO\u003csub\u003e2\u003c/sub\u003e is a more stable catalyst.\u003c/p\u003e"},{"header":"2. Materials and Methods","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e\n \u003ch2\u003e2.1. Catalyst Preparations\u003c/h2\u003e\n \u003cp\u003eThe catalyst was synthesized by an impregnation method [\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e]. In detail, ammonium metavanadate and ammonium cerium nitrate were dissolved in 100 mL of deionized water at 70\u0026deg;C. TiO\u003csub\u003e2\u003c/sub\u003e (5 g) was dispersed into the above solution, and stirred for 2 h. After a well mixing, the solution was dried at 105\u0026deg;C before being calcined at 450\u0026deg;C for 2 h. The prepared catalysts were milled to 50 mesh and denoted as V/Ti and CeV/Ti. The metal contents of these catalysts were detected by which were an Inductively Coupled Plasma-Atomic Emission Spectrometry (IRIS Advantage 1000, Thermo Fisher) after the standard digestion. V/Ti resulted in a V-loading amount of 5 wt.%. In CeV/Ti, molar ratio between Ce and V was around 1:1.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec4\" class=\"Section2\"\u003e\n \u003ch2\u003e2.2. Catalytic Performances\u003c/h2\u003e\n \u003cp\u003eCatalytic oxidation of toluene and NH\u003csub\u003e3\u003c/sub\u003e-SCR were carried out on a fixed-bed reactor [\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e], which is showed in \u003cstrong\u003eFig. \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e\u003c/strong\u003e in the Supporting Information. Setup details are also provided below the figure. Removals of toluene (X\u003csub\u003eT\u003c/sub\u003e) and NO (X\u003csub\u003eNO\u003c/sub\u003e) are calculated according to Eqs.\u0026nbsp;(1) and (2). N\u003csub\u003e2\u003c/sub\u003e selectivity is calculated accordingly by Eq.\u0026nbsp;(3). In these equations, the subscripts \u0026ldquo;in\u0026rdquo; and \u0026ldquo;out\u0026rdquo; stands for concentrations in the inflow and outflow, respectively.\u003c/p\u003e\n \u003cdiv class=\"gridtable\"\u003e\n \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003cimg 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\" width=\"609\" height=\"261\"\u003e\u003c/div\u003e\n \u003c/div\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec5\" class=\"Section2\"\u003e\n \u003ch2\u003e2.3. Characterizations\u003c/h2\u003e\n \u003cp\u003eX-ray diffraction (XRD) was carried out using a powder diffractometer (MiniFlex600, Rigaku) equipped with Cu K\u0026alpha; radiation. Textural properties were detected by Autosorb-IQ2. Temperature-programmed desorption of NH\u003csub\u003e3\u003c/sub\u003e (NH\u003csub\u003e3\u003c/sub\u003e-TPD) and temperature-programmed reduction of H\u003csub\u003e2\u003c/sub\u003e (H\u003csub\u003e2\u003c/sub\u003e-TPR) were carried on a VD Sorb-91i (Quzhou Vodo instrument Co. Ltd., China). Binding energies of elements were analyzed by a K-Alpha X-ray photoelectron spectroscopy (XPS, Thermo Scientific, USA). \u003cem\u003eIn-situ\u003c/em\u003e Diffuse Reflection Fourier Transform Infrared Spectrometer (DRIFTs) was carried out on Nicolet IS10 (Thermo Scientific) with an MCT detector at a resolution of 4 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e [\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e]. The sampling intervals are all 0, 1, 3, 5, 10, 20, and 30 min. All calculations were based on spin polarization density functional theory (DFT) such as Vienna First Principles (VASP) and projected Enhanced waves (PAW). The exchange correlation function used was a local density approximation with generalized gradient correction, called GGA-PBE [\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e, \u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e]. The energy of the plane wave was truncated to 400 eV for all atoms, and the ion positions of all structures were relaxed until the force converges to 0.03eV\u0026middot;\u0026Aring;.\u003c/p\u003e\n\u003c/div\u003e"},{"header":"3. Results and Discussion","content":"\u003cdiv id=\"Sec7\" class=\"Section2\"\u003e \u003ch2\u003e3.1. Simultaneous Catalytic Removal of NO and Toluene\u003c/h2\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eFigure S2A investigates the possibility of using toluene as the reductant of SCR process. Unfortunately, the NO removals are close to zero at the tested temperatures. If the O\u003csub\u003e2\u003c/sub\u003e is removed from the inflow gas, both the conversions of NO and toluene are close to zero (\u003cb\u003eFig. S2B\u003c/b\u003e). However, if the temperature is further increased to 350\u0026deg;C, both NO and toluene conversions are increased to about 20\u0026thinsp;\u0026minus;\u0026thinsp;30%. Considering this, even the toluene is feasible to be used as the reductant of SCR, the suitable temperature is too high.\u003c/p\u003e \u003cp\u003eOn one hand, if V/TiO\u003csub\u003e2\u003c/sub\u003e is used in the SCR, a removal of 65% is reached at 100\u0026deg;C (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eA). When the temperature is increased to 200\u0026deg;C, the removal has been increased to 99%. In comparison, when the toluene is mixed into the inflow gas, the NO removal is obviously decreased. For example, the removal is decreased to 37% at 100\u0026deg;C. On the other hand, if V/TiO\u003csub\u003e2\u003c/sub\u003e is used in the catalytic oxidization of toluene, the ignition temperature is started between 200 and 250\u0026deg;C (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eB). When the NO and NH\u003csub\u003e3\u003c/sub\u003e are mixed into the inflow gas, the toluene removal is also affected. For example, the removal at 300\u0026deg;C is decreased from 99% to 67%.\u003c/p\u003e \u003cp\u003eWhen Ce is co-doped onto the TiO\u003csub\u003e2\u003c/sub\u003e, CeV/TiO\u003csub\u003e2\u003c/sub\u003e has a better resistant ability for co-existing toluene (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eA). The removals between 100 and 200\u0026deg;C is hardly affected. The removal is decreased from 98% to 86% at 300\u0026deg;C. The difference is 12%. In comparison, the difference is 23% using V/TiO\u003csub\u003e2\u003c/sub\u003e. As for the side of toluene, similar phenomenon is observed (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eB). The catalytic activity of CeV/TiO\u003csub\u003e2\u003c/sub\u003e is hardly affected by the co-existing NO and NH\u003csub\u003e3\u003c/sub\u003e. The conversion curves are almost overlapped. In addition, the co-catalysis has no influence on the N\u003csub\u003e2\u003c/sub\u003e selectivity either (\u003cb\u003eFig. S2C\u003c/b\u003e). After all, CeV/TiO\u003csub\u003e2\u003c/sub\u003e is more stable than V/TiO\u003csub\u003e2\u003c/sub\u003e in the simultaneous catalysis.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec8\" class=\"Section2\"\u003e \u003ch2\u003e3.2. Basic Characterizations\u003c/h2\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab1\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eTextural properties of V/TiO\u003csub\u003e2\u003c/sub\u003e and CeV/TiO\u003csub\u003e2\u003c/sub\u003e.\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"3\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\" morerows=\"1\" rowspan=\"2\"\u003e \u003cp\u003eSpecific surface area (m\u003csup\u003e2\u003c/sup\u003e\u0026middot;g\u003csup\u003e\u0026ndash;1\u003c/sup\u003e)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eV/TiO\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eCeV/TiO\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003e47.2\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003e48.5\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePore volume (cm\u003csup\u003e3\u003c/sup\u003e\u0026middot;g\u003csup\u003e\u0026ndash;1\u003c/sup\u003e)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.42\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0.43\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePore size (nm)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e38.3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e38.8\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eO\u003csub\u003eα\u003c/sub\u003e (%)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e87\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e86\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eO\u003csub\u003eβ\u003c/sub\u003e (%)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e8\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eO\u003csub\u003eγ\u003c/sub\u003e (%)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e6\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eV\u003csup\u003e3+\u003c/sup\u003e (%)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e26\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e12\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eV\u003csup\u003e4+\u003c/sup\u003e (%)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e44\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e53\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eV\u003csup\u003e5+\u003c/sup\u003e (%)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e30\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e35\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003eV/TiO\u003csub\u003e2\u003c/sub\u003e and CeV/TiO\u003csub\u003e2\u003c/sub\u003e show a similar XRD pattern (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eA). Anatase TiO\u003csub\u003e2\u003c/sub\u003e (PDF#84-1285) has diffractions at 25.3 \u0026deg; (101), 37.8 \u0026deg; (004), 48.0 \u0026deg; (200), 53.9 \u0026deg; (105), 55.1 \u0026deg; (211), and 62.7 \u0026deg; (204), while the main diffraction of rutile TiO\u003csub\u003e2\u003c/sub\u003e (PDF#87\u0026ndash;0710) is detected 27.5 \u0026deg; (110) [\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e]. Besides, both catalysts exhibits a type IV isotherm with a hysteresis loop (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eB), which is the proof of the mesoporous structure [\u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e]. In fact, the two catalysts have similar textural properties (Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e). For example, the specific surface areas are 47.2 and 48.5 m\u003csup\u003e2\u003c/sup\u003e\u0026middot;g\u003csup\u003e\u0026ndash;1\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eBr\u0026oslash;nsted-acidic sites (100\u0026ndash;250\u0026deg;C) and the Lewis-acidic sites (300\u0026ndash;450\u0026deg;C) are observed in \u003cb\u003eFig. S3A\u003c/b\u003e. The Br\u0026oslash;nsted-acid site favors the SCR [\u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e]. After the integration, the relative area of the Br\u0026oslash;nsted-acidic site in V/TiO\u003csub\u003e2\u003c/sub\u003e is 283 (a.u.), which the relative area of the Lewis-acid site is 96 (a.u.). In comparison, CeV/TiO\u003csub\u003e2\u003c/sub\u003e has 148 (a.u.) of Br\u0026oslash;nsted-acidic sites and 169 (a.u.) of Lewis-acid sites. This explains why V/TiO\u003csub\u003e2\u003c/sub\u003e has a better SCR activity than CeV/TiO\u003csub\u003e2\u003c/sub\u003e. H\u003csub\u003e2\u003c/sub\u003e-TPR stands for the reduction of both VOx and CeOx (\u003cb\u003eFig. S3B\u003c/b\u003e). The overall reductive ability is reduced after co-doping Ce in V/TiO\u003csub\u003e2\u003c/sub\u003e.\u003c/p\u003e \u003cp\u003eThe peak of XPS O 1s at 528\u0026ndash;534 eV is typically made up to lattice oxygen (O\u003csub\u003eα\u003c/sub\u003e), oxygen vacancy (O\u003csub\u003eβ\u003c/sub\u003e), and surface hydroxyl (O\u003csub\u003eγ\u003c/sub\u003e) [\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e]. Figure\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eC are fitted into these components and the results are listed in Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e. V/TiO\u003csub\u003e2\u003c/sub\u003e and CeV/TiO\u003csub\u003e2\u003c/sub\u003e show similar amounts of these oxygen species. Their main components are O\u003csub\u003eα\u003c/sub\u003e, which occupies 86\u0026ndash;87% of all oxygen species. Figure\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eD further compares the XPS V 2p of these two catalysts. The V 2p is usually fitted into three species, including V\u003csup\u003e5+\u003c/sup\u003e (517 eV), V\u003csup\u003e4+\u003c/sup\u003e(516 eV), and V\u003csup\u003e3+\u003c/sup\u003e (515 eV) [\u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e]. Between the two catalysts, V/TiO\u003csub\u003e2\u003c/sub\u003e exhibits a higher proportion of low-valence V species (70%), which enhances the redox cycle on the catalyst surface [\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e]. This is consistent with the H\u003csub\u003e2\u003c/sub\u003e-TPR result.\u003c/p\u003e \u003cp\u003eAccording to the above comparisons, the reason is revealed why V/TiO\u003csub\u003e2\u003c/sub\u003e has better catalytic performances than CeV/TiO\u003csub\u003e2\u003c/sub\u003e in separate removal of toluene and NO. However, the above similarity and differentia is infeasible to explain why CeV/TiO\u003csub\u003e2\u003c/sub\u003e has a more stable performance in simultaneous removal of toluene and NO.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec9\" class=\"Section2\"\u003e \u003ch2\u003e3.3. Catalytic Processes\u003c/h2\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eWhen the catalytic oxidation occurs on CeV/TiO\u003csub\u003e2\u003c/sub\u003e at 250\u0026deg;C (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eA), several obvious peaks are observed at 3029, 2930, 1644, and 1513 cm\u003csup\u003e\u0026ndash;1\u003c/sup\u003e. According to previous reports, clear bands at 1513and 1644 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e are associated with the vibration of aromatic rings [\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e]. 2931 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e is attributed to the antisymmetric peaks of CH in CH\u003csub\u003e2\u003c/sub\u003e, i.e., the benzyl radicals are generated [\u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e]. 3029 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e is derived from C‒H stretching vibration in benzene ring [\u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e]. After NH\u003csub\u003e3\u003c/sub\u003e flows into the reactor, the peaks are hardly affected at 1513 and 1644 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. However, new peaks are observed at 1451 and 1173 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, which are attributed to adsorbed NH\u003csub\u003e3\u003c/sub\u003e species on Br\u0026oslash;nsted and Lewis acid sites, respectively [\u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e]. At the same time, the peaks at 3029 and 2930 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e are placed by new peaks at 3250 and 3151 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e step by step. They belongs to ascribed to N\u0026ndash;H stretching vibration modes of NH\u003csub\u003e3\u003c/sub\u003e and NH\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e+\u003c/sup\u003e, respectively [\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e, \u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e]. This indicates that two possibilities. One is that intermediates of toluene decomposition are replaced by NH\u003csub\u003e3\u003c/sub\u003e-derived species. The other is that these intermediates even react with NH\u003csub\u003e3\u003c/sub\u003e. Whatever the possibility, NH\u003csub\u003e3\u003c/sub\u003e-derived species are feasible to be adsorbed onto the catalyst surface. After NO\u0026thinsp;+\u0026thinsp;O\u003csub\u003e2\u003c/sub\u003e flows into the reactor, the peaks at 1513 and 1644 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e still exists even after 30 min. On the contrary, the intensities of NH\u003csub\u003e3\u003c/sub\u003e-derived species are all decreased along with time. This indicates that NH\u003csub\u003e3\u003c/sub\u003e molecules are first adsorbed on the catalyst surface and then react with NO, which is called an Eley-Rideal (E-R) mechanism.\u003c/p\u003e \u003cp\u003eIn comparison, when V/TiO\u003csub\u003e2\u003c/sub\u003e is used in the catalytic oxidation of toluene (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eB), the peak at 1400 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e represents the shorter carboxylate species (especially acetate) [\u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e]. In addition, peaks are also observed at 3029, 2930, 1644, and 1513 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. After NH\u003csub\u003e3\u003c/sub\u003e flows into the reactor, above peaks are hardly affected. Although the peaks at 3029 and 2930 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e are obviously decreased, no NH\u003csub\u003e3\u003c/sub\u003e-derived species are formed. After NO\u0026thinsp;+\u0026thinsp;O\u003csub\u003e2\u003c/sub\u003e flows into the reactor, the relative intensities at 1644 and 1513 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e are decreased. The peak intensity at 1400 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e is stable. Thus, the intermediate shorter carboxylate species is hard to be replaced. After all, no NO\u0026thinsp;+\u0026thinsp;O\u003csub\u003e2\u003c/sub\u003e derived species are formed. In other words, the intermediates of toluene decomposition disturb the SCR on V/TiO\u003csub\u003e2\u003c/sub\u003e. This is different from CeV/TiO\u003csub\u003e2\u003c/sub\u003e, which functions normally in SCR even with the intermediates.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eIn Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eA, NO\u0026thinsp;+\u0026thinsp;O\u003csub\u003e2\u003c/sub\u003e flows into the reactor after the catalytic oxidation of toluene for 30 min. The peaks at 3029 and 2930 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e removed from the catalyst surface by the NO\u0026thinsp;+\u0026thinsp;O\u003csub\u003e2\u003c/sub\u003e flow. An overlapping peak at 1538 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e is formed and attributed to NO\u003csub\u003e2\u003c/sub\u003e on Lewis acid sides. After NH\u003csub\u003e3\u003c/sub\u003e flows into the reactor, these peaks are hardly affected). Besides, peaks are formed at 3250 and 3151 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. These phenomena at least suggest that NH\u003csub\u003e3\u003c/sub\u003e are adsorbed. As is well-known, if NH\u003csub\u003e3\u003c/sub\u003e reacts with the pre-adsorbed NO\u0026thinsp;+\u0026thinsp;O\u003csub\u003e2\u003c/sub\u003e, the SCR is carried out by the Langmuir-Hinshelwood (L-H mechanism). However, it is hard to judge whether SCR is carried out by this mechanism.\u003c/p\u003e \u003cp\u003eAfter NO\u0026thinsp;+\u0026thinsp;O\u003csub\u003e2\u003c/sub\u003e flows into the reactor (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eB), the peak intensities are decreased at 1644, and 1513 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. However, the three peaks still observed after 30 min. Although the peak intensities are also decreased at 3029 and 2930 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, no obvious NO\u0026thinsp;+\u0026thinsp;O\u003csub\u003e2\u003c/sub\u003e-derived species are recognized. Similarly, after NH\u003csub\u003e3\u003c/sub\u003e flows into the reactor, no further change is observed. According to the previous reports, the V/TiO\u003csub\u003e2\u003c/sub\u003e-based catalyst participates in the SCR by both L-H and E-R mechanisms [\u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e35\u003c/span\u003e, \u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e36\u003c/span\u003e]. Considering this, the catalytic oxidation of toluene interferes the L-H mechanism by both the catalysts but only interferes the E-R mechanism by V/TiO\u003csub\u003e2\u003c/sub\u003e. This is the reason why CeV/TiO\u003csub\u003e2\u003c/sub\u003e is more stable than V/TiO\u003csub\u003e2\u003c/sub\u003e in the simultaneous catalysis of toluene and NO.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec10\" class=\"Section2\"\u003e \u003ch2\u003e3.4. Catalytic Mechanism\u003c/h2\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab2\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 2\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eAdsorption energies of different gases on V/TiO\u003csub\u003e2\u003c/sub\u003e and CeV/TiO\u003csub\u003e2\u003c/sub\u003e.\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"3\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\" morerows=\"1\" rowspan=\"2\"\u003e \u003cp\u003eCO\u003csub\u003e2\u003c/sub\u003e adsorption\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eV/TiO\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eCeV/TiO\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003e4.127\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003e2.885\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eNH\u003csub\u003e3\u003c/sub\u003e adsorption\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e-1.693\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e-1.688\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eNO adsorption\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e11.572\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e4.441\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eNO\u003csub\u003e2\u003c/sub\u003e adsorption\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e-0.959\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e-0.841\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003eDFT calculations are used to compare the adsorption energies of different gases (including CO\u003csub\u003e2\u003c/sub\u003e, NH\u003csub\u003e3\u003c/sub\u003e, NO, and NO\u003csub\u003e2\u003c/sub\u003e) on V/TiO\u003csub\u003e2\u003c/sub\u003e (\u003cb\u003eFig. S4A\u003c/b\u003e) and CeV/TiO\u003csub\u003e2\u003c/sub\u003e (\u003cb\u003eFig. S4B\u003c/b\u003e). The detailed values are listed in Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e. A negative adsorption energy indicates a spontaneous adsorption on the surface. Besides, the more negative the adsorption energy, the stronger the adsorption [\u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e37\u003c/span\u003e]. Therefore, both NH\u003csub\u003e3\u003c/sub\u003e and NO\u003csub\u003e2\u003c/sub\u003e can be adsorbed spontaneously by both V/TiO\u003csub\u003e2\u003c/sub\u003e and CeV/TiO\u003csub\u003e2\u003c/sub\u003e. However, V/TiO\u003csub\u003e2\u003c/sub\u003e has a stronger adsorption than CeV/TiO\u003csub\u003e2\u003c/sub\u003e since its adsorption energies are more negative. On the contrary, a positive value indicates that the adsorption process is endothermic [\u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e38\u003c/span\u003e]. Therefore, the adsorption energy of CO\u003csub\u003e2\u003c/sub\u003e is significantly decreased from 4.127 eV (V/TiO\u003csub\u003e2\u003c/sub\u003e) to 2.885 eV (CeV/TiO\u003csub\u003e2\u003c/sub\u003e). CO\u003csub\u003e2\u003c/sub\u003e is an important intermediate of toluene decomposition. Its release from the catalyst surface is determining to the continuous catalysis. A lower adsorption energy indicates that the molecule is easier to be replaced by other gases. Similarly, the adsorption energy of NO is significantly decreased from 11.572 eV (V/TiO\u003csub\u003e2\u003c/sub\u003e) to 4.441 eV (CeV/TiO\u003csub\u003e2\u003c/sub\u003e).\u003c/p\u003e \u003cp\u003eA more stable simultaneous catalysis of toluene and NO is attributed to lower adsorption energies on the catalyst surface after co-doping Ce. When the toluene are adsorbed by V/TiO\u003csub\u003e2\u003c/sub\u003e and CeV/TiO\u003csub\u003e2\u003c/sub\u003e. Intermediates are formed on the surfaces (\u003cb\u003eFig. S4CI\u003c/b\u003e). On one hand, NH\u003csub\u003e3\u003c/sub\u003e is feasible to replace these intermediates on the CeV/TiO\u003csub\u003e2\u003c/sub\u003e but infeasible to replace those on the V/TiO\u003csub\u003e2\u003c/sub\u003e (\u003cb\u003eFig. S4CII\u003c/b\u003e). As a result, NOx can react with the NH\u003csub\u003e3\u003c/sub\u003e-dervied species to complete the E-R mechanism on CeV/TiO\u003csub\u003e2\u003c/sub\u003e (\u003cb\u003eFig. S4CIII\u003c/b\u003e and \u003cb\u003e3\u003c/b\u003e). On the other hand, NO is infeasible to replace the intermediates on V/TiO\u003csub\u003e2\u003c/sub\u003e and CeV/TiO\u003csub\u003e2\u003c/sub\u003e (\u003cb\u003eFig. S4CIV\u003c/b\u003e). As a result, the L-H mechanism is hindered on both these catalysts (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e).\u003c/p\u003e \u003c/div\u003e"},{"header":"4. Conclusion","content":"\u003cp\u003eIn this work, V/TiO\u003csub\u003e2\u003c/sub\u003e and CeV/TiO\u003csub\u003e2\u003c/sub\u003e were synthesized and compared in simultaneous SCR and catalytic oxidation of toluene. CeV/TiO\u003csub\u003e2\u003c/sub\u003e was more stable than V/TiO\u003csub\u003e2\u003c/sub\u003e in the simultaneous catalysis. The reason was revealed that CeV/TiO\u003csub\u003e2\u003c/sub\u003e had weaker adsorption abilities for various pollutants and derived intermediates. These species are easier to be replaced by each other on the catalyst surface. Therefore, this work put forward a successful example of designing a suitable catalyst instead of a merely active one.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eAcknowledgements\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eWe appreciate the help of the Instrumental Analysis \u0026amp; Research Center of Shanghai University in sample characterization.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eFunding\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThis project was financially supported by the Natural Science Foundation of Shanghai 2021 Science and Technology Innovation Action Plan (21ZR1424000).\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthor Information\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthors and Affiliations\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eYu Yan,\u003csup\u003e1\u003c/sup\u003e Linmin Lao,\u003csup\u003e1\u003c/sup\u003e Chengyan Li,\u003csup\u003e2\u003c/sup\u003e Yang Yue,\u003csup\u003e1,3\u003c/sup\u003e Guangren Qian,\u003csup\u003e3\u003c/sup\u003e Jia Zhang \u003csup\u003e1,3\u003c/sup\u003e\u003c/p\u003e\n\u003cp\u003e\u003csup\u003e1\u003c/sup\u003e SHU Center of Green Urban Mining \u0026amp; Industry Ecology, School of Environmental and Chemical Engineering, Shanghai University, No. 381 Nanchen Road, Shanghai 200444, P. R. China\u003c/p\u003e\n\u003cp\u003e\u003csup\u003e2\u003c/sup\u003e Nanjing Institute of Environmental Sciences, Ministry of Ecology and Environment of the People\u0026rsquo;s Republic of China, Nanjing 210042, China\u003c/p\u003e\n\u003cp\u003e\u003csup\u003e3\u003c/sup\u003e MGI of Shanghai University, Xiapu Town, Xiangdong District, Pingxiang City, Jiangxi, 337022, P. R. China;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eContributions\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eYu Yan\u003c/strong\u003eand\u003cstrong\u003e\u0026nbsp;Linmin Lao\u003c/strong\u003econtributes to experiment design, data acquisition and analysis, and manuscript drafting. \u003cstrong\u003eChengyan Li\u0026nbsp;\u003c/strong\u003eand \u003cstrong\u003eYang Yue\u003c/strong\u003e contribute to characterizations. \u003cstrong\u003eGuangren Qian\u003c/strong\u003e contributes to resources.\u003cstrong\u003e\u0026nbsp;Jia Zhang\u003c/strong\u003e contributes to interpretation of data and critical revision of the manuscript.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCorresponding Author\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCorrespondence to Jia Zhang.\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eEthics Declarations\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eEthics Approval and Consent to Participate\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eNot applicable.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eConsent for Publication\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eNot applicable.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCompeting Interests\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors have no relevant financial or non-financial interests to disclose.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eSupporting Information\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eSupplementary data Supplementary data to this article can be found online.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eLiang J, Hang J, Jia S et al (2025) O\u003csub\u003e3\u003c/sub\u003e\u0026ndash;NOx\u0026ndash;VOCs photochemical pollutant dispersion in 2D street canyon under effects of solar radiation. 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React Kinet Mech Catal 137:3265\u0026ndash;3296\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"Catalytic oxidation, Catalytic reduction, Volatile organic compounds, Nitrogen oxide, Titanium dioxide","lastPublishedDoi":"10.21203/rs.3.rs-9218535/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-9218535/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eSimultaneous catalytic removal of nitrogen oxide and volatile organic compounds at low temperature is a challenge since these two pollutants have a competitive effect for the catalytic active site. This work has compared the different behaviors of V/TiO\u003csub\u003e2\u003c/sub\u003e and CeV/TiO\u003csub\u003e2\u003c/sub\u003e in separate and simultaneous catalytic removal of NO and toluene. Both the catalysts have been detailly characterized and compared. The catalytic oxidation of toluene obviously disturbed the catalytic reduction of NO by V/TiO\u003csub\u003e2\u003c/sub\u003e. NO removal was decreased from 99% to 72% at 250°C. In comparison, the toluene only decreased the NO removal of CeV/TiO\u003csub\u003e2\u003c/sub\u003e from 95% to 85%. From the viewpoint of toluene, the NO slightly decreased the toluene removal of V/TiO\u003csub\u003e2\u003c/sub\u003e but hardly affected the toluene removal of CeV/TiO\u003csub\u003e2\u003c/sub\u003e. The more stable performance of CeV/TiO\u003csub\u003e2\u003c/sub\u003e was attributed to its lower adsorption energies/abilities for various pollutants and derived intermediates.\u003c/p\u003e","manuscriptTitle":"A stable catalyst for simultaneous catalytic removal of nitrogen oxide and toluene at low temperature","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2026-03-30 13:46:43","doi":"10.21203/rs.3.rs-9218535/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"f0421acb-6713-4713-8f2d-886f2c9d794f","owner":[],"postedDate":"March 30th, 2026","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[],"tags":[],"updatedAt":"2026-04-23T06:40:23+00:00","versionOfRecord":[],"versionCreatedAt":"2026-03-30 13:46:43","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-9218535","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-9218535","identity":"rs-9218535","version":["v1"]},"buildId":"XKTyCvWXoU3ODBz1xrDgd","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}