Ti Doped Layered Manganese Oxide as an Efficient Catalyst for the Low-Temperature SCR of No with NH₃

Abstract:

To address the issues of environmental pollution caused by nitrogen oxides (NOx) and limitation of catalytic efficiency windows, a series of Mn-Ti catalysts were prepared for low-temperature selective catalytic reduction (SCR) of NOx with NH₃. It was found that the doped layered manganese oxide catalysts (Ti-Bir) exhibited remarkable SCR activity and superior SO₂ resistance, achieving 100% NO removal at 80°C, outperforming both the composite metal oxide MnOx-TiOx and the supported metal oxide MnOx/TiOx. Through comprehensive characterization by XRD, N₂ adsorption–desorption test, H₂-TPR, O₂-TPD, NH₃-TPD, XPS, SEM and TEM, it was found that Ti-Bir successfully formed a birnessite-type layered structure with an extensive specific surface area (317 m²/g) and total pore volume (0.49 cm³/g). It contained abundant Mn⁴⁺ species and rich surface chemisorbed oxygen represented by relatively high percentages of Mn⁴⁺ and Oα. And faster oxygen mobility and better redox properties was shown with Ti-Bir. The doping of Ti into the birnessite enhanced the Mn-Ti contact, promoted efficient electron transfer and facilitated the redox cycles of Mn⁴⁺-Mn³⁺ and Ti⁴⁺-Ti³⁺. These factors together contributed to the outstanding catalytic performance of Ti-Bir in the low-temperature SCR reaction of NO with NH₃.

• Periodical: Materials Science Forum (Volume 1171)
• Pages: 69-83
• DOI: https://doi.org/10.4028/p-12LVmn
• Online since: December 2025
• Authors: Hong Wei Zhang*, Xin Xiao, Song Shu, Lang Bo Jiang, Jian Jun Li
• Keywords: Birnessite-Type Layered Structure, Layered Manganese Oxide, Low-Temperature SCR, Ti Doped

References

[1] Shu S, Guo JX, Li J, Fang NJ, Yuan SD. The enhanced performance of Ti doped MnOx for the removal of NO with NH3. J. Taiwan. Inst. Chem. Eng. 100 (2019) 168-177.

DOI: 10.1016/j.jtice.2019.04.019

[2] Zhai SY, Su YT, Weng XL, Li RN, Wang HQ, Wu ZB. Synergistic elimination of NOx and chlorinated organics over VOx/TiO2 catalysts: a combined experimental and DFT study for exploring vanadate domain effect. Environ. Sci. Tech. 55 (2021) 12862–12870.

DOI: 10.1021/acs.est.1c02997.s001

[3] Gao FY, Tang XL, Yi HH, Li JY, Zhao SZ, Wang JG, Chu C, Li CL. Promotional mechanisms of activity and SO2 tolerance of Co- or Ni-doped MnOx-CeO2 catalysts for SCR of NOx with NH3 at low temperature. Chem. Eng. J. 317 (2017) 20-31.

DOI: 10.1016/j.cej.2017.02.042

[4] Lian ZH, Wei J, Shan, WP, Yu YB, Radjenovic P M, Zhang H, He GZ, Liu, FD, Li J-F, Tian Z-Q, He H. Adsorption-induced active vanadium species facilitate excellent performance in low-temperature catalytic NOx abatement. J. Am. Chem. Soc. 143 (2021) 10454–10461.

DOI: 10.1021/jacs.1c05354

[5] Moliner M, Franch C, Palomares E, Grill M, Corma A. Cu–SSZ-39, an active and hydrothermally stable catalyst for the selective catalytic reduction of NOx. Chem. Commun. 48 (2012) 8264-8266.

DOI: 10.1039/c2cc33992g

[6] Gao FY, Tang XL, Yi HH, Zhao SZ, Li CL, Li JY, Shi YR, Meng XM. A Review on Selective Catalytic Reduction of NOx by NH3 over Mn–Based Catalysts at Low Temperatures: Catalysts, Mechanisms, Kinetics and DFT Calculations. Catalysts. 7 (2017) 199.

DOI: 10.3390/catal7070199

[7] Liu C, Shi J-W, Gao C, Niu CM. Manganese oxide-based catalysts for low-temperature selective catalytic reduction of NOx with NH3 : A review. Appl. Catal. A. 522 (2016) 54-69.

DOI: 10.1016/j.apcata.2016.04.023

[8] Wu ZB, Jin RB, Liu Y, Wang HQ. Ceria modified MnOx/TiO2 as a superior catalyst for NO reduction with NH3 at low-temperature. Catal. Commun. 9 (2008) 2217-2220.

DOI: 10.1016/j.catcom.2008.05.001

[9] Ren S, Li XD, He C, Chen L, Wang L, Li FG. Surface tailoring on bifunctional CuOx/MnO2 catalyst to promote the selective catalytic reduction of NO with NH3 and oxidation of CO with O2. Sep. Purif. Technol. 346 (2024) 127471.

DOI: 10.1016/j.seppur.2024.127471

[10] Wang S, Zhu N, Xu PP, Li S, Chen D. Si-modified Mn–Ce oxide catalysts for selective catalytic reduction of NOx with NH3 at low temperatures. New. J. Chem. 47 (2023) 12893-12901.

DOI: 10.1039/d3nj02345a

[11] Liu FD, He H. Selective catalytic reduction of NO with NH3 over manganese substituted iron titanate catalyst: Reaction mechanism and H2O/SO2 inhibition mechanism study. Catal. Today. 153 (2010) 70-76.

DOI: 10.1016/j.cattod.2010.02.043

[12] Thirupathi B., Smirniotis P G. Co-doping a metal (Cr, Fe, Co, Ni, Cu, Zn, Ce, and Zr) on Mn/TiO2 catalyst and its effect on the selective reduction of NO with NH3 at low-temperatures. Appl. Catal. B. 10 (2011) 195-206.

DOI: 10.1016/j.apcatb.2011.09.001

[13] Li HX, Li ZH, Jin LY, Zhang Y, Zhang AC, Sun ZJ. Effect of Mn content in Mn2−2yCoyCryOx catalyst on catalytic performance for SCR at low temperature. Chem. Phys. Lett. 831 (2023) 140843.

DOI: 10.1016/j.cplett.2023.140843

[14] Boningari T, Ettireddy P R, Somogyvari A, Liu Y, Vorontsov A, McDonald C A, Smirniotis P G. Influence of elevated surface texture hydrated titania on Ce-doped Mn/TiO2 catalysts for the low-temperature SCR of NOx under oxygen-rich conditions. J. Catal. 325 (2015) 145-155.

DOI: 10.1016/j.jcat.2015.03.002

[15] Yang SJ, Wang CZ, Li JH, Yan NQ, Ma L, Chang HZ. Low temperature selective catalytic reduction of NO with NH3 over Mn–Fe spinel: Performance, mechanism and kinetic study. Appl. Catal. B. 110 (2011) 71-80.

DOI: 10.1016/j.apcatb.2011.08.027

[16] Wang JL, Li DD, Li PL, Zhang PY, Xu QL, Yu JG. Layered manganese oxides for formaldehyde-oxidation at room temperature: the effect of interlayer cations. RSC. Adv. 5 (2015) 100434-100442.

DOI: 10.1039/c5ra17018d

[17] Yin H, Feng XH, Qiu GH, Tan WF, Liu F. Characterization of Co-doped birnessites and application for removal of lead and arsenite. J. Hazard. Mater. 188 (2011) 341-349.

DOI: 10.1016/j.jhazmat.2011.01.129

[18] Wang JL, Zhang GK, Zhang PY. Layered birnessite-type MnO2 with surface pits for enhanced catalytic formaldehyde oxidation activity. J. Mater. Chem. A. 5 (2017) 5719-5725.

DOI: 10.1039/c6ta09793f

[19] Ye Q, Lu H, Zhao J, Cheng SY, Kang TF, Wang D, Dai HX. A comparative investigation on catalytic oxidation of CO, benzene, and toluene over birnessites derived from different routes. Appl. Surf. Sci. 317 (2014) 892-901.

DOI: 10.1016/j.apsusc.2014.08.126

[20] Ma N, Kosasang S, Chomkhuntod P, Duangdangchote S, Phattharasupakun N, Klysubun W, Sawangphruk M. Insight into the unusual intercalation/deintercalation phenomena of alkali cations in the layered manganese oxide for electrochemical capacitors. J. Power. Sources. 455 (2020) 227969.

DOI: 10.1016/j.jpowsour.2020.227969

[21] Zhu L, Wang JL, Rong SP, Wang HY, Zhang PY. Cerium modified birnessite-type MnO2 for gaseous formaldehyde oxidation at low temperature. Appl. Catal. B. 211 (2017) 212-221.

DOI: 10.1016/j.apcatb.2017.04.025

[22] Wang JL, Li JG, Jiang CJ, Zhou P, Zhang PY, Yu JG. The effect of manganese vacancy in birnessite-type MnO2 on room-temperature oxidation of formaldehyde in air. Appl. Catal. B. 204 (2017) 147-155.

DOI: 10.1016/j.apcatb.2016.11.036

[23] Wang JL, Zhang GK, Zhang PY. Layered birnessite-type MnO2 with surface pits for enhanced catalytic formaldehyde oxidation activity. J. Mater. Chem. A. 5 (2017) 5719-5725.

DOI: 10.1039/c6ta09793f

[24] Wang, JL, Zhang PY, Li JG, Jiang CJ, Yunus R, Kim J. Room-Temperature Oxidation of Formaldehyde by Layered Manganese Oxide: Effect of Water. Environ. Sci. Technol. 49 (2015) 12372-12379.

DOI: 10.1021/acs.est.5b02085

[25] Lu L, Tian H, He JH, Yang QW. Graphene-MnO2 Hybrid Nanostructure as a New Catalyst for Formaldehyde Oxidation. J. Phys. Chem. C. 120 (2016) 23660-23668.

DOI: 10.1021/acs.jpcc.6b08312

[26] Liu FD, He H, Ding Y, Zhang CB. Effect of manganese substitution on the structure and activity of iron titanate catalyst for the selective catalytic reduction of NO with NH3. Appl. Catal. B. 93 (2009) 194-204.

DOI: 10.1016/j.apcatb.2009.09.029

[27] Ettireddy P R, Ettireddy N, Mamedov S, Boolchand P, Smirniotis P G. Surface characterization studies of TiO2 supported manganese oxide catalysts for low temperature SCR of NO with NH3. Appl. Catal. B. 76 (2007) 123-134.

DOI: 10.1016/j.apcatb.2007.05.010

[28] Deorsola F. A, Andreoli S, Armandi M, Bonelli B, Pirone R. Unsupported nanostructured Mn oxides obtained by Solution Combustion Synthesis: Textural and surface properties, and catalytic performance in NOx SCR at low temperature. Appl. Catal. A. 552 (2016) 120-129.

DOI: 10.1016/j.apcata.2016.05.002

[29] France L J, Yang Q, Li W, Chen ZB, Guang JY, Guo DW, Wang LF, Li XH. Ceria modified FeMnOx—Enhanced performance and sulphur resistance for low-temperature SCR of NOx. Appl. Catal. 206 (2017) 203-215.

DOI: 10.1016/j.apcatb.2017.01.019

[30] Lv SS, Zhang XL, Dong HY, Jin S, Wang XY. Microstructure and Catalytic Activity of MnSbOx Catalysts for Selective Catalytic Reduction of NO with NH3. Chem. Eng. Technol. 46 (2023) 2214-2225.

DOI: 10.1002/ceat.202300148

[31] Cao J, Rohani S, Liu WZ, Liu HH, Lu ZQ, Wu HL, Jiang LJ, Kong M, Liu QC, Yao XJ. Influence of phosphorus on the NH3-SCR performance of CeO2TiO2 catalyst for NOx removal from co-incineration flue gas of domestic waste and municipal sludge. J. Colloid. Interface. Sci. 610 (2022) 463–473.

DOI: 10.1016/j.jcis.2021.11.013

[32] Zhao XT, Mao L, Dong GJ. Mn-Ce-V-WOx/TiO2 SCR Catalysts: Catalytic Activity, Stability and Interaction among Catalytic Oxides. Catalysts. 8 (2018) 76.

DOI: 10.3390/catal8020076

[33] Shu S, Guo JX, Li J, Fang NJ, Li JJ, Yuan SD. Effect of post-treatment on the selective catalytic reduction of NO with NH3 over Mn3O4. Mater. Chem. Phys. 237 (2019) 121845.

DOI: 10.1016/j.matchemphys.2019.121845

[34] Post J. E, Veblen D.R. Crystal structure determinations of synthetic sodium, magnesium, and potassium birnessite using TEM and the Rietveld method. Am. Mineral. 75 (1990) 477-489.

[35] Yang YR, Wang MH, Tao ZL, Liu Q, Fei ZY, Chen X, Zhang ZX, Tang JH, Cui MF, Qiao X. Mesoporous Mn–Ti amorphous oxides: a robust low-temperature NH3-SCR catalyst. Catal. Sci. Technol. 8 (2018) 6396-6406.

DOI: 10.1039/c8cy01313f

[36] Jia BH, Guo JX, Shu S, Fang NJ, Li JJ, Chu YH. Effects of different Zr/Ti ratios on NH3–SCR over MnOx /ZryTi1-yO2: Characterization and reaction mechanism. Mol. Catal. 443 (2017) 25-37.

DOI: 10.1016/j.mcat.2017.09.019

[37] Yin H, Li H, Wang Y, Ginder-Vogel M, Qiu GH, Feng XH, Zheng LR, Liu F. Effects of Co and Ni co-doping on the structure and reactivity of hexagonal birnessite. Chem. Geol. 381 (2014) 10-20.

DOI: 10.1016/j.chemgeo.2014.05.017

[38] Kim S S, Hong S C. Improving the activity of Mn/TiO2 catalysts through control of the pH and valence state of Mn during their preparation. J. Air. Waste. Manage. Assoc. 62 (2012) 362-369.

DOI: 10.1080/10473289.2011.653515

[39] Kang M, Park E D, Kim J M, Yie J E. Manganese oxide catalysts for NOx reduction with NH3 at low temperatures. Appl. Catal. A. 327 (2007) 261-269.

DOI: 10.1016/j.apcata.2007.05.024

[40] Raj A.M E, Victoria S.G, Jothy V.B, Ravidhas C, Wollschlager J, Suendorf M, Neumann M, Jayachandran M, Sanjeeviraja C. XRD and XPS characterization of mixed valence Mn3O4 hausmannite thin films prepared by chemical spray pyrolysis technique. Appl. Surf. Sci. 256 (2010) 2920-2926.

DOI: 10.1016/j.apsusc.2009.11.051

[41] Yuan S, Sheng QR, Zhang JL, Yamashita H, He DN. Synthesis of thermally stable mesoporous TiO2 and investigation of its photocatalytic activity. Microporous. Mesoporous. Mater. 110 (2008) 501-507.

DOI: 10.1016/j.micromeso.2007.06.039

[42] Ismail A, Li MY, Zahid M, Fan LM, Zhang C, Li ZB, Zhu YJ. Effect of strong interaction between Co and Ce oxides in CoxCe1-xO2-δ oxides on its catalytic oxidation of toluene. Mol. Catal. 502 (2021) 111365.

DOI: 10.1016/j.mcat.2020.111356

[43] Lei ZH, Cheng PF, Wang YL, Xu LP, Lv L, Li X, Sun SF, Hao XD, Zhang YQ, Zhang Y, Weng Z. Pt-doped α-Fe2O3 mesoporous microspheres with low-temperature ultrasensitive properties for gas sensors in diabetes detection. Appl. Surf. Sci. 607 (2023) 154558.

DOI: 10.1016/j.apsusc.2022.154558

[44] Liu C, Xian H, Jiang Z, Wang LH, Zhang J, Zheng LR, Tan YS, Li XG. Insight into the improvement effect of the Ce doping into the SnO2 catalyst for the catalytic combustion of methane. Appl. Catal. B. 176-177 (2015) 542-552.

DOI: 10.1016/j.apcatb.2015.04.042

[45] Thirupathi B, Smirniotis P G. Nickel-doped Mn/TiO2 as an efficient catalyst for the low-temperature SCR of NO with NH3: Catalytic evaluation and characterizations. J. Catal. 288 (2012) 74-83.

DOI: 10.1016/j.jcat.2012.01.003

[46] Kijlstra W.S, Brands D.S, Poels E.K, Bliek A. Mechanism of the Selective Catalytic Reduction of NO by NH3 over MnOx/Al2O3. J. Catal. 171 (1997) 208-218.

DOI: 10.1006/jcat.1997.1788

[47] Maqbool M S, Pullur A K, Ha H P. Novel sulfation effect on low-temperature activity enhancement of CeO2-added Sb-V2O5/TiO2 catalyst for NH3-SCR. Appl. Catal. B. 152-153 (2014) 28-37.

DOI: 10.1016/j.apcatb.2014.01.017

[48] Lu XN, Song CY, Jia SH, Tong ZS, Tang XL, Teng YX. Low-temperature selective catalytic reduction of NOx with NH3 over cerium and manganese oxides supported on TiO2–graphene. Chem. Eng. J. 260 (2015) 776-784.

DOI: 10.1016/j.cej.2014.09.058

[49] Li JY, Cui W, Sun YJ, Chu YH, Cen WL, Dong F. Directional electron delivery via a vertical channel between g-C3N4 layers promotes photocatalytic efficiency. J. Mater. Chem. A. 5 (2017) 9358-9364.

DOI: 10.1039/c7ta02183f

[50] Royer S, Duprez D, Kaliaguine S. Role of bulk and grain boundary oxygen mobility in the catalytic oxidation activity of LaCo1-xFexO3. J. Catal. 364 (2005) 364-375.

DOI: 10.1016/j.jcat.2004.11.041

[51] Gac W, Stowik G, Zawadzki W. Structural and surface changes of copper modified manganese oxides. Appl. Surf. Sci. 370 (2016) 536-544.

DOI: 10.1016/j.apsusc.2016.02.136

[52] Sakai M, Nagai Y, Aoki Y, Takahashi N. Investigation into the catalytic reduction of NOx at copper–ceria interface active sites. Appl. Catal. A. 510 (2016) 57-63.

DOI: 10.1016/j.apcata.2015.11.007