NO hydrogenation to NH₃ over FeCu/TiO₂ catalyst with improved activity

Abstract

Ammonia is crucial in industry and agriculture, but its production is hindered by environmental concerns and energy-intensive processes. Hence, developing an efficient and environmentally friendly catalyst is imperative. In this study, we employed a straightforward and efficient impregnation technique to create various Cu-doped catalysts. Notably, the optimized 10Fe-8Cu/TiO₂ catalyst exhibited exceptional catalytic performance in converting NO to NH₃, achieving an NO conversion rate exceeding 80% and an NH₃ selectivity exceeding 98% at atmospheric pressure and 350 °C. We employed in situ diffuse reflectance Fourier transform infrared spectroscopy and conducted density functional theory calculations to investigate the intermediates and subsequent adsorption. Our findings unequivocally demonstrate that Cu doping enhances the rate-limiting hydrogenation step and lowers the energy barrier for NH₃ desorption, thereby resulting in improved NO conversion and enhanced selectivity toward ammonia. This study presents a pioneering approach toward energy-efficient ammonia synthesis and recycling of nitrogen sources.

Graphical abstract

Keywords

NO hydrogenation / synthetic ammonia / 10Fe-xCu/TiO₂ / high selectivity

References

[1] Légaré M A, Bélanger-Chabot G, Dewhurst R D, Welz E, Krummenacher I, Engels B, Braunschweig H. Nitrogen fixation and reduction at boron. Science, 2018, 359(6378): 896–900

[2] Guo X, Gu J, Lin S, Zhang S, Chen Z, Huang S. Tackling the activity and selectivity challenges of electrocatalysts toward the nitrogen reduction reaction via atomically dispersed biatom catalysts. Journal of the American Chemical Society, 2020, 142(12): 5709–5721

[3] Peng X, Cai H, Zhou Y, Ni J, Wang X, Lin B, Lin J, Zheng L, Au C T, Jiang L. Studies of a highly active cobalt atomic cluster catalyst for ammonia synthesis. ACS Sustainable Chemistry & Engineering, 2022, 10(5): 1951–1960

[4] An Q, Mcdonald M, Fortunelli A, Goddard W A III. Si-doped Fe catalyst for ammonia synthesis at dramatically decreased pressures and temperatures. Journal of the American Chemical Society, 2020, 142(18): 8223–8232

[5] Chen J G, Crooks R M, Seefeldt L C, Bren K L, Bullock R M, Darensbourg M Y, Holland P L, Hoffman B, Janik M J, Jones A K. . Beyond fossil fuel—driven nitrogen transformations. Science, 2018, 360(6391): eaar6611

[6] Yang X, Nash J, Anibal J, Dunwell M, Kattel S, Stavitski E, Attenkofer K, Chen J G, Yan Y, Xu B. Mechanistic insights into electrochemical nitrogen reduction reaction on vanadium nitride nanoparticles. Journal of the American Chemical Society, 2018, 140(41): 13387–13391

[7] Lv X, Wei W, Li F, Huang B, Dai Y. Metal-free B@g-CN: visible/infrared light-driven single atom photocatalyst enables spontaneous dinitrogen reduction to ammonia. Nano Letters, 2019, 19(9): 6391–6399

[8] Xu W, Fan G, Chen J, Li J, Zhang L, Zhu S, Su X, Cheng F, Chen J. Nanoporous palladium hydride for electrocatalytic N₂ reduction under ambient conditions. Angewandte Chemie International Edition, 2020, 59(9): 3511–3516

[9] Rajavel K, Shen S, Ke T, Lin D. Photocatalytic and bactericidal properties of MXene-derived graphitic carbon-supported TiO₂ nanoparticles. Applied Surface Science, 2021, 538: 148083

[10] Li S, Chen X, Wang F, Xie Z, Hao Z, Liu L, Shen B. Promotion effect of Ni doping on the oxygen resistance property of Fe/CeO₂ catalyst for CO-SCR reaction: activity test and mechanism investigation. Journal of Hazardous Materials, 2022, 431: 128622

[11] Zhao R, Wei X, Chu B, Chen K, Qin Q, Liu H, Zhou Y, Li B, Dong L. Multi-phase coexisting metal oxide derived by MOFs for the CO-SCR reaction at low temperature and in situ DRIFTS study on reaction mechanism. Applied Surface Science, 2022, 580: 152277

[12] Wang C, Cheng Q, Wang X, Ma K, Bai X, Tan S, Tian Y, Ding T, Zheng L, Zhang J, Li X. Enhanced catalytic performance for CO preferential oxidation over CuO catalysts supported on highly defective CeO₂ nanocrystals. Applied Surface Science, 2017, 422: 932–943

[13] Liu Q, Mi J, Chen X, Wang S, Chen J, Li J. Effects of phosphorus modification on the catalytic properties and performance of CuCeZr mixed metal catalyst for simultaneous removal of CO and NO_x. Chemical Engineering Journal, 2021, 423: 130228

[14] Zhang J, Qu H. Low-temperature selective catalytic reduction of NO_x with NH₃ over Fe-Cu mixed oxide/ZSM-5 catalysts containing Fe₂CuO₄ phase. Research on Chemical Intermediates, 2015, 41(7): 4961–4975

[15] Ali S, Chen L, Yuan F, Li R, Zhang T, Bakhtiar S H, Leng X, Niu X, Zhu Y. Synergistic effect between copper and cerium on the performance of Cu_x-Ce_0.5−x-Zr_0.5 (x = 0.1–0.5) oxides catalysts for selective catalytic reduction of NO with ammonia. Applied Catalysis B: Environmental, 2017, 210: 223–234

[16] Chen K, Zhang Y, Xiang J, Zhao X, Li X, Chu K. P-block antimony single-atom catalysts for nitric oxide electroreduction to ammonia. ACS Energy Letters, 2023, 8(3): 1281–1288

[17] Zhang H, Li Y, Cheng C, Zhou J, Yin P, Wu H, Liang Z, Zhang J, Yun Q, Wang A L. . Isolated electron—rich ruthenium atoms in intermetallic compounds for boosting electrochemical nitric oxide reduction to ammonia. Angewandte Chemie International Edition, 2023, 62(4): e202213351

[18] Long J, Chen S, Zhang Y, Guo C, Fu X, Deng D, Xiao J. Direct electrochemical ammonia synthesis from nitric oxide. Angewandte Chemie International Edition, 2020, 59(24): 9711–9718

[19] Zhan C G, Nichols J A, Dixon D A. Ionization potential, electron affinity, electronegativity, hardness, and electron excitation energy: molecular properties from density functional theory orbital energies. Journal of Physical Chemistry A, 2003, 107(20): 4184–4195

[20] McPherson I J, Sudmeier T, Fellowes J, Tsang S C E. Materials for electrochemical ammonia synthesis. Dalton Transactions (Cambridge, England), 2019, 48(5): 1562–1568

[21] Jia H P, Quadrelli E A. Mechanistic aspects of dinitrogen cleavage and hydrogenation to produce ammonia in catalysis and organometallic chemistry: relevance of metal hydride bonds and dihydrogen. Chemical Society Reviews, 2014, 43(2): 547–564

[22] Guo C, Ran J, Vasileff A, Qiao S Z. Rational design of electrocatalysts and photo (electro) catalysts for nitrogen reduction to ammonia (NH₃) under ambient conditions. Energy & Environmental Science, 2018, 11(1): 45–56

[23] Li K, Xian X, Wang J, Yu N. First-principle study on honeycomb fluorated-InTe monolayer with large Rashba spin splitting and direct bandgap. Applied Surface Science, 2019, 471: 18–22

[24] Perdew J P, Burke K, Ernzerhof M. Generalized gradient approximation made simple. Physical Review Letters, 1996, 77(18): 3865–3868

[25] Wei L, Cui S, Guo H, Ma X. Study on the role of Mn species in low temperature SCR on MnO_x/TiO₂ through experiment and DFT calculation. Molecular Catalysis, 2018, 445: 102–110

[26] Hernández-Haro N, Ortega-Castro J, Martynov Y B, Nazmitdinov R G, Frontera A. DFT prediction of band gap in organic-inorganic metal halide perovskites: an exchange-correlation functional benchmark study. Chemical Physics, 2019, 516: 225–231

[27] LiJZhuJFuSTaoLChuBQinQWangJLiBDongL. Insight into copper-cerium catalysts with different Cu valence states for CO-SCR and in-situ DRIFTS study on reaction mechanism. Fuel, 2022, 126962

[28] Yi X, Wang J, Liu Y, Chen Y, Chen J. Promotional effect of Fe and Ce co-doping on a V₂O₅-WO₃/TiO₂ catalyst for SCR of NO_x with high K and Pb resistance. Catalysis Science & Technology, 2022, 12(13): 4169–4180

[29] Xie S, Li L, Jin L, Wu Y, Liu H, Qin Q, Wei X, Liu J, Dong L, Li B. Low temperature high activity of M (M = Ce, Fe, Co, Ni) doped M-Mn/TiO₂ catalysts for NH₃-SCR and in situ DRIFTS for investigating the reaction mechanism. Applied Surface Science, 2020, 515: 146014

[30] Cao J, Liu W, Kang K, Chen L, Qiao X, Yao X. Effects of the morphology and crystal-plane of TiO₂ on NH₃-SCR performance and K tolerance of V₂O₅-WO₃/TiO₂ catalyst. Applied Catalysis A, General, 2021, 623: 118285

[31] Tian J, Wang C, Yu F, Zhou X, Zhang J, Yang S, Dan J, Cao P, Dai B, Wang Q, Zhang J. Mn-Ce-Fe-Al mixed oxide nanoparticles via a high shear mixer facilitated coprecipitation method for low temperature selective catalytic reduction of NO with NH₃. Applied Catalysis A, General, 2019, 586: 117237

[32] GoodmanD. “Catalytically active Au on titania”: Yet another example of a strong metal support interaction (SMSI)? Catalysis Letters, 2005, 99(1–2): 1–4

[33] Ali S, Chen L, Li Z, Zhang T, Li R, Leng X, Yuan F, Niu X, Zhu Y. Cu_x-Nb_1.1−x (x = 0.45, 0.35, 0.25, 0.15) bimetal oxides catalysts for the low temperature selective catalytic reduction of NO with NH₃. Applied Catalysis B: Environmental, 2018, 236: 25–35

[34] Kwak J H, Tonkyn R G, Kim D H, Szanyi J, Peden C H. Excellent activity and selectivity of Cu-SSZ-13 in the selective catalytic reduction of NO_x with NH₃. Journal of Catalysis, 2010, 275(2): 187–190

[35] Hou Y, Wang J, Li Q, Liu Y, Bai Y, Zeng Z, Huang Z. Environmental-friendly production of FeNbTi catalyst with significant enhancement in SCR activity and SO₂ resistance for NO_x removal. Fuel, 2021, 285: 119133

[36] Wang X, Shi Y, Li S, Li W. Promotional synergistic effect of Cu and Nb doping on a novel Cu/Ti-Nb ternary oxide catalyst for the selective catalytic reduction of NO_x with NH₃. Applied Catalysis B: Environmental, 2018, 220: 234–250

[37] Ma Z, Wu X, Härelind H, Weng D, Wang B, Si Z. NH₃-SCR reaction mechanisms of NbO_x/Ce_0.75Zr_0.25O₂ catalyst: DRIFTS and kinetics studies. Journal of Molecular Catalysis A Chemical, 2016, 423: 172–180

[38] Li Y, Han X, Hou Y, Guo Y, Liu Y, Cui Y, Huang Z. Role of CTAB in the improved H₂O resistance for selective catalytic reduction of NO with NH₃ over iron titanium catalyst. Chemical Engineering Journal, 2018, 347: 313–321

[39] Yao X, Chen L, Cao J, Chen Y, Tian M, Yang F, Sun J, Tang C, Dong L. Enhancing the deNO_x performance of MnO_x/CeO₂-ZrO₂ nanorod catalyst for low-temperature NH₃-SCR by TiO₂ modification. Chemical Engineering Journal, 2019, 369: 46–56

[40] Liu H, Fan Z, Sun C, Yu S, Feng S, Chen W, Chen D, Tang C, Gao F, Dong L. Improved activity and significant SO₂ tolerance of samarium modified CeO₂-TiO₂ catalyst for NO selective catalytic reduction with NH₃. Applied Catalysis B: Environmental, 2019, 244: 671–683

[41] He C, Yang H, Xi M, Fu L, Huo J, Zhao C. Efficient electrocatalytic reduction of NO to ammonia on BC3 nanosheets. Environmental Research, 2022, 212: 113479

[42] He C, Wang J, Fu L, Zhao C, Huo J. Associative vs. dissociative mechanism: electrocatalysis of nitric oxide to ammonia. Chinese Chemical Letters, 2022, 33(2): 1051–1057

[43] He C, Sun R, Fu L, Huo J, Zhao C, Li X, Song Y, Wang S. Defect engineering for high-selection-performance of NO reduction to NH₃ over CeO₂ (111) surface: a DFT study. Chinese Chemical Letters, 2022, 33(1): 527–532

[44] Huang B, Chen B, Zhu G, Peng J, Zhang P, Qian Y, Li N. Electrochemical ammonia synthesis via NO reduction on 2D-MOF. ChemPhysChem, 2022, 23(4): e202100785

Competing interest

The authors declare that they have no competing interests.

RIGHTS & PERMISSIONS

2023 Higher Education Press