Cracking the Selectivity Code: Unveiling the Catalyst Secrets in NH3-SCR of NO


Selective Catalytic Reduction (SCR) is a method of converting nitrogen oxides, which are harmful pollutants, into nitrogen (N2) and water (H2O) by reacting them with ammonia. This reaction takes place in the presence of a catalyst, typically at high temperatures. The commercial catalysts are usually made of vanadium, tungsten (or molybdenum), and titanium composite metal oxides. These materials are chosen for their ability to facilitate the reaction without being consumed in the process.

The primary reaction is: 4NO + 4NH3 + O2 → 4N2 + 6H2O. Secondary reactions may also occur, depending on the operating conditions and the catalyst used. SCR systems are installed in the exhaust streams of power plants, industrial boilers, and even in vehicles. In these systems, an ammonia-based reagent (like anhydrous ammonia, aqueous ammonia, or urea) is injected into the exhaust stream before it passes over the catalyst. The primary importance of SCR is its role in reducing air pollution. NOx gases are significant contributors to the formation of haze and acid rain,  all of which have serious environmental and health impacts.

In NH3-SCR, the primary challenge is achieving the desired selectivity towards N2 while minimizing the formation of N2O, a potent greenhouse gas and ozone-depleting substance. In a new paper published in the peer-reviewed journal Environmental Science & Technology led by Professor Guangzhi He and Professor Hong He and conducted by Meng Gao, Zhuocan Li, Yulong Shan, and Yu Sun, the authors highlighted that various oxide catalysts, such as Mn-based, Fe-based, and V-based catalysts, exhibit distinct characteristics of activity and selectivity. Notably, Mn-based catalysts demonstrate exceptional low-temperature activity but poor N2 selectivity, primarily due to N2O formation. Conversely, Fe- and V-based catalysts showed better N2 selectivity but lower low-temperature activity. Indeed, the new research work addressed the long-standing puzzle of the trade-off between activity and selectivity in NH3-SCR and provided critical insights for designing high-performance catalysts with balanced activity and selectivity, a crucial aspect in addressing environmental concerns related to NOx emissions.

The authors combined experimental measurements and density functional theory (DFT) calculations to unravel the selectivity mechanism of these catalysts. The focus is on understanding the energy barriers involved in the formation of N2 and N2O from the key intermediate NH2NO. The study suggests that these energy barriers dictate the selectivity of the catalysts. The authors prepared nanocrystals of α-MnO2 and α-Fe2O3 through hydrothermal methods, and a V2O5/TiO2 catalyst via an impregnation method. N2O formation tests under NH3-SCR conditions and temperature-programmed surface reaction (TPSR) experiments with isotopic labeling are conducted to understand the reaction pathways and mechanisms. They employed DFT calculations to evaluate the thermodynamics and kinetics of the reactions on the catalyst surfaces. These calculations help identify the energy barriers for different reaction pathways and the transition states involved. They found that the gap in energy barriers for N2 and N2O formation from NH2NO is a critical determinant of the selectivity of oxide catalysts. Mn-based catalysts have a smaller energy barrier gap, leading to lower N2 selectivity due to the easier formation of N2O. In contrast, Fe- and V-based catalysts have larger energy barrier gaps, favoring N2 formation and thus showing better N2 selectivity. In conclusion, the study conducted by Professor Guangzhi He and Professor Hong He with their colleagues opens avenues for further research in catalyst design, particularly in fine-tuning the properties of catalysts to achieve desired reaction outcomes. Understanding the atomic-level mechanisms of catalysis can lead to the development of more efficient and environmentally friendly catalytic processes, not only in NH3-SCR but also in other catalytic systems where selectivity is a key concern.

About the author

Prof. Hong He is a professor of the Research Center for Eco-Environmental Sciences (RCEES), Chinese Academy of Sciences (CAS) and the Director of Institute of Urban Environment, CAS. Prof. He received his doctorate (PhD) at the University of Tokyo in 1994. He studied and worked in Japan, the United States and Canada for 11 years, and thereafter joined RCEES through the “Hundred Talents Program” of the CAS in 2001. His research has mainly focused on fundamental and applied research in environmental catalysis and heterogeneous atmospheric chemistry, with a series of achievements in the areas of diesel emission control technologies, catalytic indoor air purification and haze formation mechanisms. He is the author of more than 610 peer-reviewed scientific publications, with over 35,000 citations. Prof. He is the first inventor on more than 70 authorized patents, some of which have already been implemented in commercial applications. He has also written a scholarly book in Chinese, “The Principles and Application of Environmental Catalysis,” and two chapters in related English language books. Prof. He was awarded the National Technology Invention Award (China, Second Class) in 2011, the National Science and Technology Progress Award (China, Second Class) in 2014, the National Natural Science Award (China, Second Class) in 2019 and the Ho Leung Ho Lee Foundation Prize for Scientific and Technological Innovation in 2017. He was elected as a member of the Chinese Academy of Engineering in 2017.

About the author

Prof. Guangzhi He is a professor of the Research Center for Eco-Environmental Sciences (RCEES), Chinese Academy of Sciences (CAS). Prof. He is primarily engaged in research on environmental catalysis and air pollution control, and has published more than 80 academic papers. He has achieved a series of innovative results in the field of catalytic purification of nitrogen oxides and has published as the first/corresponding author in Sci. Adv., Nat. Commun., Angew. Chem., Environ. Sci. Technol., and other journals. Prof. He has been selected into the National Youth Talent Support Program and the Youth Innovation Promotion Association of CAS. He has also received the President Prize of CAS for Excellent Ph.D. Graduates.


Meng Gao, Zhuocan Li, Guangzhi He,* Yulong Shan, Yu Sun, and Hong He*. Unveiling the Origin of Selectivity in the Selective Catalytic Reduction of NO with NH3 over Oxide Catalysts. Environ. Sci. Technol. 2023, 57, 8426−8434.

Go to Environ. Sci. Technol.

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