Performance and mechanism of cobalt-aluminum spinel catalyzed oxidation of nitric oxide

LIU Baiyun; ZHANG Jianning; ZHANG Yihuai; ZHANG Tao

doi:10.13205/j.hjgc.202606007

Volume 44 Issue 6

Jun. 2026

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LIU Baiyun, ZHANG Jianning, ZHANG Yihuai, ZHANG Tao. Performance and mechanism of cobalt-aluminum spinel catalyzed oxidation of nitric oxide[J]. ENVIRONMENTAL ENGINEERING , 2026, 44(6): 60-71. doi: 10.13205/j.hjgc.202606007

Citation:

LIU Baiyun, ZHANG Jianning, ZHANG Yihuai, ZHANG Tao. Performance and mechanism of cobalt-aluminum spinel catalyzed oxidation of nitric oxide[J]. ENVIRONMENTAL ENGINEERING , 2026, 44(6): 60-71. doi: 10.13205/j.hjgc.202606007

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Performance and mechanism of cobalt-aluminum spinel catalyzed oxidation of nitric oxide

doi: 10.13205/j.hjgc.202606007

1. School of Chemistry and Life Resources, Renmin University of China, Beijing 100872, China;
2. College of Science, China University of Petroleum (Beijing), Beijing 102249, China

Received Date: 2025-02-08
Accepted Date: 2025-03-01
Rev Recd Date: 2025-02-21

Available Online: 2026-07-06

Abstract

Abstract

Spinel metal oxides derived from cobalt-aluminum hydrotalcite were synthesized using hydrothermal， coprecipitation， and sol-gel methods， and their performance in catalytic NO oxidation was studied. The outcomes derived from X-ray photoelectron spectroscopy （XPS）， O₂temperature-programmed desorption （O₂-TPD）， H₂ temperature-programmed reduction （H₂-TPR）， and Raman spectroscopy collectively demonstrate that disparate synthesis methodologies exert a substantial impact on the surface Co²⁺/Co³⁺ ratio of the catalyst， which in turn modulates the formation of surface oxygen vacancies. Compared with coprecipitation and sol-gel methods， the catalysts synthesized through the hydrothermal method exhibit a superior density of surface oxygen vacancies. This enhanced vacancy density confers a heightened capacity for the adsorption and activation of gaseous oxygen molecules， culminating in the most effective NO oxidation performance among the examined catalysts. Additionally， NO temperature-programmed desorption （NO-TPD）， NO+O₂ temperature-programmed desorption （NO+O₂-TPD）， and in situ diffuse reflectance infrared Fourier transform spectroscopy （in situ DRIFTS） indicate that nitrates are the key intermediates for NO oxidation to NO₂ on these catalysts， primarily following the Langmuir-Hinshelwood （L-H） reaction mechanism.
- NO,
- cobalt-aluminum composite metal oxides,
- Co²⁺/Co³⁺ ratio,
- oxygen vacancies,
- Langmuir-Hinshelwood reaction mechanism

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References(63)

References

[1]	XING Y，ZHANG H，SU W，et al. Mineral derived catalysts optimized for selective catalytic reduction of NO _x with NH₃[J]. Journal of Cleaner Production，2021，289：125756.
[2]	ZHANG L，GAO H，CHANG X，et al. An application of green surfactant synergistically metal supported cordierite catalyst in denitration of selective catalytic oxidation[J]. Journal of Cleaner Production，2020，249：119307.
[3]	PALOMARES A，UZCÁTEGUI A，CORMA A，et al. NO _x storage/reduction catalysts based in cobalt/copper hydrotalcites[J]. Catalysis Today，2008，137（2/4）：261-266.
[4]	CHANG H，CHEN X，LI J，et al. Improvement of activity and SO₂ tolerance of Sn-modified MnO _x-CeO₂ catalysts for NH₃-SCR at low temperatures[J]. Environmental Science& Technology，2013，47（10）：5294-5301.
[5]	BUSCA G，LIETTI L，RAMIS G，et al. Chemical and mechanistic aspects of the selective catalytic reduction of NO_x by ammonia over oxide catalysts：A review[J]. Applied Catalysis B：Environmental，1998，18（1/2）：1-36.
[6]	CUI M，LI Y，WANG X，et al. Effect of preparation method on MnO _x-CeO₂ catalysts for NO oxidation[J]. Journal of Rare Earths，2013，31（6）：572-576.
[7]	YANG W，ZHOU B，ZHANG Y，et al. A novel low-temperature Fe-Fe double-atom catalyst for a“fast SCR” reaction[J]. Molecular Catalysis，2022，533：112769.
[8]	SCHEJBAL M，STEPANEK J，MAREK M，et al. Modelling of soot oxidation by NO₂ in various types of diesel particulate filters[J]. Fuel，2010，89（9）：2365.
[9]	YOON D，LIM E，KIM Y，et al. NO oxidation activity of Ag-doped perovskite catalysts[J]. Journal of Catalysis，2014，319：182-193.
[10]	SALMAN A，ENGER B，AUVRAY X，et al. Catalytic oxidation of NO to NO₂ for nitric acid production over a Pt/Al₂O₃ catalyst[J]. Applied Catalysis A：General，2013，564：142-146.
[11]	BENARD S，RETAILLEAU L，GAILLARD F，et al. Supported platinum catalysts for nitrogen oxide sensors[J]. Applied Catalysis B：Environmental，2005，55（1）：11-21.
[12]	WULLA S，CHEN N，CUMARANATUNGE L，et al. Effect of potassium and water vapor on the catalytic reaction of nitric oxide and dioxygen over platinum[J]. Catalysis Today，2006，114（1）：57-63.
[13]	XUE E，SESHAN K，ROSS J，et al. Roles of supports，Pt loading and Pt dispersion in the oxidation of NO to NO₂ and of SO₂ to SO₃[J]. Applied Catalysis B：Environmental，1996，11（1）：65-79.
[14]	HONG Z，WANG Z，LI X，et al. Catalytic oxidation of nitric oxide（NO）over different catalysts：an overview[J]. Catalysis Science& Technology，2017，7（16）：3440-3452.
[15]	SHANG D，ZHONG Q，CAI W，et al. High performance of NO oxidation over Ce-Co-Ti catalyst：The interaction between Ce and Co[J]. Applied Surface Science，2015，325：211-216.
[16]	REN W，DING T，YANG Y，et al. Identifying oxygen activation/oxidation sites for efficient soot combustion over silver catalysts interacted with nanoflower-like hydrotalcite-derived CoAlO metal oxides[J]. ACS Catalysis，2019，9（9）：8772-8784.
[17]	QIAN P，ZHONG W，LIU K，et al. Cobalt-aluminum spinel supported on modified γ-alumina for peroxymonosulfate activation：Si-Al ratio of support to optimize performance and reusability[J]. Journal of Environmental Management，2023，345：118905.
[18]	ASLAM R，USMAN M，IRFAN M，et al. A comparative study of LHHW and ER kinetic models for NO oxidation over Co₃O₄ catalyst[J]. Journal of Environmental Chemical Engineering，2016，4（3）：2871-2877.
[19]	MA L，ZHANG W，WANG Y，et al. Catalytic performance and reaction mechanism of NO oxidation over Co₃O₄ catalysts[J]. Applied Catalysis B：Environmental，2020，267：118371.
[20]	JABŁOŃSKA M，NOTHDURFT K，NOCUŃM，et al. Redox-performance correlations in Ag-Cu-Mg-Al，Ce-Cu-Mg-Al，and Ga-Cu-Mg-Al hydrotalcite derived mixed metal oxides[J]. Applied Catalysis B：Environmental，2017，207：385-396.
[21]	SZYMASZEK-WAWRYCA A，SUMMA P，DURACZYŃSKA D，et al. Hydrotalcite-modified clinoptilolite as the catalyst for selective catalytic reduction of NO with ammonia（NH₃-SCR）[J]. Materials，2020，15（22）：7884.
[22]	ZHAO S，HU F，LI J. Hierarchical core-shell Al₂O₃@Pd-CoAlO microspheres for low temperature toluene combustion[J]. ACS Catalysis，2016，6（6）：3433-3441.
[23]	YANG Q，WANG X，WANG H，et al. Surface tailoring on SrMnO₃@SmMn₂O₅ for boosting the performance in diesel oxidation catalyst[J]. Applied Catalysis B：Environmental，2023，320：121993.
[24]	WANG X，YANG Q，LI X，et al. Exploring the dynamic evolution of lattice oxygen on exsolved-Mn₂O₃@SmMn₂O₅ interfaces for NO Oxidation[J]. Nature Communications，2024，15：7613.
[25]	FAHAMI A，AL-HAZMI F，AL-GHAMDI A，et al. Structural characterization of chlorine intercalated Mg-Al layered double hydroxides：A comparative study between mechanochemistry and hydrothermal methods[J]. Journal of Alloys and Compounds，2016，683：100-107.
[26]	POLATO C，HENRIQUES C，RODRIGUES A，et al. De-SO _x additives based on mixed oxides derived from Mg，Al-hydrotalcite-like compounds containing Fe，Cu，Co or Cr[J]. Catalysis Today，2008，133-135：534-540.
[27]	JAUBERTIE C，HOLGADO M，ROMÁN M SAN，et al. Structural characterization and delamination of lactate-intercalated Zn，Al-layered double hydroxides[J]. Chemistry of Materials，2006，18（13）：3114-3121.
[28]	ZHONG S，SUN Y，XIN H，et al. NO oxidation over Ni-Co perovskite catalysts[J]. Chemical Engineering Journal，2015，275：351-356.
[29]	WU E，LIN D，CHEN Y，et al. N-doped CoAl oxides from hydrotalcites with enhanced oxygen vacancies for excellent low-temperature propane oxidation[J]. Journal of Environmental Sciences，2022，116：79-89.
[30]	HUO W，DONG X，YUAN J，et al. Synthesis of Bi₂WO₆ with gradient oxygen vacancies for highly photocatalytic NO oxidation and mechanism study[J]. Chemical Engineering Journal，2019，361：129-138.
[31]	ZHANG R，LIU Y，JIANG X，et al. Vital role of synthesis temperature in Co-Cu layered hydroxides and their fenton-like activity for RhB degradation[J]. Catalysts，2022，12（6）：646.
[32]	MO S，LI S，LI J，et al. Rich surface Co（III）ions-enhanced Co nanocatalyst benzene/toluene oxidation performance derived from Co^ⅡCo^Ⅲ layered double hydroxide[J]. Nanoscale，2016，8（34）：15763-15773.
[33]	ZHAO M，DENG J，LIU J，et al. Roles of surface-active oxygen species on 3DOM cobalt-based spinel catalysts M_x Co_3- _x O₄（M=Zn and Ni）for NO _x assisted soot oxidation[J]. ACS Catalysis，2019，9（8）：7548-7567.
[34]	SHI Q，ZHANG Y，CHEN K，et al. Cobalt vacancies assisted ion diffusion in Co₂AlO₄ carbon nanofibers for enhancing lithium battery performance[J]. Dalton Transactions，2020，49（29）：10127-10137.
[35]	WANG X，LIU Y，ZHANG T，et al. Geometrical-site-dependent catalytic activity of ordered mesoporous Co-based spinel for benzene oxidation：In situ DRIFTS study coupled with Raman and XAFS spectroscopy[J]. ACS Catalysis，2017，7（3）：1626-1636.
[36]	ZHAO Q，ZHANG Y，LIU Q，et al. Boosting the catalytic performance of volatile organic compound oxidation over platelike MnO₂/CoAlO catalyst by weakening the Co-O bond and accelerating oxygen activation[J]. ACS Catalysis，2023，13（2）：1492-1502.
[37]	LIAO W，ZHANG S，QIN Y，et al. Highly disordered MnO _x catalyst for NO oxidation at medium-low temperatures[J]. Chemical Engineering Journal，2024，483：149275.
[38]	LIU F，HE H. Structure-activity relationship of iron titanate catalysts in the selective catalytic reduction of NO _x with NH₃[J]. The Journal of Physical Chemistry. C，2010，114（40）：16929-16936.
[39]	LIU Z，GAO X，WANG K，et al. Designing hydrotalcite-derived CoAlO catalysts for highly selective catalytic CO₂ methanation[J]. Fuel Processing Technology，2023，241：107628.
[40]	ZHAO Q，GE Y，FU K，et al. Oxidation of acetone over Co-based catalysts derived from hierarchical layer hydrotalcite：Influence of Co/Al molar ratios and calcination temperatures[J]. Chemosphere，2018，204：257-266.
[41]	MUÑOZ M，MORENO S，MOLINA R，et al. Synthesis of Ce and Pr-promoted Ni and Co catalysts from hydrotalcite type precursors by reconstruction method[J]. International Journal of Hydrogen Energy，2012，37（24）：18827-18842.
[42]	CASTAÑO M，MOLINA H，MORENO S，et al. Catalytic oxidation of VOCs on MnMgAlO _x mixed oxides obtained by auto-combustion[J]. Journal of Molecular Catalysis A：Chemical，2015，398：358-367.
[43]	WANG H，CHEN H，WANG Y，et al. Performance and mechanism comparison of manganese oxides at different valence states for catalytic oxidation of NO[J]. Chemical Engineering Journal，2019，361：1161-1172.
[44]	CHEN L，ZHANG C，LI Y，et al. Hierarchically hollow MnO₂@CeO₂ heterostructures for NO oxidation：Remarkably promoted activity and SO₂ tolerance[J]. ACS Catalysis，2021，11（17）：10988-10996.
[45]	MAO H，LUO H，CHEN Q，et al. Catalytic oxidation of NO over Fe-doped MnO₂ catalyst[J]. Industrial& Engineering Chemistry Research，2022，61（46）：16992-17000.
[46]	CHEN H，WANG Y，LYU Y，et al. High catalytic activity of Mn-based catalyst in NO oxidation at low temperature and over a wide temperature span[J]. Molecular Catalysis，2018，454：21-29.
[47]	GUO L，BO L，LI Y，et al. Sr doping on the structure property and NO oxidation performance of dual-site doped perovskite La（Sr）Co（Fe）O₃[J]. Solid State Sciences，2021，113：106519.
[48]	WANG X，LI X，MU J，et al. Oxygen vacancy-rich porous Co₃O₄ nanosheets toward boosted NO reduction by CO and CO oxidation：Insights into the structure-activity relationship and performance enhancement mechanism[J]. ACS Applied Materials& Interfaces，2019，11（45）：41988-41999.
[49]	KASHIF M，YUAN M，ABDUALLAH M，et al. Fully selective catalytic oxidation of NO to NO₂ over most active Ga-PCH catalyst[J]. Journal of Environmental Chemical Engineering，2020，8（2）：103524.
[50]	YANG Q，WANG X，WANG X，et al. Surface reconstruction of a mullite-type catalyst via selective dissolution for NO oxidation[J]. ACS Catalysis，2021，11（23）：14507-14520.
[51]	TANG X，GAO F，XIANG Y，et al. Effect of potassium-precursor promoters on catalytic oxidation activity of Mn-CoO _x catalysts for NO removal[J]. Industrial& Engineering Chemistry Research，2015，54（37）：9116-9123.
[52]	ZHAO B，RAN R，YANG L，et al. Comparative study of La_1- _x Ce _x MnO_3+δ perovskites and Mn-Ce mixed oxides for NO catalytic oxidation[J]. Journal of Rare Earths，2020，38（8）：863-872.
[53]	WANG W，LI W，GUO R，et al. A CeFeO _x catalyst for catalytic oxidation of NO to NO₂[J]. Journal of Rare Earths，2016，34（9）：876-881.
[54]	ZUO S，WANG P，HE M，et al. Three-dimensional ordered macroporous LaFe_1- _x Mn _x O₃ with high stability for efficient NO oxidation and sulfur resistance[J]. Chemical Communications，2024，60（39）：5157-5160.
[55]	JI Y，BAI S，CROCKER M，et al. Al₂O₃-based passive NO _x adsorbers for low temperature applications[J]. Applied Catalysis B：Environmental，2015，170/171：283-292.
[56]	THAMPY S，ZHENG Y，DILLON S，et al. Superior catalytic performance of Mn-Mullite over Mn-Perovskite for NO oxidation[J]. Catalysis Today，2018，310（15）：195-201.
[57]	HADJIIVANOV K I. Identification of neutral and charged N _x O _y surface species by IR spectroscopy[J]. Catalysis Reviews：Science and Engineering，2000，42（1/2）：71-144.
[58]	LIU Y，GAO F，YI H，et al. Recent advances in selective catalytic oxidation of nitric oxide（NO-SCO）in emissions with excess oxygen：a review on catalysts and mechanisms[J]. Environmental Science and Pollution Research，2021，28：2549-2571.
[59]	HE D，DING X，LI S，et al. Constructing a Pt/YMn₂O₅ interface to form multiple active centers to improve the hydrothermal stability of NO oxidation[J]. ACS Applied Materials& Interfaces，2022，14（18）：20875-20887.
[60]	XIN Y，CHENG L，LÜ Y，et al. Experimental and theoretical insight into the facet-dependent mechanisms of NO oxidation catalyzed by structurally diverse Mn₂O₃ nanocrystals[J]. ACS Catalysis，2022，12（1）：397-410.
[61]	JONATHAN H，RESHMA R，LIVIA G，et al. Regulating oxygen activity of perovskites to promote NO _x oxidation and reduction kinetics[J]. Nature Catalysis，2021（4）：663-673.
[62]	CHEN L，WANG Y，HOU X，et al. Mesoporous Co₃O₄ nanoparticles with enriched oxygen defects for efficient NO oxidation[J]. Industrial& Engineering Chemistry Research，2024，63（32）：14043-14051.
[63]	ATRIBAK I，AZAMBRE B，LÓPEZ A B，et al. Effect of NO _x adsorption/desorption over ceria-zirconia catalysts on the catalytic combustion of model soot[J]. Applied Catalysis B：Environmental，2009，92（1-2）：126-137.