钴铝尖晶石催化氧化一氧化氮的性能与机理研究

刘白云; 张健宁; 张艺怀; 张涛

doi:10.13205/j.hjgc.202606007

钴铝尖晶石催化氧化一氧化氮的性能与机理研究

doi: 10.13205/j.hjgc.202606007

刘白云¹,
张健宁^1,2,
张艺怀¹,
张涛^1, ,

1. 中国人民大学化学与生命资源学院, 北京 100872;
2. 中国石油大学(北京) 理学院, 北京 102249

基金项目:

国家自然科学基金项目（22176216）

详细信息

作者简介:
刘白云(1999-),女,硕士,主要研究方向为大气污染控制。liubaiyun@ruc.edu.cn

通讯作者:
张涛(1985-),男,副教授。zhangt@ruc.edu.cn

计量
- 文章访问数: 28
- HTML全文浏览量: 1
- PDF下载量: 0
- 被引次数: 0
出版历程
- 收稿日期: 2025-02-08
- 录用日期: 2025-03-01
- 修回日期: 2025-02-21
- 网络出版日期: 2026-07-06

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

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

摘要

摘要: 分别采用水热法、共沉淀法和溶胶凝胶法合成了水滑石衍生的尖晶石型钴铝金属氧化物，并对其催化氧化NO性能进行了研究。X射线光电子能谱（XPS）、O₂程序升温脱附（O₂-TPD）、H₂程序升温还原（H₂-TPR）和拉曼（Raman）光谱分析结果表明，不同制备方法显著影响了催化剂表面Co²⁺/Co³⁺的比例，从而影响了其表面氧空位的生成。相比于共沉淀法和溶胶凝胶法，水热法制备的钴铝金属氧化物具有更多的表面氧空位，对气态氧分子的吸附活化能力更强，展现出更佳的NO氧化性能。此外，NO程序升温脱附（NO-TPD）、NO+O₂程序升温脱附（NO+O₂-TPD）和原位红外（in situ DRIFTS）的结果表明，硝酸盐是该系列催化剂表面NO氧化为NO₂的关键中间产物，并且NO氧化路径主要遵循Langmuir-Hinshelwood（L-H）反应机制。
- 一氧化氮 /
- 钴铝复合金属氧化物 /
- Co²⁺/Co³⁺比 /
- 氧空位 /
- Langmuir-Hinshelwood反应机制
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

HTML全文

参考文献(63)

[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.