磷酸改性CeO2纳米棒负载Pt催化剂催化丙烷燃烧性能的研究

doi:10.19964/j.issn.1006-4990.2023-0192

无机盐工业 ›› 2024, Vol. 56 ›› Issue (1): 141-148.doi: 10.19964/j.issn.1006-4990.2023-0192

• 催化材料 • 上一篇

磷酸改性CeO₂纳米棒负载Pt催化剂催化丙烷燃烧性能的研究

金声势¹^,²(), 刘凯杰², 刘秋文², 张一波¹^,²(), 杨向光¹^,²()

1.中国科学技术大学稀土学院，安徽合肥 230026
2.中国科学院赣江创新研究院，江西赣州 341000

收稿日期:2023-04-03 出版日期:2024-01-10 发布日期:2024-01-18
通讯作者: 张一波（1985— ），男，博士，研究员，主要研究方向为稀土功能材料、环境催化与大气污染控制；E-mail：yibozhang@gia.cas.cn;
杨向光（1962— ），男，博士，研究员，主要研究方向为环境催化；E-mail：xgyang@gia.cas.cn。
作者简介:金声势（1998— ），男，硕士，主要从事稀土催化材料研究；E-mail：jss20@gia.cas.cn。
基金资助:
国家自然科学基金项目(22072141);国家自然科学基金项目(22176185);中国科学院青年创新促进会人才项目(2018263);江西省双千计划（青年）项目(jxsq2020101047);中国科学院重点部署项目(ZDRW-CN-2021-3);中国科学院赣江创新研究院自主部署项目(E355C001);国家重点研发计划项目(2022YFB3504200);江西省杰出青年基金项目(20232ACB213004)

Study on catalytic performance of phosphoric acid modified CeO₂ nanorod supported Pt catalyst for propane combustion

JIN Shengshi¹^,²(), LIU Kaijie², LIU Qiuwen², ZHANG Yibo¹^,²(), YANG Xiangguang¹^,²()

1. School of Rare Earths，University of Science and Technology of China，Hefei 230026，China
2. Ganjiang Innovation Academy，Chinese Academy of Sciences，Ganzhou 341000，China

Received:2023-04-03 Published:2024-01-10 Online:2024-01-18

摘要/Abstract

摘要：

机动车和石油化工等污染源排放造成的环境污染日益严重，其中以丙烷为代表的低碳烷烃结构稳定，难以实现低温完全氧化，亟需开发高效低碳烷烃低温催化氧化催化剂。以氧化铈纳米棒为载体，通过酸改性合成不同量磷酸改性的1%Pt/CeO₂-yPO_x 催化剂，发现磷酸改性之后丙烷催化燃烧T₅₀降低了60 ℃。通过XRD、TEM、EDS mapping等表征发现Pt和P均匀分布在氧化铈表面，且在磷酸改性和Pt负载过程后，氧化铈结构保持稳定。XPS和原位CO-DRIFTs表征结果表明磷酸改性之后，Pt在催化剂表面颗粒大小随磷酸改性程度增加而逐渐变大，并存在最优的Pt²⁺和Pt⁴⁺比，有利于丙烷在催化剂表面吸附和反应。H₂-TPR和NH₃-TPD表征结果表明，磷酸改性之后，催化剂表面产生了大量的酸性位，而磷酸改性并未大幅降低催化剂的氧化还原能力，从而提高了铈基催化剂的丙烷燃烧活性。

关键词: 铈基催化剂, 磷酸改性, 丙烷氧化, 贵金属, 稀土催化剂

Abstract:

With the increasingly serious environmental pollution caused by the emission of pollution sources such as motor vehicles and petrochemicals，the structure of low-carbon alkanes represented by propane is stable，and it is difficult to achieve complete oxidation at low temperature.Therefore，it is urgent to develop high-efficiency low-temperature catalytic oxidation catalysts.The different amounts of phosphoric acid modified 1%Pt/CeO₂-yPO_x catalysts were synthesized by acid modification with cerium oxide nanorods as carrier.It was found that the T₅₀ of propane catalytic combustion was reduced by 60 ℃ after phosphoric acid modification.Through XRD，TEM，EDS mapping and other characterization，it was found that Pt and P were evenly distributed on the surface of cerium oxide，and the structure of cerium oxide remained stable after phosphoric acid modification and Pt loading process.XPS and in-situ CO-DRIFTs showed that after phosphoric acid modification，the particle size of Pt on the surface of the catalyst was increased with the increase of the modification degree of phosphoric acid.There was an optimal Pt²⁺/Pt⁴⁺ ratio，which was beneficial to the adsorption and reaction of propane on the catalyst surface.H₂-TPR and NH₃-TPD showed that a large number of acid sites were generated on the surface of the catalyst after phosphoric acid modification，while phosphoric acid modification did not significantly reduce the redox ability of the catalyst，thus improving the propane combustion activity of the cerium-based catalyst.

Key words: cerium-based catalyst, phosphoric acid modification, propane oxidation, precious metals, rare earth catalysts

中图分类号:

O643.3

金声势, 刘凯杰, 刘秋文, 张一波, 杨向光. 磷酸改性CeO₂纳米棒负载Pt催化剂催化丙烷燃烧性能的研究[J]. 无机盐工业, 2024, 56(1): 141-148.

JIN Shengshi, LIU Kaijie, LIU Qiuwen, ZHANG Yibo, YANG Xiangguang. Study on catalytic performance of phosphoric acid modified CeO₂ nanorod supported Pt catalyst for propane combustion[J]. Inorganic Chemicals Industry, 2024, 56(1): 141-148.

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参考文献 20

1	HE Chi， CHENG Jie， ZHANG Xin，et al.Recent advances in the catalytic oxidation of volatile organic compounds：A review based on pollutant sorts and sources［J］.Chemical Reviews，2019，119（7）：4471-4568.
2	YANG Xinwei， LI Qing， LU Erjun，et al.Taming the stability of Pd active phases through a compartmentalizing strategy toward nanostructured catalyst supports［J］.Nature Communications，2019，10：1611.
3	XING Feilong， NAKAYA Y， YASUMURA S，et al.Ternary platinum-cobalt-indium nanoalloy on ceria as a highly efficient catalyst for the oxidative dehydrogenation of propane using CO₂ ［J］.Nature Catalysis，2022，5（1）：55-65.
4	LI Weijing， LI Tingyu， WEY M Y.Preferred enhancement of fast-SCR by Mn/CeSiO_x catalyst：Study on Ce/Si promotion and shape dependence［J］.Chemical Engineering Journal，2021，403：126317.
5	YOSHIDA H， YAZAWA Y， HATTORI T.Effects of support and additive on oxidation state and activity of Pt catalyst in propane combustion［J］.Catalysis Today，2003，87（1/2/3/4）：19-28.
6	BARAKAT T， ROOKE J C， TIDAHY H L，et al.Noble-metal-based catalysts supported on zeolites and macro-mesoporous metal oxide supports for the total oxidation of volatile organic compoun- ds［J］.ChemSusChem，2011，4（10）：1420-1430.
7	ZHANG Ling， PENG Yuexin， ZHANG Juan，et al.Adsorptive and catalytic properties in the removal of volatile organic compounds over zeolite-based materials［J］.Chinese Journal of Catalysis，2016，37（6）：800-809.
8	HU Zong， LIU Xiaofei， MENG Dongmei，et al.Effect of ceria crystal plane on the physicochemical and catalytic properties of Pd/ceria for CO and propane oxidation［J］.ACS Catalysis，2016，6（4）：2265-2279.
9	ZHU Liang， JIN Xin， ZHANG Yuyang，et al.Visualizing anisotropic oxygen diffusion in ceria under activated conditions［J］.Physical Review Letters，2020，124（5）：056002.
10	HAN Xinyu， LIU Kaijie， BIAN Mengyao，et al.CeO_2–_δ nanoparticles supported on SnNb₂O₆ nanosheets for selective catalytic reduction of NO_x with NH₃ ［J］.ACS Applied Nano Materials，2022，5（9）：13529-13541.
11	HUANG Zhenpeng， CAO Shiying， YU Jihang，et al.Total oxidation of light alkane over phosphate-modified Pt/CeO₂ catalys-ts［J］.Environmental Science & Technology，2022，56（13）：9661-9671.
12	MA Lei， SEO C Y， NAHATA M，et al.Shape dependence and sulfate promotion of CeO₂ for selective catalytic reduction of NO_x with NH₃ ［J］.Applied Catalysis B：Environmental，2018，232：246-259.
13	CHEN Linxiao， AGRAWAL V， TAIT S L.Sulfate promotion of selective catalytic reduction of nitric oxide by ammonia on ceria［J］.Catalysis Science & Technology，2019，9（8）：1802-1815.
14	XIE Yu， WU Jinfang， JING Guojuan，et al.Structural origin of high catalytic activity for preferential CO oxidation over CuO/CeO₂ nanocatalysts with different shapes［J］.Applied Catalysis B：Environmental，2018，239：665-676.
15	TSUHAKO M， DANJO M， BABA Y，et al.Preparation and chemical properties of a novel layered cerium（Ⅳ） phosphate［J］.Bulletin of the Chemical Society of Japan，1997，70（1）：143-148.
16	DING Yilun， MIAO Dengyun， FENG Jingyao，et al.Enhanced formation of multi-branched isoparaffins in syngas conversion by ZnCrO_x -MCM-22 composites［J］.Applied Catalysis B：Environmental，2022，316：121628.
17	ZHANG Lunliang， HUANG Siyu， WENG Yao，et al.Preparation of Ni-P-Ti₃C₂T_x -Ce composite coating with enhanced wear resistance and electrochemical corrosion behavior on the surface of low manganese steel［J］.Surface and Coatings Technology，2022，441：128508.
18	YANG Bin， ZENG Yiqing， ZHANG Mingjia，et al.Highly efficient K-doped Mn-Ce catalysts with strong K-Mn-Ce interaction for toluene oxidation［J］.Journal of Rare Earths，2023，41（3）：374-380.
19	POZDNYAKOVA O， TESCHNER D， WOOTSCH A，et al.Preferential CO oxidation in hydrogen（PROX） on ceria-supported catalysts，part I：Oxidation state and surface species on Pt/CeO₂ under reaction conditions［J］.Journal of Catalysis，2006，237（1）：1-16.
20	韩新宇，刘凯杰，边梦瑶，等.Ce-MnO_x 低温净化氮氧化物和一氧化碳的催化性能研究［J］.无机盐工业，2021，53（12）：35-42.
	HAN Xinyu， LIU Kaijie， BIAN Mengyao，et al.Catalytic performance study of Ce-MnO_x for low-temperature purification of nitrogen oxides and carbon monoxide［J］.Inorganic Chemicals Industry，2021，53（12）：35-42.

催化剂	CO滴定量/cm³	n（Pt）/ mol	分散度/ %	铂粒径/nm
1%Pt/CeO₂	0.083	5.04×10^-6	73.60	2.57
1%Pt/CeO₂-0.01PO_x	0.079	5.07×10^-6	69.40	2.73
1%Pt/CeO₂-0.03PO_x	0.075	5.13×10^-6	65.50	2.89
1%Pt/CeO₂-0.05PO_x	0.071	5.23×10^-6	60.40	3.14
1%Pt/CeO₂-0.07PO_x	0.065	5.20×10^-6	55.60	3.41
1%Pt/CeO₂-0.10PO_x	0.053	4.78×10^-6	49.20	3.85
1%Pt/CeO₂-0.15PO_x	0.046	4.83×10^-6	42.40	4.47
1%Pt/CeO₂-0.20PO_x	0.030	4.93×10^-6	27.30	6.94

催化剂	峰面积占比/%
催化剂	Ce³⁺	Ce⁴⁺
1%Pt/CeO₂	23.11	76.89
1%Pt/CeO₂-0.01PO_x	19.80	80.20
1%Pt/CeO₂-0.03PO_x	20.18	79.82
1%Pt/CeO₂-0.05PO_x	19.23	80.77
1%Pt/CeO₂-0.07PO_x	21.40	78.60
1%Pt/CeO₂-0.10PO_x	23.78	76.22
1%Pt/CeO₂-0.15PO_x	24.71	75.29
1%Pt/CeO₂-0.20PO_x	25.90	74.10

催化剂	峰面积占比/%
催化剂	Pt²⁺	Pt⁴⁺
1%Pt/CeO₂	100	0
1%Pt/CeO₂-0.01PO_x	95.3	4.7
1%Pt/CeO₂-0.03PO_x	88.2	11.8
1%Pt/CeO₂-0.05PO_x	73.7	26.3
1%Pt/CeO₂-0.07PO_x	68.0	32.0
1%Pt/CeO₂-0.10PO_x	44.6	55.4
1%Pt/CeO₂-0.15PO_x	34.1	65.9
1%Pt/CeO₂-0.20PO_x	27.9	72.1

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磷酸改性CeO₂纳米棒负载Pt催化剂催化丙烷燃烧性能的研究

Study on catalytic performance of phosphoric acid modified CeO₂ nanorod supported Pt catalyst for propane combustion

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