CO oxidation performance of Pt catalysts supported on CeO2-Al2O3 supports synthesized via urea homogeneous precipitation

doi:10.11949/0438-1157.20250252

Abstract

Abstract:

Four precipitating agents (ammonium hydroxide, ammonium carbonate, ammonium bicarbonate, and urea) were selected to synthesize CeO₂-Al₂O₃ supports via a precipitation method, using high-surface-area Al₂O₃ as a non-soluble aluminum source and Ce(NO₃)₃·6H₂O as a cerium precursor. Pt/CeO₂-Al₂O₃ catalysts were subsequently prepared by Pt impregnation to investigate the effect of precipitating agents on CO catalytic oxidation performance. Characterization results show that the catalyst prepared by urea uniform precipitation method exhibits the best activity, which is attributed to the enhanced Pt-CeO₂ interface interaction. The type of precipitant affects the dispersion, distribution uniformity, morphology of CeO₂, and the interaction between Pt and CeO₂ by altering crystallization kinetics and precursor types. In the urea homogeneous precipitation process with the presence of Al₂O₃, the slow precipitation mechanism within confined channels promotes both uniform distribution and high dispersion of nanorod-like CeO₂ particles inside the Al₂O₃ pores. This approach avoids the aggregation and surface enrichment of spherical CeO₂ nanoparticles on the outer surface of Al₂O₃ caused by rapid precipitation when using ammonia as a precipitant. Thereby, it strengthens the interaction between Pt and CeO₂, ultimately achieving enhanced catalytic performance.

Key words: cerium dioxide, alumina, homogeneous precipitation, platinum, carbon monoxide, catalysis

摘要：

选取氨水、碳酸铵、碳酸氢铵和尿素为沉淀剂，以高比表面积Al₂O₃作为非溶解性铝源，Ce(NO₃)₃·6H₂O作为可溶性铈源，通过沉积沉淀法合成CeO₂-Al₂O₃载体，经Pt浸渍负载制备了Pt/CeO₂-Al₂O₃催化剂，考察了沉淀剂类型对CO催化氧化性能的影响。表征结果表明，尿素均匀沉淀法制备的催化剂展现出最优活性，被归因于增强的Pt-CeO₂界面相互作用。沉淀剂类型通过调控结晶动力学和前体种类，影响了CeO₂的分散度、分布均匀性、形貌特征及其与Pt的相互作用。在Al₂O₃存在的尿素均匀沉淀中，限制孔道内的缓慢沉淀机制促进了纳米棒状CeO₂粒子在Al₂O₃孔道内的均匀分布且高度分散，避免了氨水沉淀剂因快速沉淀而引起的纳米球状CeO₂在Al₂O₃外表面上的富集团聚，从而强化了Pt与CeO₂间的相互作用，最终实现催化性能的提升。

关键词: 氧化铈, 氧化铝, 均匀沉淀, 铂, 一氧化碳, 催化

CLC Number:

TQ 426.8

Yupeng DU, Chunliang GE, Leilin DING, Li ZHANG, Jiajun HU, Fengping YU, Yi LIN, Feng WANG, Shi JIANG, Yu GUO. CO oxidation performance of Pt catalysts supported on CeO₂-Al₂O₃ supports synthesized via urea homogeneous precipitation[J]. CIESC Journal, 2025, 76(10): 5114-5127.

杜宇鹏, 葛春亮, 丁垒琳, 张力, 胡家俊, 俞峰苹, 林益, 王峰, 蒋师, 郭燏. 尿素均匀沉淀法合成CeO₂-Al₂O₃载体负载Pt催化剂的CO氧化性能[J]. 化工学报, 2025, 76(10): 5114-5127.

Figures/Tables 13

Fig.1 CO conversion obtained on different catalysts

Fig.2 XRD patterns of different catalysts

Table 1 Specific surface area， pore volume， pore size， CeO2 grain size， Pt dispersion， and T90 on different catalysts

Sample	Specific surface area/(m²/g)	Total pore volume/(cm³/g)	Average pore diameter/nm	CeO₂grain size^①/nm	Pt dispersion^②/%	T₉₀/℃
Pt/CeAl-PAH	133	0.463	14.0	5.6	29	165
Pt/CeAl-PAC	130	0.459	14.1	11.8	49	161
Pt/CeAl-PAB	133	0.461	13.9	13.0	63	159
Pt/CeAl-HPU	133	0.449	13.6	9.3	69	149
Pt/CeAl-I	112	0.425	15.2	8.9	57	162
Pt/Al-I	140	0.476	13.3	—	41	174
Al₂O₃	142	0.478	13.5	—	—	—

Fig.3 XPS spectra of different catalysts

Table 2 Surface Ce atomic concentration， Pt0 ratio， Ce3+ ratio， and Osur ratio on different catalysts

Sample	Ce atomic concentration/%	[Pt⁰/(Pt ^δ⁺+Pt⁰)]/%	[Ce³⁺/(Ce³⁺+Ce⁴⁺)]/%	[O_sur/(O_sur+O_lat)]/%
Pt/CeAl-PAH	7.8	20.7	13.6	36.4
Pt/CeAl-PAC	9.9	27.2	15.3	38.0
Pt/CeAl-PAB	8.6	21.6	14.5	38.2
Pt/CeAl-HPU	1.7	51.2	20.8	43.0
Pt/CeAl-I	4.0	18.7	15.3	38.3
Pt/Al-I	—	30.6	—	32.6

Fig.4 H2-TPR profiles of different catalysts

Fig.5 Relationships between T90 (a), Pt dispersion (b), Ce3+ ratio (c), Osur ratio (d), low-temperature peak temperature of H₂-TPR (e), and binding energy shift of Pt 4f (f) on different catalysts

Fig.6 Variation of pH with time during the urea homogeneous precipitation process

Fig.7 Effects of contents of Ce3+(a), Al2O3(b), and urea(c) on the time-dependent pH variation trend during the urea homogeneous precipitation

Fig.8 XRD patterns of samples prepared by different precipitation methods

Fig.9 Thermogravimetric analysis of Ce-HPU-AD and CeAl-HPU-AD samples

Fig.10 TEM images and surface elemental distribution of different samples

Table 3 Effect of urea content in the homogeneous precipitation process on the grain size of CeO2， specific surface area， Pt dispersion， LTRP in H2-TPR， and T90

Sample	Ce³⁺/Al₂O₃/urea	CeO₂ grain size/nm	Specific surface area/(m²/g)	Pt dispersion	LTRP of H₂-TPR/℃	CO T₉₀/℃
Pt/CeAl-HPU₅	0.1/1.1/0.5	9.3	132	0.69	87	149
Pt/CeAl-HPU₁₅	0.1/1.1/1.5	11.4	137	0.61	97	154
Pt/CeAl-HPU₂₅	0.1/1.1/2.5	13.7	135	0.51	112	160

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CO oxidation performance of Pt catalysts supported on CeO₂-Al₂O₃ supports synthesized via urea homogeneous precipitation

尿素均匀沉淀法合成CeO₂-Al₂O₃载体负载Pt催化剂的CO氧化性能

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