Ca, Sr共掺杂铈氧化物及其在甲烷氧化偶联反应中的应用

doi:10.7503/cjcu20160467

高等学校化学学报 ›› 2016, Vol. 37 ›› Issue (12): 2206.doi: 10.7503/cjcu20160467

Ca, Sr共掺杂铈氧化物及其在甲烷氧化偶联反应中的应用

杨艳玲, 董玲玉, 夏文生(), 万惠霖()

厦门大学化学化工学院, 固体表面物理化学国家重点实验室,醇醚酯化工清洁生产国家工程实验室, 福建省理论计算化学重点实验室, 厦门 361005

收稿日期:2016-07-01 出版日期:2016-12-10 发布日期:2016-11-18
作者简介:联系人简介: 夏文生, 男, 博士, 教授, 主要从事甲烷转化方面的研究. E-mail:wsxia@xmu.edu.cn; 万惠霖, 男, 教授, 中国科学院院士, 主要从事甲烷转化方面的研究. E-mail:hlwan@xmu.edu.cn
基金资助:
国家自然科学基金(批准号: 21373169)和教育部“长江学者和创新团队发展计划”项目(批准号: IRT1036)资助

Ca, Sr co-Doped Ceria and Its Application in Oxidative Coupling of Methane^†

YANG Yanling, DONG Lingyu, XIA Wensheng^*(), WAN Huilin^*()

State Key Laboratory of Physical Chemistry of Solid State Surfaces, National Engineering Laboratory for Green Chemical Productions of Alcohols-Ethers-Esters, Fujian Province Key Laboratory of Theoretical and Computational Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China

Received:2016-07-01 Online:2016-12-10 Published:2016-11-18
Contact: XIA Wensheng,WAN Huilin E-mail:wsxia@xmu.edu.cn;hlwan@xmu.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(No.21373169) and the Program for Changjiang Scholars and Innovative Research Team in the University, China(No.IRT1036)

摘要/Abstract

摘要：

采用柠檬酸法制备了Ca, Sr共掺杂的CeO₂催化剂, 发现共掺杂催化剂较单掺杂或未掺杂催化剂呈现出更好的催化甲烷氧化偶联(OCM)反应性能. 通过表征可知, Ca, Sr共掺杂催化剂的物相为CeO₂和SrCO₃, Ca高度分散或掺杂于CeO₂之中; CeO₂的粒径明显变小; 表面呈中等程度碱性; Ce基催化剂上的亲电氧物种数量随着碱土金属的掺杂而增大, 亲电氧物种与晶格氧摩尔比(O₂^2-+O₂^-/+O₂^-的大小顺序(CeSrCa>CeSr>CeO₂)与C2选择性一致; 且SrCO₃相的存在有助于Ce基氧化物催化甲烷氧化偶联反应(OCM)性能的改善.

关键词: 碱土金属, 掺杂, CeO2, 碳酸盐, 甲烷氧化偶联

Abstract:

The Ca and Sr co-doped ceria catalysts were synthesized with a citric acid method and their performances in oxidative coupling of methane(OCM) were significantly enhanced when compared with the single or none doped ceria catalysts. By X-ray diffraction(XRD), CO₂ temperature programmed desorption(CO₂-TPD), O₂ temperature programmed desorption(O₂-TPD), X-ray photoelectron spectroscopy(XPS) characterizations, we found that the Ca and Sr co-doped catalysts were consisted of the phases CeO₂ and SrCO₃, along with Ca highly dispersed or doped in ceria. They exhibited the decreased size of ceria particles and the medium basicity. The number of electrophilic oxygen species and the ratio of electrophilic oxygen species to lattice oxygen species on the catalyst surfaces were changed in the order of CeSrCa>CeSr>CeO₂, corresponding to the C2 selectivity in OCM. In addition, the presence of SrCO₃was beneficial to improve on catalytic performances of OCM over Ce-based oxide catalysts.

Key words: Alkali earth, Dope, Ceria, Carbonate, Oxidative coupling of methane

TrendMD:

杨艳玲, 董玲玉, 夏文生, 万惠霖. Ca, Sr共掺杂铈氧化物及其在甲烷氧化偶联反应中的应用. 高等学校化学学报, 2016, 37(12): 2206.

YANG Yanling, DONG Lingyu, XIA Wensheng, WAN Huilin. Ca, Sr co-Doped Ceria and Its Application in Oxidative Coupling of Methane^†. Chem. J. Chinese Universities, 2016, 37(12): 2206.

图/表 12

Fig.1 Catalytic performances of Ce0.5Sr0.4M0.1Ox for OCM reation■ Ce0.5Sr0.5Ox; ▲ Ce0.5Sr0.4Mg0.1Ox; ● Ce0.5Sr0.4Ca0.1Ox; ▼ Ce0.5Sr0.4Ba0.1Ox.

Fig.2 Catalytic performances of Ce0.5Sr0.5-mCamOx(m=0—0.25) for OCM reation■ Ce0.5Sr0.5Ox; ▲ Ce0.5Sr0.45Ca0.05Ox; ● Ce0.5Sr0.4Ca0.1Ox; ★ Ce0.5Sr0.35Ca0.15Ox;▼ Ce0.5Sr0.3Ca0.2Ox; ◆ Ce0.5Sr0.25Ca0.25Ox.

Fig.3 Life test of the catalysts Ce0.5Sr0.5Ox(A) and Ce0.5Sr0.4Ca0.1Ox(B) in the oxidative coupling of methane a. Sel(C2); b. conv(CH4); c. Y(C2).

Table 1 Comparisons of OCM performances over some Ce-based and relevant catalysts at selected temperatures

Catalyst	T/℃	Conv(CH₄)(%)	Conv(O₂)(%)	Sel(CO_x)(%)	Sel(C2)(%)	Y(C2)(%)
Blank	750	1.2	2.3	59.0	41.0	0.5
	800	2.3	4.5	61.8	38.3	0.9
CeO₂	450	2.0	5.8	100.0	0	0
	500	17.9	100.0	98.0	2.0	0.4
	550	18.0	100.0	97.8	2.2	0.4
	700	19.1	100.0	95.1	4.9	0.9
Ce_0.5Sr_0.5O_x	500	1.1	2.9	100.0	0	0
	550	24.9	93.9	65.1	34.9	8.7
	650	28.6	100.0	52.8	47.2	13.5
	700	29.4	100.0	50.6	49.4	14.5
Ce_0.5Ca_0.5O_x	500	1.8	5.3	100.0	0	0
	550	24.3	98.0	63.7	36.3	8.8
	650	25.1	100.0	60.8	39.2	9.8
	700	24.4	100.0	64.0	35.9	8.8
Ce_0.5Sr_0.4Ca_0.1O_x	500	1.2	3.2	100.0	0	0
	550	28.1	97.0	54.8	45.2	12.7
	650	30.2	100.0	49.5	50.5	15.2
	700	30.4	100.0	48.5	51.5	15.7
Ce_0.5Sr_0.5O_x(MM)^*	550	0	0
(CeO₂+SrO)	700	1.6	4.1	85.4	14.6	0.2
	750	3.5	8.1	73.6	36.5	1.3
	800	9.3	19.9	52.0	48.0	4.5
Ce_0.5Sr_0.5O_x(MM)^*	550	19.1	98.5	92.8	7.2	1.4
(CeO₂+SrCO₃)	700	26.0	100.0	57.4	42.6	11.1
	750	27.5	100.0	52.4	47.6	13.1
	800	28.0	100.0	51.2	48.8	13.6
CaO	700	2.4	6.3	88.4	11.6	0.3
	750	6.2	14.9	65.7	34.3	2.1
	800	24.7	57.9	58.1	41.9	10.4
SrO	700	0.9	1.9	66.3	33.7	0.3
	750	2.3	4.0	40.4	59.7	1.4
	800	8.9	14.0	41.3	58.8	5.3
CaCO₃	700	18.1	53.4	66.4	33.6	6.1
	750	26.9	85.2	57.4	42.6	11.5
	800	28.7	98.8	58.0	42.0	12.1
SrCO₃	700	1.5	3.0	66.0	34.0	0.5
	750	3.1	6.3	67.8	32.2	1.0
	800	9.0	17.4	54.5	45.5	4.1

Table 2 Specific surface areas(SBET), porous volumes(Vp), porous sizes(Dp), CeO2 crystalline sizes(D) and lattice parameters(a) of the catalysts

Catalyst	S_BET/(m²·g^-1)	V_p/(cm³·g^-1)	D_p/nm	D/nm	a/nm
CeO₂	12.0	0.075	20.4	96.6	0.05394
Ce_0.5Sr_0.5O_x	3.0	0.018	21.5	48.3	0.05440
Ce_0.5Sr_0.4Ca_0.1O_x	5.5	0.028	18.8	18.7	0.05438

Fig.4 XRD patterns of the catalystsa. CeO2; b. Ce0.5Sr0.5Ox; c. Ce0.5Sr0.4Ca0.1Ox; d. CaCO3, PDF No. 99-0022; e. CeO2, PDF No. 01-081-0792;f. SrCO3, PDF No. 01-084-1778.

Fig.5 UV-Vis spectra of the catalystsa. CeO2; b. Ce0.5Sr0.5Ox; c. Ce0.5Sr0.4Ca0.1Ox.

Fig.6 O2-TPD profiles of the catalystsa. CeO2; b. Ce0.5Sr0.5Ox; c. Ce0.5Sr0.4Ca0.1Ox.

Fig.7 CO2-TPD profiles of the catalystsa. CeO2; b. Ce0.5Sr0.5Ox;c. Ce0.5Sr0.4Ca0.1Ox.

Fig.8 XPS Spectra for Ce3d of the catalystsa. CeO2; b. Ce0.5Sr0.5Ox;c. Ce0.5Sr0.4Ca0.1Ox.

Fig.9 XPS spectra for O1s of the catalysts(A) CeO2; (B) Ce0.5Sr0.5Ox; (C) Ce0.5Sr0.4Ca0.1Ox.

Table 3 Curve-fitting results from XPS spectra for O1s of the catalysts

Catalyst	E_b/eV(FWHM^*)					Amount of oxygen species(%)				n( $O 2 2 -$ + $O 2 -$ )/ n(O^2-)
Catalyst	O^2-	$O 2 2 -$	$O 2 -$		C $O 3 2 -$		O^2-	$O 2 2 -$	$O 2 -$	C $O 3 2 -$
CeO₂	528.6(1.2)	529.7(1.2)	530.9(1.2)	532.1(1.2)		72.8	11.0	11.7	4.3	0.3
Ce_0.5Sr_0.5O_x	528.4(1.7)	530.3(1.7)		531.3(1.7)		23.6	65.5		10.9	2.8
Ce_0.5Sr_0.4Ca_0.1O_x	528.2(1.6)	530.5(1.6)		532.0(1.6)		22.7	66.1		11.2	3.0

Table 3 Curve-fitting results from XPS spectra for O1s of the catalysts

Catalyst	E_b/eV(FWHM^*)					Amount of oxygen species(%)				n( $O 2 2 -$ + $O 2 -$ )/ n(O^2-)
Catalyst	O^2-	$O 2 2 -$	$O 2 -$		C $O 3 2 -$		O^2-	$O 2 2 -$	$O 2 -$	C $O 3 2 -$
CeO₂	528.6(1.2)	529.7(1.2)	530.9(1.2)	532.1(1.2)		72.8	11.0	11.7	4.3	0.3
Ce_0.5Sr_0.5O_x	528.4(1.7)	530.3(1.7)		531.3(1.7)		23.6	65.5		10.9	2.8
Ce_0.5Sr_0.4Ca_0.1O_x	528.2(1.6)	530.5(1.6)		532.0(1.6)		22.7	66.1		11.2	3.0

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Ca, Sr共掺杂铈氧化物及其在甲烷氧化偶联反应中的应用

Ca, Sr co-Doped Ceria and Its Application in Oxidative Coupling of Methane^†

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Ca, Sr共掺杂铈氧化物及其在甲烷氧化偶联反应中的应用

Ca, Sr co-Doped Ceria and Its Application in Oxidative Coupling of Methane†

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Ca, Sr co-Doped Ceria and Its Application in Oxidative Coupling of Methane^†