Regulation of metal-support interface of Ni/CeO2 catalyst and the performance of low temperature chemical looping dry reforming of methane
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摘要: 本研究合成了四种CeO2形貌的Ni/CeO2催化剂（纳米棒、纳米立方体、纳米八面体和纳米多面体），并探讨了催化剂低温化学链甲烷干重整反应的结构依赖性。材料表征表明，Ni物种高度分散在CeO2载体表面，部分Ni离子进入CeO2晶格，从而引起氧空位的增加。化学链干重整性能测试结果表明，棒状结构Ni/CeO2催化剂表现出最高的还原性，具有最多氧空位和最高储氧能力。多面体状Ni/CeO2催化剂的结构为形状不规则的约10.3 nm的CeO2纳米单晶，具有较大的比表面积和较高的还原性，表现出低温甲烷反应活性，在550 ℃低温化学链甲烷干重整中显示最高的氧化还原活性和循环稳定性。本研究为设计高效的金属/CeO2催化剂提供了一种新策略，有望促进铈基催化剂在化学链技术中应用。Abstract: Interface regulation is an effective strategy to improve the interaction between carrier and active metal center, which can improve the catalytic activity and oxygen storage capacity of the catalysts. In this paper, Ni/CeO2 catalysts supported on CeO2 with different morphologies (nanorods, nanocubes, nanoctahedrons and nanopolyhedrons) were synthesized. The structure dependence of the catalysts for the low temperature chemical looping dry reforming of methane (CL-DRM) was investigated. The characterization results showed that Ni species were highly dispersed on the surface of CeO2 carrier, and some Ni ions entered the CeO2 lattice, resulting in the increase of oxygen vacancies. The Ni/ceria-rods catalyst had the highest reducibility, the most oxygen vacancies and the highest oxygen storage capacity. The irregular CeO2 nano single crystal of about 10.3 nm in the Ni/ceria-polyhedra led to high specific surface area and high reducibility which exhibited the highest redox activity and redox stability in low-temperature chemical looping dry reforming of methane at 550 ℃. This study provided a new strategy for the design of efficient metal/CeO2 catalysts, which was expected to promote the application of cerium-based catalysts in chemical looping technology.
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Key words:
- chemical looping /
- CeO2 /
- carbon dioxide /
- methane /
- crystal facets
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图 2 （a）CeO2、（b）NiO/CeO2和（（c）、（d））Ni/CeO2的XRD谱图
Figure 2 XRD patterns of (a) CeO2, (b) NiO/CeO2, and ((c), (d)) Ni/CeO2
图 3 (a)Ni/CeO2-R、(b)Ni/CeO2-C、(c)Ni/CeO2-P的N2吸附-解吸等温线和孔径分布(插图)
Figure 3 N2 adsorption-desorption isotherms and pore size distribution (inset) of (a) Ni/CeO2-R, (b) Ni/CeO2-C, (c) Ni/CeO2-P
图 4 新鲜制备的CeO2的SEM、TEM和HRTEM照片
Figure 4 SEM, TEM and HRTEM images of as-obtained CeO2 ((a), (b), (c)) CeO2-R, ((d), (e), (f)) CeO2-C, ((g), (h), (i)) CeO2-P and ((j), (k), (l)) CeO2-O
图 5 Ni/CeO2的TEM和HRTEM照片
Figure 5 TEM and HRTEM images of Ni/CeO2
((a), (d)) Ni/CeO2-R, ((b), (e)) Ni/CeO2-C and ((c), (f)) Ni/CeO2-P
图 6 （a）CeO2样品，（b）Ni/CeO2样品的拉曼光谱谱图
Figure 6 Raman spectra of (a) CeO2 samples (b) Ni/CeO2 samples
图 7 CH4的温度程序反应（CH4-TPR）曲线：（a）Ni/CeO2-R，（b）Ni/CeO2-C，（c）Ni/CeO2-P；(d）Ni/CeO2：（e）CH4-TPR过程中生成物形成的起始温度
Figure 7 Temperature-programmed reaction of CH4 (CH4-TPR) profiles over (a) Ni/CeO2-R, (b) Ni/CeO2-C, (c) Ni/CeO2-P; (d) Ni/CeO2, (e) starting temperature of products formation during the CH4-TPR
图 8 （a）Ni/CeO2-R、（b）Ni/CeO2-C、（c）Ni/CeO2-P和（d）Ni/CeO2的氧化还原反应产生的气体
Figure 8 Gases from the second redox reactions over (a) Ni/CeO2-R, (b) Ni/CeO2-C and (c) Ni/CeO2-P和（d）Ni/CeO2
图 9 (a)在不同的Ni/CeO2氧化还原催化剂上，甲烷氧化步骤中CH4的转化率、CO的选择性和CO2的转化率；(b)甲烷氧化步骤中H2、CO和CO2的产率和CO2分裂步骤中CO的产率。
Figure 9 (a) CH4 conversion, CO selectivity and CO2 conversion in methane oxidation step over different Ni/CeO2 redox catalyst; (b)Yields of H2, CO and CO2 in methane oxidation step and CO yield in CO2 splitting step
图 10 用于CLDRM的Ni/CeO2氧化还原催化剂的氧化还原稳定性：(a)在550 ℃下，三种Ni/CeO2氧化还原催化剂在连续氧化还原循环中的CH4转化和CO2转化；(b) 在Ni/CeO2-P氧化还原催化剂上，甲烷氧化步骤中H2、CO和CO2的产率以及CO2分裂步骤中CO的产率
Figure 10 Redox stability of Ni/CeO2 redox catalysts for CL-DRM (a) CH4 conversion and CO2 conversion in successive redox cycles over three Ni/CeO2 catalyst at 550 ℃; (b) Yield of H2, CO and CO2 in methane oxidation step and CO yield in CO2 splitting step over Ni/CeO2-P catalyst at 550 ℃ for 50 redox cycles
表 1 CeO2纳米结构水热合成条件
Table 1 Hydrothermal synthesis conditions of CeO2 nanostructures
Support ${{C} }_{ {\rm{NaOH/Na_3PO_4} } }$
(mol·L−1)t/℃ t/h Structure Shape CeO2-R 6 100 24 cubic rods CeO2-C 7 180 24 cubic cubes CeO2-P 0.5 100 24 cubic particles CeO2-O 0.0003 170 10 cubic octahedra Note: Synthesized under [Ce3+] = 0.4 mol/L 
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表 2 Ni/CeO2样品中CeO2的晶格参数（a0）、结晶尺寸和微应变（ε）
Table 2 Lattice parameter (a0), crystalline size, and the microstrain (ε) of ceria in Ni/CeO2 samples
Sample d(111)-spacing/nm Lattice parameter/nm CeO2 crystalline size/nm ε/% (111) (220) (311) avg. Ni/CeO2-R 0.31122 0.541134 11.2 11.2 11.4 11.4 0.084 Ni/CeO2-C 0.31186 0.541058 > 100 > 100 > 100 319.7 0.020 Ni/CeO2-P 0.31207 0.540609 10.2 10.5 10.7 10.3 0.027 Ni/CeO2-O 0.31044 0.539575 60.1 53.9 51.3 55.1 0.058
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表 3 煅烧后的Ni/CeO2催化剂的织构性能
Table 3 Textural properties and redox behaviors of calcined Ni/CeO2 catalysts
Sample SBET/(m2·g−1) Pore
volume/(cm3·g−1)Average pore
size/nmNi/CeO2-R 57.88 0.26 61.0 Ni/CeO2-C 7.93 0.02 19.2 Ni/CeO2-P 60.91 0.17 47.4 Ni/CeO2-O 12.01 0.03 24.5
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