Ni-Co and Ni-Cu bimetallic alloy catalysts for CO methanation
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摘要: 以钙钛矿型复合氧化物LaNi0.9Co0.1O3和LaNi0.9Cu0.1O3为前驱体制备了Ni-Co/La2O3和Ni-Cu/La2O3双金属合金催化剂。结果表明,双金属合金催化剂中,各组分间相互稀释,具有较强的抗烧结性能;催化剂表面的积炭主要取决于CO在催化剂表面的吸附形态,Ni-Co双金属催化剂中,Co掺杂改变了CO在催化剂表面的吸附形式和吸附强度,使得Ni-Co双金属催化剂具有较强的抗积炭性能。Ni-Co双金属合金催化剂用于CO甲烷化反应时,显现出较好的活性、选择性和稳定性。Abstract: Ni-Co/La2O3 and Ni-Cu/La2O3 bimetallic alloy catalysts were prepared by using LaNi0.9Co0.1O3 and LaNi0.9Cu0.1O3 perovskite-type oxides precursors. The results demonstrate that the components are diluted with each other in the bimetallic alloy catalyst and exhibit strong anti-sintering ability. The carbon deposited on the catalyst surface mainly depends on the adsorption state of CO, the modulated adsorption state and adsorption strength of CO contribute to the strong anti-carbon deposition ability of the Ni-Co bimetallic catalysts. The Ni-Co bimetallic alloy catalysts show remarkable activity, selectivity, and stability in the CO methanation reaction.
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Key words:
- CO methanation /
- perovskite oxide /
- nickel /
- bi-metal /
- alloy catalyst
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图 3 N/L、NCo/L和NCu/L催化剂还原后的La 3d和Ni 2p的XPS谱图(a);NCo/L催化剂还原后的Co 2p的XPS谱图(b);NCu/L催化剂还原后的Cu 2p的XPS谱图(c)
Figure 3 XPS spectra for La 3d and Ni 2p of the N/L, NCo/L and NCu/L catalysts after reduction (a); XPS spectra for Co 2p of NCo/L after reduction (b); XPS spectra for Cu 2p of NCu/L catalysts after reduction (c)
表 1 LaNiO3、LaNi0.9Co0.1O3和LaNi0.9Cu0.1O3前驱体的耗氢量
Table 1 H2 consumption of the LaNiO3, LaNi0.9Co0.1O3 and LaNi0.9Cu0.1O3 precursors
Sample Experiment values/(μmol·(0.05 gcat)-1)a Theoretical values/(μmol·(0.05 gcat)-1) TL TH Ni3+-Ni2+ Co3+-Co2+ Cu2+-Cu+ Ni2+-Ni0 Co2+-Co0 Cu+-Cu0 NO 102.0 202.7 101.8 - - 203.6 - NCoO 101.6 203.6 91.6 10.2 - 183.2 20.4 NCuO 101.6 192.3 91.4 - 10.15 182.9 - 10.15 a: calculated by using the TPR peak area of pure CuO as benchmark 表 2 N/L、NCo/L和NCu/L催化剂及其稳定性测试后的晶粒粒径
Table 2 Average crystalline size of the N/L, NCo/L and NCu/L catalysts before and after the stability tests
Sample Dmetala /nm Degree of sinteringb/% after reduction after stability test N/L 12.1 18.6 52.7 NCo/L 15.8 20.9 32.3 NCu/L 14.9 20.8 39.6 a: calculated from XRD results with Scherrer formula:$D = k\lambda /\left( {\beta \cos \theta } \right) $;
b: calculated from XRD results by the design formula:${\rm{De}}{{\rm{g}}_{{\rm{sinter}}}} = \frac{{\left( {{D_{{\rm{spent}}}} - {D_{{\rm{reduction}}}}} \right)}}{{{D_{{\rm{reduction}}}}}} $ -
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