Promotional effects of defects on Ni/HAP catalyst for carbon resistance and durability during dry reforming of methane
Promotional effects of defects on Ni/HAP catalyst for carbon resistance and durability during dry reforming of methane
复制标题
甲烷干重整过程中缺陷对Ni/HAP催化剂抗碳性和耐久性的促进作用
DOI：
10.1016/j.fuel.2021.122363
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发表时间：
2022
期刊：
影响因子：
7.4
通讯作者：
Piao Guilin
中科院分区：
文献类型：
--
作者：
Meng Junguang;Gu Tingting;Pan Wei;Bu Changsheng;Zhang Jubing;Wang Xinye;Liu Changqi;Xie Hao;Piao Guilin
优异的抗炭性和稳定的操作对于甲烷催化干重整（DRM）的工业化至关重要。在本研究中，使用一系列Ni/HAP和Ni/HAP-D催化剂来研究它们的DRM反应性能，包括活性、耐久性和抗积碳性。结合H2-TPR和XPS结果，Ni/HAP中的Ni更倾向于取代羟基磷灰石中外部的Ca原子。固有的“Ca缺陷”HAP-D载体有利于Ni金属的更稳健的锚定位，并且大部分Ni原子将以Ni 2 +[I]和Ni 2 +[II]的形式嵌入羟基磷灰石的内部结构中。Ni/HAP-D系列催化剂对CH 4和CO2的催化活性明显高于Ni/HAP系列催化剂，表明Ni的形态、Ni与载体的结合形式对DRM反应起着至关重要的作用。在200小时的耐久性测试中，Ni 0.5/HAP-D催化剂对CH 4和CO2的失活速率分别仅为0.008%h-1和0.007%h-1。在反应118 h后的Ni 0. 5/HAP催化剂中，检测到NiO晶相的存在，表明部分Ni在反应过程中被CO2氧化，同时检测到无定形碳和石墨碳。相反，在反应200小时后，在废Ni/HAP-D催化剂中没有检测到NiO晶相，并且仅观察到痕量的石墨碳，表明Ni 0.5/HAP-D的Ni存在模式有助于其稳定性和抗碳沉积性。这项工作为DRM应用提供了对负载型镍基催化剂的设计的见解，该催化剂具有优异的稳定性和令人惊讶的抗积碳性。
Excellent carbon resistance and stable operations are essential for the industrialization of catalytic dry reforming of methane (DRM). In this study, a series of Ni/HAP and Ni/HAP-D catalysts are used to investigate their DRM reaction performance, including activity, durability, and resistance to carbon deposition. Combined with H2-TPR and XPS results, Ni in the Ni/HAP prefers to replace the external Ca atoms in hydroxyapatite. The inherently “Ca-deficient” HAP-D support facilitates a more robust anchor positioning for the Ni metal, and a significant fraction of the Ni atoms will be embedded in the inner structure of hydroxyapatite in the form of Ni2+[I] and Ni2+[II]. The catalytic activity of the Ni/HAP-D series of catalysts for CH4and CO2is significantly higher than that of the Ni/HAP series of catalysts, demonstrating that the Ni morphology, the combined form between Ni and support plays a crucial role in the DRM reaction. The deactivation rate of the Ni0.5/HAP-D catalyst is only 0.008% h−1and 0.007% h−1for CH4and CO2, respectively, in a 200-h durability test. In the spent Ni0.5/HAP catalyst after 118-h reaction, the presence of NiO crystalline phase is detected, indicating that partial Ni is oxidized by CO2during the reaction, and amorphous carbon and graphitic carbon are also detected. In contrast, no NiO crystalline phase is detected in the spent Ni/HAP-D catalyst after 200-h reaction, and only trace amounts of graphitic carbon are observed, indicating that the Ni presence pattern of Ni0.5/HAP-D contributes to its stability and resistance to carbon deposition. This work provides insights into the design of supported nickel-based catalysts with both excellent stability and surprisingly resistant to carbon deposits for DRM applications.
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影响因子：
13.1
作者：
Liu, Wenming;Li, Le;Peng, Honggen
通讯作者：
Peng, Honggen
影响因子：
22.1
作者：
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通讯作者：
Lopez-Fonseca, Ruben
孔结构对用于甲烷干重整的羟基磷灰石负载镍催化剂（Ni/HAP）的影响
影响因子：
7.5
作者：
Li Bin;Yuan Xiaoqing;Li Baitao;Wang Xiujun
通讯作者：
Wang Xiujun
影响因子：
7.2
作者：
Bruna Rego de Vasconcelos;Doan Pham Minh;E. Martins;A. Germeau;P. Sharrock;A. Nzihou
通讯作者：
Bruna Rego de Vasconcelos;Doan Pham Minh;E. Martins;A. Germeau;P. Sharrock;A. Nzihou
影响因子：
6.7
作者：
Hongyan Liu;Riguang Zhang;R. Yan;Baojun Wang;K. Xie
通讯作者：
Hongyan Liu;Riguang Zhang;R. Yan;Baojun Wang;K. Xie