TY - JOUR
T1 - Boosting CO2 hydrogenation of Fe-based monolithic catalysts via 3D printing technology-induced heat/mass-transfer enhancements
AU - Wang, Yang
AU - Lin, Shiyuan
AU - Li, Meng
AU - Zhu, Chuanyong
AU - Yang, Hao
AU - Dong, Pei
AU - Lu, Mingjie
AU - Wang, Wenhang
AU - Cao, Jianlin
AU - Liu, Qiang
AU - Feng, Xiang
AU - Hu, Han
AU - Tsubaki, Noritatsu
AU - Wu, Mingbo
N1 - Publisher Copyright:
© 2023 Elsevier B.V.
PY - 2024/1
Y1 - 2024/1
N2 - The direct transformation of CO2 into valuable chemicals with the aid of sustainable energy-generated H2 has attracted enormous interest owing to the integrated functions of carbon elimination and non-fossil fuel-derived products supply. As one of the most promising catalysts for CO2 hydrogenation, the chemical properties of Fe-based catalysts, such as electronic structure and coordination environment, have been widely studied. However, the mass/heat transfer effects in Fe-based catalysts are also crucial to the targeted product selectivity and catalytic stability, but have been rarely investigated due to the lack of facile fabrication protocols. Herein, we precisely fabricate and tailor the architecture of the Fe-based monolithic catalysts by a direct ink writing (DIW)-type three-dimensional (3D) printing technology under the guidance of the computationally controlled printing procedure. The Fe-based monolithic catalyst with spiral-type architecture delivers extremely high light olefins selectivity (52.6%) and space time yield (STY, 451.8 gCH2 kgcat−1 h−1) from CO2 hydrogenation. Based on the mass-transfer simulation, the spiral-structured channels in the Fe-based monolithic catalyst lower the coverage of intermediates and products on the catalytic interface due to the optimal mass-transfer effect, thus maximizing the utilization of active sites and timely terminating the carbon-chain growth. More in-depth, the density functional theoretical (DFT) simulations verify that the relatively electron-rich catalytic interface with low intermediate coverage could facilitate the desorption of olefins and decelerate the C-C coupling step, which synergistically guarantee the enhanced light olefins synthesis performance. Furthermore, the enhanced heat-transfer effect endowed by the 3D architecture prolongs the life-time of catalyst by avoiding undesirable active site aggregation and carbon deposition. The powerful strategy for catalyst fabrication not only provides a new concept of regulating the CO2 hydrogenation performance of Fe-based catalysts but also holds a great promise to spread into other catalytic systems for targeted synthesis.
AB - The direct transformation of CO2 into valuable chemicals with the aid of sustainable energy-generated H2 has attracted enormous interest owing to the integrated functions of carbon elimination and non-fossil fuel-derived products supply. As one of the most promising catalysts for CO2 hydrogenation, the chemical properties of Fe-based catalysts, such as electronic structure and coordination environment, have been widely studied. However, the mass/heat transfer effects in Fe-based catalysts are also crucial to the targeted product selectivity and catalytic stability, but have been rarely investigated due to the lack of facile fabrication protocols. Herein, we precisely fabricate and tailor the architecture of the Fe-based monolithic catalysts by a direct ink writing (DIW)-type three-dimensional (3D) printing technology under the guidance of the computationally controlled printing procedure. The Fe-based monolithic catalyst with spiral-type architecture delivers extremely high light olefins selectivity (52.6%) and space time yield (STY, 451.8 gCH2 kgcat−1 h−1) from CO2 hydrogenation. Based on the mass-transfer simulation, the spiral-structured channels in the Fe-based monolithic catalyst lower the coverage of intermediates and products on the catalytic interface due to the optimal mass-transfer effect, thus maximizing the utilization of active sites and timely terminating the carbon-chain growth. More in-depth, the density functional theoretical (DFT) simulations verify that the relatively electron-rich catalytic interface with low intermediate coverage could facilitate the desorption of olefins and decelerate the C-C coupling step, which synergistically guarantee the enhanced light olefins synthesis performance. Furthermore, the enhanced heat-transfer effect endowed by the 3D architecture prolongs the life-time of catalyst by avoiding undesirable active site aggregation and carbon deposition. The powerful strategy for catalyst fabrication not only provides a new concept of regulating the CO2 hydrogenation performance of Fe-based catalysts but also holds a great promise to spread into other catalytic systems for targeted synthesis.
KW - 3D printing
KW - CO hydrogenation
KW - Light olefins
KW - Mass/heat-transfer enhancements
KW - Reaction mechanism
UR - http://www.scopus.com/inward/record.url?scp=85175607651&partnerID=8YFLogxK
U2 - 10.1016/j.apcatb.2023.123211
DO - 10.1016/j.apcatb.2023.123211
M3 - 学術論文
AN - SCOPUS:85175607651
SN - 0926-3373
VL - 340
JO - Applied Catalysis B: Environmental
JF - Applied Catalysis B: Environmental
M1 - 123211
ER -