TY - JOUR
T1 - Multiple-site activation induced by guanidine ionic liquid decorated chromium (III) terephthalate for coupling of carbon dioxide with epoxides
AU - Feng, Nengjie
AU - Cheng, Linyan
AU - Zhang, Yukun
AU - Tao, Yujie
AU - Wan, Hui
AU - Chen, Chong
AU - Guan, Guofeng
N1 - Publisher Copyright:
© 2025 Elsevier Inc.
PY - 2025/6
Y1 - 2025/6
N2 - Cycloaddition, as a sound strategy for high-value utilization of carbon dioxide (CO2), has been long pursued, wherein the challenging substrate activation process is a top priority for devising novel heterogeneous catalysts. In this study, a guanidine-based ionic liquid tethering –NH2 groups was designed and integrated with chromium (III) terephthalate (MIL-101(Cr)) through the coordination with unsaturated Cr3+ centers. The developed [NH2TMG]Br@MIL-101(Cr) (TMG represents tetramethylguanidine) decorated with plentiful basic functional groups created a fast channel for the capturing and binding of CO2, while the highly-accessible Lewis acidic sites (Cr3+) and hydrogen bond donors (N+-H) embedded within the nanocomposite synergized to activate the epoxide, synchronously. Under the reaction conditions optimized by response surface methodology (RSM) (103.2 °C, 1.03 MPa, 1.85 h, and 2.53 wt% of catalyst), a satisfactory chloropropene carbonate (CPC) yield of 98.2 % with a selectivity of 99.2 % were achieved. We further demonstrated the heterogeneity and recyclability of [NH2TMG]Br@MIL-101(Cr), and ascertained the substrate expansibility. Moreover, the in-situ diffuse reflectance infrared Fourier-transform spectra (DRIFTS) and density functional theory (DFT) computations afforded deep insights into the proposed multiple-site activation mechanism for CO2 coupling. This study highlighted an innovative pathway for constructing durable IL@MOFs nanocomposites and presented a tangible route to effectively converting CO2.
AB - Cycloaddition, as a sound strategy for high-value utilization of carbon dioxide (CO2), has been long pursued, wherein the challenging substrate activation process is a top priority for devising novel heterogeneous catalysts. In this study, a guanidine-based ionic liquid tethering –NH2 groups was designed and integrated with chromium (III) terephthalate (MIL-101(Cr)) through the coordination with unsaturated Cr3+ centers. The developed [NH2TMG]Br@MIL-101(Cr) (TMG represents tetramethylguanidine) decorated with plentiful basic functional groups created a fast channel for the capturing and binding of CO2, while the highly-accessible Lewis acidic sites (Cr3+) and hydrogen bond donors (N+-H) embedded within the nanocomposite synergized to activate the epoxide, synchronously. Under the reaction conditions optimized by response surface methodology (RSM) (103.2 °C, 1.03 MPa, 1.85 h, and 2.53 wt% of catalyst), a satisfactory chloropropene carbonate (CPC) yield of 98.2 % with a selectivity of 99.2 % were achieved. We further demonstrated the heterogeneity and recyclability of [NH2TMG]Br@MIL-101(Cr), and ascertained the substrate expansibility. Moreover, the in-situ diffuse reflectance infrared Fourier-transform spectra (DRIFTS) and density functional theory (DFT) computations afforded deep insights into the proposed multiple-site activation mechanism for CO2 coupling. This study highlighted an innovative pathway for constructing durable IL@MOFs nanocomposites and presented a tangible route to effectively converting CO2.
KW - CO cycloaddition
KW - Guanidine ionic liquid
KW - MIL-101(Cr)
KW - Multiple-site activation
UR - http://www.scopus.com/inward/record.url?scp=85217957163&partnerID=8YFLogxK
U2 - 10.1016/j.jcis.2025.02.087
DO - 10.1016/j.jcis.2025.02.087
M3 - 文章
AN - SCOPUS:85217957163
SN - 0021-9797
VL - 687
SP - 561
EP - 572
JO - Journal of Colloid and Interface Science
JF - Journal of Colloid and Interface Science
ER -