INORGANICA CHIMICA ACTA
·
2022
·
IF 3.118
Wei Wang,Jing-Zhe Li,Shi-Jian Luo,Zi-Xuan Yao,Kuan-Guan Liu
Using the atomic precisely structurally characterized clusters as electrocatalysts can provide some possible structure information about the active intermediate during the electrocatalytic N 2 reduction reaction (NRR) process. A Cu4 cluster, named [(bpy) 4 Cu 4 (C 10 H 8 SO 3 ) 4 (OH) 4 ]•4H 2 O ( 1 ), has been synthesized and fully characterized by IR, SXRD, XPS, EPR, et al. Single crystal structural analysis reveals that the core structure of the cluster has a step-scheme conformation with two μ 2 -OH and two μ 3 -OH groups. Electro-catalysis studies of this cluster show that it can achieve a highest NH 3 yield of 2.18 μg h −1 mg −1 and a FE of 0.97 % at −0.6 V. The excellent NRR performance may be attributable to the additional μ 3 -OH groups, based on the contrastively study of the other electrocatalysts of the Cu powder and the Cu 2 complex, named [(μ 2 -OH)(μ 2 -Cl)(bpy) 2 Cu 2 Cl 2 ] ( 2 ), with one μ 2 -OH group in its structure. This work provides some structure information about the possible active sites during the NRR process and inspires us to develop new cluster as efficient electrocatalysts for advancing sustainable NH 3 production. Using the atomic precisely structurally characterized clusters as electrocatalysts can provide some possible structure information about the active intermediate during the electrocatalytic N 2 reduction reaction (NRR) process. A Cu4 cluster, named [(bpy) 4 Cu 4 (C 10 H 8 SO 3 ) 4 (OH) 4 ]•4H 2 O ( 1 ), has been synthesized and fully characterized by IR, SXRD, XPS, EPR, et al. Single crystal structural analysis reveals that the core structure of the cluster has a step-scheme conformation with two μ 2 -OH and two μ 3 -OH groups. Electro-catalysis studies of this cluster show that it can achieve a highest NH 3 yield of 2.18 μg h −1 mg −1 and a FE of 0.97 % at −0.6 V. The excellent NRR performance may be attributable to the additional μ 3 -OH groups, based on the contrastively study of the other electrocatalysts of the Cu powder and the Cu 2 complex, named [(μ 2 -OH)(μ 2 -Cl)(bpy) 2 Cu 2 Cl 2 ] ( 2 ), with one μ 2 -OH group in its structure. This work provides some structure information about the possible active sites during the NRR process and inspires us to develop new cluster as efficient electrocatalysts for advancing sustainable NH 3 production.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF MOLECULAR STRUCTURE
·
2026
·
IF 4.9
Di-Ming Chen,Yu-Ting Shi,Xue-Jing Zhang,Shao-Ming Fang
A robust Al-MOF built from octanuclear [Al 8 (μ 2 -OH) 8 (COO) 12 ] clusters with oxygen-rich 1D channels has been prepared. • It exhibits a high C₂H₆ uptake of 147.6 cm 3 /g and an IAST selectivity of 1.69 for equimolar C 2 H 6 /C 2 H 4 at 298 K and 1 bar. • The separation potential (ΔQ = 1.42 mmol/g) outperforms many reported Al-MOFs, reflecting a balanced capacity–selectivity trade-off. • Combined GCMC, DFT, and MD simulations reveal that multiple C–H···O contacts and greater charge transfer govern the ethane preference. The separation of ethane (C 2 H 6 ) from ethylene (C 2 H 4 ) represents a critically important yet highly challenging process in the petrochemical industry, as these two hydrocarbons possess nearly identical molecular sizes and boiling points. In this work, we report the C 2 H 6 adsorption and separation performance of a three-dimensional aluminum-based metal–organic framework (Al-MOF) constructed from octanuclear aluminum clusters and a tricarboxylate linker, featuring one-dimensional channels decorated with abundant strongly electronegative oxygen atoms originating from coordinated formate groups and μ 3 -OH moieties. The presence of these electron-rich oxygen sites creates a polar pore environment that establishes multiple C–H···O short interactions with C 2 H 6 molecules, thereby imparting a distinct recognition preference toward the paraffin over the olefin. Upon activation, the material exhibits a C 2 H 6 adsorption capacity of 147.6 cm 3 /g at 298 K and 1 bar. The ideal adsorbed solution theory (IAST) selectivity for an C 2 H 6 /C 2 H 4 (10/90) mixture reaches 1.69 at 298 K and 1 bar. Furthermore, the separation potential (Δ Q ), which integrates both adsorption capacity and selectivity, is determined to be 1.42 mmol/g, indicating a well-balanced performance profile. The different adsorption performance of 1a toward C 2 H 6 /C 2 H 4 was thoroughly studied via a combination of GCMC, DFT and MD calculations, which demonstrates that deliberate introduction of electron-rich oxygen functionalities into the pore walls of Al-MOFs represents an effective strategy for enhancing ethane-selective adsorption, positioning the present material as a competitive candidate for energy-efficient ethylene purification. Graphical -Synopsis A robust Al-MOF with octanuclear clusters and oxygen-rich pore walls was synthesized for C 2 H 6 /C 2 H 4 separation. It exhibits preferential C₂H₆ adsorption (147.6 cm 3 /g at 298 K, 1 bar), an IAST selectivity of 1.69 for equimolar mixtures, and a separation potential of 1.42 mmol/g. Combined GCMC, DFT, and MD simulations reveal that stronger C–H···O hydrogen bonding and greater charge difference lead to a more favorable host–guest interaction energy (–1.34 vs. –1.27 eV) for ethane. This work demonstrates that engineering electronegative oxygen sites in Al-MOFs is an effective strategy for energy-efficient ethylene purification. Graphical -Pictogram Download: Download high-res image (322KB) Download: Download full-size image
✓ 已验证
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
Liyan Chen,Meng Rong,Jiemiao Yu,Qiyu Meng,Shan Ni,Xia Wu,Li Wang,Huifang Xing,Huizhou Liu,Liangrong Yang
Due to the biotoxicity and ecological hazards of 2,4-toluene diamine (TDA) and 4,4′-methylene dianiline (MDA), it is the key process for upcycling polyurethane (PU) waste to remove them from the PU bio-hydrolysate with high selectivity and efficiency. Herein, MIL-53 series metal–organic frameworks (MOFs) were prepared and applied to remove aromatic diamines. Besides, the effects of their different structural units on the adsorption performance were investigated. Among the three metal nodes (Cr 3+ , Al 3+ , Fe 3+ ) of MIL-53, MIL-53(Al) demonstrated the highest adsorption capacities upon TDA (4.17 mmol/g) and MDA (2.00 mmol/g) due to its more μ 2 -OH sites and higher porosity. Compared with MIL-53(Al), DUT-4 and DUT-5 owned longer linkers but exhibited inferior aromatic diamine adsorption performance, which was ascribed to the more appropriate pore size and more μ 2 -OH sites of MIL-53(Al). Notably, MIL-53(Al) exhibited excellent selectivity towards aromatic diamines, while the removal efficiency reached over 90 %. In addition, spectral analysis before and after adsorption revealed the mechanism, which involved host–guest interactions, H-bonding interactions, and π-π stacking. The results indicate the great potential of applying the optimal MIL-53(Al) as an alternative adsorbent for removing hazardous aromatic diamines from the PU bio-hydrolysate.
研究领域:
环境科学
·
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）