Cu cluster embedded porous nanofibers for high-performance CO_(2) electroreduction

Metal-doped carbon materials, as one of the most important electrocatalytic catalysts for CO_(2)reduction reaction(CO_(2)RR), have attracted increasing attention. Herein, a series of Cu cluster embedded highly porous nanofibers have been prepared through the carbonization of electro-spun MOF/PAN nanofibers.The obtained Cu cluster doped porous nanofibers possessed fibrous morphology, high porosity, conductivity, and uniformly dispersed Cu clusters, which could be applied as promising CO_(2)RR catalysts. Specifically, best of them, MCP-500 exhibited high catalytic performance for CO_(2)RR, in which the Faradaic efficiency of CO(FECO) was as high as 98% at-0.8 V and maintained above 95% after 10 h continuous electrocatalysis. The high performance might be attributed to the synergistic effect of tremendously layered graphene skeleton and uniformly dispersed Cu clusters that could largely promote the electron conductivity, mass transfer and catalytic activity during the electrocatalytic CO_(2)RR process. This attempt will provide a new idea to design highly active CO_(2)RR electrocatalyst.

Boosting CO_(2) electroreduction performance over fullerene-modified MOF-545-Co promoted by π –π interaction

Metal-organic frameworks(MOFs) have showed high promise in CO_(2)-electroreduction, yet their generally insufficient conductivity or low electron-transfer efficiency have largely restricted the wide-spread applications. Herein, fullerene molecules(i.e., C60and C70) have been successfully introduced into the pore-channels of a Co-porphyrin based MOF through a facile strategy. Thus-obtained hybrid materials present higher electron-transfer ability, enhanced CO_(2)adsorption-enthalpy and CO_(2)electroreduction activity. Notably, the charge transfer resistance(Rct) of C60@MOF-545-Co is almost 5 times lower of than that of MOF-545-Co, as well as 1.5 times increased for the CO_(2)adsorption enthalpy. As expect, the FECO of C60@MOF-545-Co(97.0%) is largely higher than MOF-545-Co(70.2%), C60@MOF-545(19.4%), C60(11.5%)and physical mixture(70.3%) and presented as one of the best CO_(2)electroreduction catalysts reported in H-cell system. The facile strategy would give rise to new insight into the exploration of powerful MOFbased hybrid materials in high-efficiency CO_(2)electroreduction.

Self-assembly of single metal sites embedded covalent organic frameworks into multi-dimensional nanostructures for efficient CO_(2) electroreduction

Morphology-controlled electrocatalysts with the ability of CO_(2) adsorption/activation, mass transfer, high stability and porosity are much desired in electrochemical CO_(2) reduction reaction (CO_(2)RR). Here, three kinds of multi-dimensional nanostructures (i.e., hollow sphere, nanosheets and nanofibers) have been successfully produced through the modulation of porphyrin-based covalent organic frameworks (COFs) with various modulators. The obtained nanostructures with high-stability, large surface-area, and single metal sites enable efficient CO_(2)RR into CH_(4). Notably, they all exhibit higher FE (hollow sphere, 68.2%;nanosheet, 64.2% and nanofiber, 71.0%, -0.9 V) than COF-366-Cu (43.0%, -0.9 V) after morphology control. Noteworthy, the FE of COF-366-Cu (HS) keeps higher than 52.4% over a wide potential range from -0.9 V to -1.1 V and the achieved FECH_(4) + C_(2)H_(4) (82.8%, -0.9 V) is superior to most of reported COFs and copper-based electrocatalysts. This work paves a new way in the exploration of COF-based multi-dimensional nanostructures applicable in efficient CO_(2)RR to CH_(4).