Carbon Fiber Film with Multi-Hollow Channels to Expedite Oxygen Electrocatalytic Reaction Kinetics for Flexible Zn-Air Battery.

The high oxygen electrocatalytic overpotential of flexible cathodes due to sluggish reaction kinetics result in low energy conversion efficiency of wearable zinc-air batteries (ZABs). Herein, lignin, as a 3D flexible carbon-rich macromolecule, is employed for partial replacement of polyacrylonitrile and constructing flexible freestanding air electrodes (FFAEs) with large amount of mesopores and multi-hollow channels via electrospinning combined with annealing strategy. The presence of lignin with disordered structure decreases the graphitization of carbon fibers, increases the structural defects, and optimizes the pore structure, facilitating the enhancement of electron-transfer kinetics. This unique structure effectively improves the accessibility of graphitic-N/pyridinic-N with oxygen reduction reaction (ORR) activity and pyridinic-N with oxygen evolution reaction (OER) activity for FFAEs, accelerating the mass transfer process of oxygen-active species. The resulting N-doped hollow carbon fiber films (NHCFs) exhibit superior bifunctional ORR/OER performance with a low potential difference of only 0.60 V. The rechargeable ZABs with NHCFs as metal-free cathodes possess a long-term cycling stability. Furthermore, the NHCFs can be used as FFAEs for flexible ZABs which have a high specific capacity and good cycling stability under different bending states. This work paves the way to design and produce highly active metal-free bifunctional FFAEs for electrochemical energy devices.

Reversible covalent chemistry of carbon dioxide unlocks the recalcitrance of cellulose for its enzymatic saccharification.

To overcoming the natural recalcitrance of cellulose for glucose production via enzymatic hydrolysis, a new strategy of destroying hydrogen bond donor to reconstruct cellulose's hydrogen bonding network was developed via a mild reversible reaction of cellulose with CO2 catalyzed by organic bases. The reaction dynamics of cellulose with CO2 in the presence of organic bases was studied by using in situ IR. Investigation also included how the organic bases in pretreatment media and pretreatment parameters including CO2 pressure, pretreatment temperature and time affected the physical-chemical structure of cellulose by Fourier Transform Infrared Spectroscopy (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM) and Atomic force microscopy (AFM) and subsequent enzymatic scarification of cellulose. The findings showed that dissolution activation efficiency significantly correlated to various parameters, that can be optimized to be the tetramethyl guanidine (TMG)/CO2/DMSO solvent system at 50 °C, 2 MPa of CO2 for 2 h, by which a complete transformation the cellulose crystalline structure from I to II, and 100% glucose yield were achieved. The recyclability and usability are also investigated.

Preparation of Cellulose Films from Sustainable CO2/DBU/DMSO System.

Cellulose films are regarded as sustainable materials having wide applications in food packaging, separation, etc. Their preparation substantially relies on sufficient dissolution. Herein, various celluloses adequately dissolved in a new solvent system of carbon dioxide,1, 8-diazabicyclo [5.4.0] undec-7-ene and dimethyl sulfoxide (CO2/DBU/DMSO) were made in to films using different regeneration reagents. The films regenerated from ethanol and methanol presented homogeneous and smooth surfaces, while those from 5 wt % NaOH (aq.) and 5 wt % H2SO4 (aq.) showed rough surfaces, as analyzed using scanning electron microscopy (SEM) and atomic force microscopy (AFM). The films regenerated from 5 wt % NaOH (aq.) and 5 wt % H2SO4 (aq.) rendered cellulose II structures, while those regenerated from alcohols had amorphous structures as evidenced using fourier transform infrared spectroscopy (FT-IR) and X-ray diffraction (XRD) results. The films made of microcrystalline cellulose had a good light transmittance of about 90% at 800 nm with a tensile strength of 55 MPa and an elongation break of 6.5%, while those from wood pulp cellulose demonstrated satisfactory flexibility with a tensile strength of 91 MPa and an elongation break of 9.0%. This research reports a simple, environmental, and sustainable method to prepare cellulose films of good mechanical properties.