RESUMO
Aqueous sodium-ion batteries (ASIBs) and aqueous ammonium-ion batteries (AAIBs) attract great attention due to their low cost, safety, and environmental friendliness, but the lack of suitable electrodes with competitive capacity and redox potential limits their practical applications. Herein, we report a porous organic polymer (POP) with multiple redox processes as anodes for ASIBs and AAIBs. This POP displays desired redox potential and shows high reversible capacity of more than 200 mAh g-1 in both ASIBs and AAIBs. Full cells configured by this POP anode also display excellent performance (about 80% and 60% capacity retention over 1000 cycles in ASIBs and AAIBs). In addition, the intercalation chemistry of inorganic NH4+ with this POP is investigated, illustrating that the pyrazine sites in this POP are the redox centers to reversibly combine with NH4+. This work provides a promising and alternative anode for ASIBs and AAIBs and paves a new way for the development of novel organic materials for other aqueous battery systems.
RESUMO
The pyrolysis treatment of waste printed circuit boards (WPCBs) shows great potential for sustainable treatment and hazard reduction. In this work, based on thermogravimetry (TG), pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS), and density functional theory (DFT), the thermal weight loss, product distribution, and kinetics of WPCBs pyrolysis were studied by single-step and multi-step pyrolysis at fast (600 °C/min) and slow (10 °C/min) heating rates. The heating rates of TG and Py-GC/MS were the same for each group of experiments. In addition, the bond dissociation energy (BDE) of WPCBs polymer monomers was calculated by DFT method. Compared with slow pyrolysis, the final weight loss of fast pyrolysis is reduced by 0.76 wt%. The kinetic analysis indicates that the activation energies of main pyrolysis stages range from 98.29 kJ/mol to 177.59 kJ/mol. The volatile products of fast pyrolysis are mainly phenols and aromatics. With the increase of multi-step pyrolysis temperature, the order of the escaping volatiles is phenols, hydrocarbyl phenols, aromatics, and benzene (or diphenyl phenol). The pyrolysis residue of WPCBs may contains phenolics and polymers. Based on the free radical reactions, the mechanism and reaction pathways of WPCBs pyrolysis were deduced by the DFT. Moreover, a large amount of benzene is produced by pyrolysis, and its formation mechanism was elaborated.
Assuntos
Calefação , Pirólise , Benzeno , Humanos , Cinética , Fenol , Termogravimetria , Redução de PesoRESUMO
A ≥ 200 °C fraction (CT200F) of low-temperature coal tar was prepared by a rotary film evaporator. The catalytic conversion experiments of CT200F and six model compounds were conducted on the pyrolysis gas chromatography-mass spectrometer. The yields of catalytic conversion products benzene, toluene, xylene, and naphthalene (BTXN) were analyzed by semi-quantitative analysis according to the chromatographic peak areas. Additionally, the possible formation pathways and mechanisms of the target products BTXN generated over different catalysts were investigated. The results show that the yield of aromatic hydrocarbons increases and the yield of acid compounds decreases during CT200F pyrolysis over ZSM-5, HY, USY, and ß-zeolite compared with that of its non-catalytic pyrolysis, especially the yields of BTXN obtained over USY and ß-zeolite increase by 128 and 108%, respectively. The pore structure of ZSM-5 is suitable to produce BTX, while the suitable acidity and pore structure of USY, HY, and ß-zeolite are more beneficial for the selective preparation of naphthalene than that of ZSM-5. The conversion pathways of six model compounds into BTXN over zeolites were obtained, and the following conclusions can be drawn: The dehydroxylation effect of zeolites shows the order of ZSM-5 > HY > USY > ß-zeolite. The catalytic effect of zeolites on the cracking and ring opening of PAHs in CT200F shows the order of ß-zeolite > USY > HY > ZSM-5. The catalytic effect of catalysts on the cracking and aromatization of aliphatic compounds shows the order of ZSM-5 > ß-zeolite > USY > HY. ß-zeolite has an outstanding catalytic performance in the conversion of PAHs into naphthalene. ZSM-5 and HY can effectively remove phenolic hydroxyl groups in phenol and naphthol. During the catalytic conversion processes of the coal tar fraction and model compounds, the catalytic effect of the pore constructions of zeolites is more important than their acidities, which determines whether large molecules can enter and whether acid sites in non-micropores can be effectively utilized.