Self-Charging Aqueous Zn//COF Battery with UltraHigh Self-Charging Efficiency and Rate.

Self-charging zinc batteries that combine energy harvesting technology with batteries are candidates for reliable self-charging power systems. However, the lack of rational materials design results in unsatisfactory self-charging performance. Here, a covalent organic framework containing pyrene-4,5,9,10-tetraone groups (COF-PTO) is reported as a cathode material for aqueous self-charging zinc batteries. The ordered channel structure of the COF-PTO provides excellent capacity retention of 98% after 18 000 cycles at 10 A g-1 and ultra-fast ion transfer. To visually assess the self-charging performance, two parameters, namely self-charging efficiency (self-charging discharge capacity/galvanostatic discharge capacity, η) and average self-charging rate (total discharge capacity after cyclic self-charging/total cyclic self-charging time, ν), are proposed for performance evaluation. COF-PTO achieves an impressive η of 96.9% and an ν of 30 mAh g-1 self-charge capacity per hour in 100 self-charging cycles, surpassing the previous reports. Mechanism studies reveal the co-insertion of Zn2+ and H+ double ions in COF-PTO of self-charging zinc batteries. In addition, the C═N and C═O (on the benzene) in COF-PTO are ortho structures to each other, which can easily form metal heterocycles with Zn ions, thereby driving the forward progress of the self-charging reaction and enhancing the self-charging performance.

Minimalist Design for Solar Energy Conversion: Revamping the π-Grid of an Organic Framework into Open-Shell Superabsorbers.

We apply a versatile reaction to a versatile solid: the former involves the electron-deficient alkene tetracyanoethylene (TCNE) as the guest reactant; the latter consists of stacked 2D honeycomb covalent networks based on the electron-rich ß-ketoenamine hinges that also activate the conjugated, connecting alkyne units. The TCNE/alkyne reaction is a [2 + 2] cycloaddition-retroelectrocyclization (CA-RE) that forms strong push-pull units directly into the backbone of the framework-i.e., using only the minimalist "bare-bones" scaffold, without the need for additional side groups of alkynes or other functions. The ability of the stacked alkyne units (i.e., as part of the honeycomb mass) to undergo such extensive rearrangement highlights the structural flexibility of these covalent organic framework (COF) hosts. The COF solids remain porous, crystalline, and air-/water-stable after the CA-RE modification, while the resulting push-pull units feature distinct open-shell/free-radical character, are strongly light-absorbing, and shift the absorption ends from 590 nm to around 1900 nm (band gaps from 2.17-2.23 to 0.87-0.95 eV), so as to better capture sunlight (especially the infrared region which takes up 52% of the solar energy). As a result, the modified COF materials achieve the highest photothermal conversion performances, holding promise in thermoelectric power generation and solar steam generation (e.g., with solar-vapor conversion efficiencies >96%).