Photoexcitation of molecular radicals can produce strong reducing agents; however, the limited lifetimes of the doublet excited states preclude many applications. Herein, we propose and demonstrate a general strategy to translate a highly energetic electron from a doublet excited state to a ZrO 2 insulator, thereby increasing the lifetime by about 6 orders of magnitude while maintaining a reducing potential less than −2.4 V vs SCE. Specifically, red light excitation of a salicylic acid modified perylene diimide radical anion PDI •− anchored to a ZrO 2 insulator yields a ZrO 2 (e − )|PDI charge separated state with an ∼10 μs lifetime in 23% yield. The ZrO 2 (e − )s were shown to drive CO 2 → CO reduction with a Re catalyst present in micromolar concentrations. More broadly, this strategy provides new opportunities to reduce important reagents and catalysts at low concentrations through diffusional electron transfer.

The integration of the glycerol oxidation reaction (GOR) with the hydrogen evolution reaction in photoelectrochemical (PEC) cells is a desirable alternative to PEC water splitting since a large quantity of glycerol is easily accessible as the byproduct from the biodiesel industry. However, the PEC valorization of glycerol to the value-added products suffers from low Faradaic efficiency and selectivity, especially in acidic conditions, which is beneficial for hydrogen production. Herein, by loading bismuth vanadate (BVO) with a robust catalyst composed of phenolic ligands (tannic acid) coordinated with Ni and Fe ions (TANF), we demonstrate a modified BVO/TANF photoanode for the GOR with a remarkable Faradaic efficiency of over 94% to value-added molecules in a 0.1 M Na 2 SO 4 /H 2 SO 4 (pH = 2) electrolyte. The BVO/TANF photoanode achieved a high photocurrent of 5.26 mA•cm −2 at 1.23 V versus reversible hydrogen electrode under 100 mW/cm 2 white light irradiation for formic acid production with 85% selectivity, equivalent to 573 mmol/(m 2 • h). Transient photocurrent and transient photovoltage techniques and electrochemical impedance spectroscopy along with intensitymodulated photocurrent spectroscopy indicated that the TANF catalyst could accelerate hole transfer kinetics and suppress charge recombination. Comprehensive mechanistic investigations reveal that the GOR is initiated by the photogenerated holes of BVO, while the high selectivity to formic acid is attributed to the selective adsorption of primary hydroxyl groups in glycerol on TANF. This study provides a promising avenue for highly efficient and selective formic acid generation from biomass in acid media via PEC cells.

Photon energy loss to interfacial charge recombination is one of the key challenges to achieving high efficiencies for solar water splitting in photoelectrochemical cells (PECs). Herein, BiVO4-based photoanodes are constructed, where BiVO4, cadmium sulfide nanosheets (CdS NSs), hole transport molecules (HTs), and oxygen evolution cocatalysts (OECs) assemble sequentially in a cascade band alignment for efficient photogenerated hole extraction and accumulation to OECs. In the photoanode assemblies, CdS NSs act as energetic barriers to suppress surface recombination. Thiolate-functionalized aryl amine HTs that anchor to CdS NSs are interfacial-charge-transfer mediators that efficiently extract the photogenerated holes. The oxidized HT (HT+) hops isoenergetically among adjacent HTs and finally accumulates oxidative equivalents to OEC. Transient absorption spectroscopy along with intensity-modulated photocurrent spectroscopy proves that HTs and CdS NSs accelerate hole-transfer kinetics and suppress recombination of surface-accumulated holes and electrons. Among the three HTs, triphenylamine shows the best performance. The best-performing photoanode assembly exhibits increased photocurrent density from 0.87 to 5.2 mA/cm2. The molecular approach to hole extraction from BiVO4 photoanodes provides a promising avenue for efficient photogenerated charge separation and collection to optimize the performance of PEC for water splitting.

Photocatalytic lignin valorization has caught widespread attention; yet the reaction systems often employed noble metal complexes, hydrogen atom transfer (HAT) agents, and/or sacrificial electron donors/acceptors that did not comply with...

This paper uses CT to gain the energy directly from the high-voltage transmission line, to address the problem of power supply for monitoring system in high voltage side of transmission line. The draw-out power coil can induce voltage from the transmission line, using single-chip microcomputer to analog and output PMW wave to control the charging module, provides a stable 3.4 V DC voltage to the load, and solve the problem of easy saturating of core. The power supply based on this kind of draw-out power coil has undergone the overall testing, and it is verified-showing that it can properly work in a non-saturated status within the current range of 50 -1000 A, and provide a stable output. The equipment also design protection circuit to improve the reliability to avid the impacts of the impulse current or short-circuit current. It effectively solves the problem of power supply for On-line Monitoring System of Transmission.