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Direct solar-to-hydrogen conversion from pure water using all-organic heterogeneous catalysts remains elusive. The challenges are twofold: (i) full-band low-frequent photons in the solar spectrum cannot be harnessed into a unified S1 excited state for water-splitting based on the common Kasha-allowed S0 → S1 excitation; (ii) the H+ → H2 evolution suffers the high overpotential on pristine organic surfaces. Here, we report an organic molecular crystal nanobelt through the self-assembly of spin-one open-shell perylene diimide diradical anions (:PDI2-) and their tautomeric spin-zero closed-shell quinoid isomers (PDI2-). The self-assembled :PDI2-/PDI2- crystal nanobelt alters the spin-dependent excitation evolution, leading to spin-allowed S0S1 → 1(TT) → T1 + T1 singlet fission under visible-light (420 nm~700 nm) and a spin-forbidden S0 → T1 transition under near-infrared (700 nm~1100 nm) within spin-hybrid chromophores. With a triplet-triplet annihilation upconversion, a newly formed S1 excited state on the diradical-quinoid hybrid induces the H+ reduction through a favorable hydrophilic diradical-mediated electron transfer, which enables simultaneous H2 and O2 production from pure water with an average apparent quantum yield over 1.5% under the visible to near-infrared solar spectrum. Achieving direct solar-to-hydrogen conversion from pure water using solely organic heterogeneous catalysts is still challenging. Here the authors report an all-organic semiconductor catalyst system for overall water splitting under visible to near-infrared light via triplet-triplet annihilation up conversion based on spin coupling. [ABSTRACT FROM AUTHOR]

During the discharge of Na–O2 batteries, O2 is reduced and combines with Na+ to form an insulating solid sodium oxide on the cathode, which severely hinders the mass transfer path, resulting in high polarization voltage, low energy efficiency, and short battery life. Hereby, we proposed a novel illumination-assisted Na–O2 battery in which bismuth vanadate (BiVO4) with few defects and high surface areas was used as the catalyst. It showed that the charge overpotential under photo assistance reduced by 1.11 V compared with that of the dark state one. Additionally, the insolating sodium oxide discharge products were completely decomposed, which was the key to running Na–O2 batteries over 200 cycles with a charge potential of no more than 3.65 V, while its counterpart (under dark condition) at 200 cycles had the charge potential higher than 4.25 V. The experiment combined with theoretical calculation shows that few defects, high surface areas, the altered electron transfer kinetics, and the low energy gap and low oxygen absorption energy of the (040) crystal face of monoclinic BiVO4 play an important role in catalyzing oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). [ABSTRACT FROM AUTHOR]

[Display omitted] • Scandium oxide functionalized carbon nitride (5-ScO-CN) is successfully prepared. • A new approach to boost PMS based oxidation is proposed. • 5-ScO-CN mediate the photoexcited electron transfer between PMS and organic contaminants. • Sc 2 O 3 causes fast oxidation of organic contaminants and activation of PMS to produce radicals. • 5-ScO-CN exhibits high stability for multiple usage and the potential of practical application. Generation of reactive radicals via photocatalytic peroxymonosulfate (PMS) is restricted by the sluggish kinetics of PMS decomposition and lack of electron transfer channel. Herein, we firstly prepared rare earth oxide functionalized carbon nitride (5-ScO-CN) by simple in-situ one-step calcination method, and surprisingly found it mediated photoexcited electron transfer between PMS and organic contaminants to boost PMS based oxidation decontamination. Rare earth oxide proceeds as active sites to mediate electron transfer from organic contaminants and PMS under visible light irradiation, it concurrently elevates fast oxidation of organic contaminant and activation of PMS to produce reactive radicals to further oxidize organic contaminants. We conducted density functional theory (DFT) calculation and galvanic oxidation process (GOP) to further unveil the role of 5-ScO-CN for mediating photoexcited electron transfer and generation of reactive radicals. This work proposes a novel mechanism for visible light boosted PMS based oxidation and provides a novel strategy for application of photocatalytic oxidation in environmental remediation field. [ABSTRACT FROM AUTHOR]

Fenton oxidation technology is a widely-used advanced oxidation technology. However, the generation of hydroxyl radicals is restrained by the sluggish recovery of Fe(II), thus affecting its long-lasting performance for water decontamination. Here, a novel niobium carbide (Nb 2 C) MXene material was applied as a green co-catalyst. Nb 2 C MXene can significantly promote Fenton reactions to produce hydroxyl radicals for degrading dimethyl phthalate (DMP) with high efficiency and high stability for long-term operation, which outperforms than various reported co-catalysts. Meanwhile, the Nb 2 C/Fe(III)/H 2 O 2 system is capable of non-selectively degrading a wide spectrum of refractory pollutants. Mechanism investigation reveals that Nb 2 C MXene as an electron donor can straight reduce Fe(III), meanwhile mediate electron shuttle from Fe(II) to H 2 O 2 to strongly expedite the generation of hydroxyl radicals. In addition, four main degradation routes of DMP were proposed. Therefore, this study offers an updated and valid strategy for the refractory organic pollutants elimination by coupling Nb 2 C MXene and Fenton oxidation. [Display omitted] • Nb 2 C MXene outperformed than a variety of co-catalysts of enhanced Fenton system. • The Nb 2 C/Fe(III)/H 2 O 2 can non-selectively degrade a wide spectrum of organic contaminants. • Nb 2 C MXene can provide electrons for direct Fe(III) reduction by cleaving Nb-C bonds. • Nb 2 C MXene can mediate electron transfer between Fe(II) and H 2 O 2 to promote Fenton reaction. [ABSTRACT FROM AUTHOR]

The low cost and high performance via a simple way of fabrication are considerable challenges for Si-based anode in the application of lithium-ion batteries. In this study, we synthesize a novel free-standing Si/C anode, consisting of yolk (Si)-shell (amorphous carbon) nanoparticles and carbon nanofibers (denoted as Si@void@C/CNFs), via a facile route of template removal and electrospun. The designed yolk-shell structure help buffer the volume expansion of silicon during the discharge/charge cycles, and the intertwined CNFs are conducive to electron fast transmission and guarantee structural integrity. As expected, with a low Si content (∼23 wt%), the self-supporting electrode of Si@void@C/CNFs exhibits a high specific capacity of ∼627.5 mAh g−1 as well as 69.3% capacity retention at 0.1 A g−1 after 100 cycles, better than Si@C/CNFs (20%) and Si/CNFs (9.5%) electrodes. The superior performance of Si@void@C/CNFs indicates that it is an attractive anode material for the practical application of Lithium-ion batteries. [Display omitted] • A facile strategy is designed to prepare free-standing Si@void@C/CNFs composite. • This structure consists of the yolk-shell structure and a 3D conducting network. • The structure can buffer the volume expansion of Si and accelerate electron transfer. • The composite demonstrates ideal cycle stability as lithium-ion batteries anode. [ABSTRACT FROM AUTHOR]

Herein, an electrochemical (EC) system was applied as "co-catalyst" to enhance the activation of peroxymonosulfate (EC/Fe(III)/PMS) for efficient Sulfamethoxazole (SMX) degradation. The cathodic reduction reaction can facilitate electron transfer to Fe(III) and trigger the sustainable Fe(III)/Fe(II) redox cycle. Unexpectedly, in addition to hydroxyl radical (•OH) and sulfate radical (SO 4 •−), non-radicals mechanism including singlet oxygen (1O 2) and Fe(IV) were also found involved in EC/Fe(III)/PMS system. The degradation of SMX in EC/Fe(III)/PMS system was accomplished by the collaboration of radicals and non-radicals oxidation. The generation routes and mechanisms of involved reactive oxygen species (ROS) were explored. The relative contributions of •OH, SO 4 •−, and nonradical species for the degradation of SMX were calculated to 4.75 %, 25.31 %, and 69.94 %, respectively. Besides, multiple degradation pathways of SMX were proposed by identifying the formed byproducts. The EC/Fe(III)/PMS process could efficiently degrade SMX under the influence of co-existing ions and inactivate pathogens in the wastewater. [Display omitted] • Electrochemical system was used as a "co-catalyst" to promote the Fe(III)/Fe(II) redox cycle. • SMX is effectively degraded with a weak electrical current consumption in EC/Fe(III)/PMS system. • EC/Fe(III)/PMS system is mainly a non-radical pathway dominated by 1O 2 and Fe(IV). • EC/Fe(III)/PMS system demonstrated the ability to simultaneously eliminate contaminants and pathogens. [ABSTRACT FROM AUTHOR]

In this study, N and O co-doping carbon materials with porous structure (NOPC-x) were applied to activate peroxymonosulfate (PMS) for bisphenol (BPA) degradation and the underlying effects in affecting NOPC-x activity were revealed. Electrochemical characterization, electron paramagnetic resonance (EPR) tests, quenching and PMS adsorption experiments were applied to clarify the mechanism of BPA degradation. It's found that BPA can be completely removed within 20 min (k obs = 0.30 min−1) in the NOPC/PMS system depending on the electron transfer path with the necessity of moderate surfaced unpaired electrons for electrons delivery, which could be regulated by the modifier dosage. However, excessive surfaced unpaired electrons were unfavorable to PMS adsorption, resulting in deterioration of BPA degradation. This study indicates that controlling the amount of surfaced unpaired electrons in an appropriate range is essential to ensure the carbonaceous materials activity in PMS activation to obtain a satisfactory BPA degradation. [Display omitted] ● NOPC exhibited superior activity for BPA degradation by PMS activation. ● Increasing heteroatomic doping enhanced the amount of surfaced unpaired electrons. ● Degradation of BPA was proposed to follow a nonradical electron transfer pathway. ● The role of surfaced unpaired electrons of NOPC in PMS activation was clarified. [ABSTRACT FROM AUTHOR]

Photoreforming of plastic waste is a novel approach, which can not only degrade plastic waste into valuable chemicals, but also produce high-energy-density hydrogen fuels. Here, we developed an in-situ derived carbon nitride-carbon nanotubes-NiMo hybrids via NiMo-assisted catalysis route, which works as an efficient and stable photocatalyst for plastics photoreforming. The strong π-π interaction between in-situ derived CNTs and CN promotes electron transfer, increases carrier lifetime and improves photocatalytic activity. The DFT calculations and single-particle PL quenching phenomenon confirmed the strong interface effect and charge transport for CN-CNTs-NM. In addition, the strong interaction between photocatalyst and ethylene glycol in plastics was observed in situ by single-particle PL. This work provides a smart strategy of utilizing in-situ derived π-π interaction as well as direct evidence of the charge transfer from the photocatalysts to ethylene glycol, which provides guidance for the rational design of highly efficient photocatalysts for plastics photoreforming. Photoreforming of plastics is a novel approach, which can not only degrade plastic waste into valuable chemicals, but also produce high-energy-density hydrogen fuels. Here, we developed an in-situ derived carbon nitride-carbon nanotubes-NiMo hybrids (CN-CNTs-NiMo) via NiMo self-catalytic route, which works as an efficient and stable photocatalyst for photoreforming of plastics under alkaline conditions. [Display omitted] • PET photoreforming can convert plastics into value-added chemicals and hydrogen using sunlight. • In situ-derived CN-CNTs-NM hybrids were synthesized NiMo-assisted catalysis route for photoreforming of PET. • Single-particle PL and DFT calculations confirm the existence of π-π interactions between CN and CNTs. • The real-world applicability of plastics photoreforming was confirmed by photoreforming of PET bottle. • The mechanism of plastics photoreforming was investigated in situ using single-particle PL. [ABSTRACT FROM AUTHOR]