Edge interface microenvironment regulation of CoOOH/commercial activated carbon nano-hybrids enabling PMS activation for degrading ciprofloxacin.

Peroxymonosulfate (PMS) is widely employed to generate oxygen-containing reactive species for ciprofloxacin (CIP) degradation. Herein, cobalt oxyhydroxide @activated carbon (CoOOH@AC) was synthesized via a wet chemical sedimentation method to activate PMS for degradation of CIP. The result suggested AC can support the vertical growth of CoOOH nanosheets to expose high-activity Co-contained edges, possessing efficient PMS activation and degradation activity and catalytic stability. In the presence of 3.0 mg of optimal CoOOH@AC and 2 mM PMS, 96.8 % of CIP was degraded within 10 min, approximately 11.6 and 9.97 times greater than those of CoOOH/PMS and AC/PMS systems. Notably, it was disclosed that the optimal CoOOH@AC/PMS system still exhibited efficient catalytic performance in a wide pH range, different organics and common co-existing ions. Quenching experiments and electron paramagnetic resonance indicated that both radical and non-radical processes contributed to the degradation of CIP, with 1O2 and direct electron transfer accounting for the non-radical pathway and SO4•- and •OH serving as the main radical active species. Finally, possible CIP degradation pathways were proposed based on high-performance liquid chromatography-mass spectrometry. This study provided an alternate method for wastewater treatment based on PMS catalyzed by cobalt-based hydroxide.

Co3O4 Nanocrystals with an Oxygen Vacancy-Rich and Highly Reactive (222) Facet on Carbon Nitride Scaffolds for Efficient Photocatalytic Oxygen Evolution.

Oxygen evolution reaction (OER) with sluggish kinetics is the rate-determining step of water splitting, which dominates the solar-to-hydrogen fuel conversion efficiency. Herein, we constructed an oxygen vacancy-rich and highly reactive (222) facet in Co3O4 nanocrystals anchored on carbon nitride nanofiber (CNF) by a solvothermal reduction method. The resulting Co3O4 nanocrystals/CNF (COCNF) demonstrated a dramatically enhanced OER with a rate of 24.9 µmol/h under visible light, which is 124 times higher than that of CNF. This excellent catalytic activity of COCNF is based on a synergistic effect between its binary components for charge separation, oxygen vacancies for enhanced conductivity, and facet (222) exposure of Co3O4 nanocrystals for improved heterogeneous kinetics. Density functional theory (DFT) calculations revealed the water oxidation mechanism at different facets and found that the formed oxygen vacancies lead to a reduction of the materials' bandgap. The correlation between Co3O4 crystal facets and the inherent OER catalytic activities under acidic solution was in the order of (222) > (220) > (311).

Probing the reversibility and kinetics of Li+ during SEI formation and (de)intercalation on edge plane graphite using ion-sensitive scanning electrochemical microscopy.

Ions at battery interfaces participate in both the solid-electrolyte interphase (SEI) formation and the subsequent energy storage mechanism. However, few in situ methods can directly track interfacial Li+ dynamics. Herein, we report on scanning electrochemical microscopy with Li+ sensitive probes for its in situ, localized tracking during SEI formation and intercalation. We followed the potential-dependent reactivity of edge plane graphite influenced by the interfacial consumption of Li+ by competing processes. Cycling in the SEI formation region revealed reversible ionic processes ascribed to surface redox, as well as irreversible SEI formation. Cycling at more negative potentials activated reversible (de)intercalation. Modeling the ion-sensitive probe response yielded Li+ intercalation rate constants between 10-4 to 10-5 cm s-1. Our studies allow decoupling of charge-transfer steps at complex battery interfaces and create opportunities for interrogating reactivity at individual sites.

"Dark Deposition" of Ag Nanoparticles on TiO2: Improvement of Electron Storage Capacity To Boost "Memory Catalysis" Activity.

"Memory catalysis" (MC) studies have received appreciable attention recently because of the unique talent to retain the catalytic performance in the dark condition. However, the MC activity is still low owing to the relatively limited electron storage capacity of the present materials. Here, a TiO2@Ag composite was synthesized by a "dark-deposition (DD)" method, which is based on the electron trap effect of TiO2. Unlike traditional photodeposition (PD), an exploration of the morphology and chemical compositions of as-prepared samples shows that DD can inhibit the growth of Ag nanoparticles and the formation of Ag2O, which greatly improve the electron storage capacity. We further demonstrated that the maximum electronic capacity was in the order of TiO2@Ag-DD (1 µmol/mg) > TiO2@Ag-PD (0.35 µmol/mg) > TiO2 (0.11 µmol/mg). Moreover, the enhanced MC activity was confirmed by various degradation experiments. Especially, the use of TiO2@Ag-DD as a round-the-clock catalyst for the degradation of multicomponent pollutants has also been achieved. This strategy opens a door for enhancing the MC activity and reveals that the coupling of photocatalysis and MC may provide a new opportunity for the continuous removal of pollutants in day and night. It also may be extended to other fields, such as energy storage and continuous disinfection.

MoS2 Quantum Dot Growth Induced by S Vacancies in a ZnIn2S4 Monolayer: Atomic-Level Heterostructure for Photocatalytic Hydrogen Production.

It is highly demanded to steer the charge flow in photocatalysts for efficient photocatalytic hydrogen reactions (PHRs). In this study, we developed a smart strategy to position MoS2 quantum dots (QDs) at the S vacancies on a Zn facet in monolayered ZnIn2S4 (Vs-M-ZnIn2S4) to craft a two-dimensional (2D) atomic-level heterostructure (MoS2QDs@Vs-M-ZnIn2S4). The electronic structure calculations indicated that the positive charge density of the Zn atom around the sulfur vacancy (Vs) was more intensive than other Zn atoms. The Vs confined in monolayered ZnIn2S4 established an important link between the electronic manipulation and activities of ZnIn2S4. The Vs acted as electron traps, prevented vertical transmission of electrons, and enriched electrons onto the Zn facet. The Vs-induced atomic-level heterostructure sewed up vacancy structures of Vs-M-ZnIn2S4, resulting in a highly efficient interface with low edge contact resistance. Photogenerated electrons could quickly migrate to MoS2QDs through the intimate Zn-S bond interfaces. As a result, MoS2QDs@Vs-M-ZnIn2S4 showed a high PHR activity of 6.884 mmol g-1 h-1, which was 11 times higher than 0.623 mmol g-1 h-1 for bulk ZnIn2S4, and the apparent quantum efficiency reached as high as 63.87% (420 nm). This work provides a prototype material for looking into the role of vacancies between electronic structures and activities in 2D photocatalytic materials and gives insights into PHR systems at the atomic level.

Organic matters removal from landfill leachate by immobilized Phanerochaete chrysosporium loaded with graphitic carbon nitride under visible light irradiation.

This study investigated the technical applicability of a combination of Phanerochaete chrysosporium (P. chrysosporium) with photocatalyst graphitic carbon nitride (g-C3N4) for organic matters removal from landfill leachate under visible light irradiation. Photocatalyst g-C3N4 was well immobilized on the hyphae surface of P. chrysosporium by calcium alginate. The typical absorption edge in visible light region for g-C3N4 was at about 460 nm, and the optical absorption bandgap of g-C3N4 was estimated to be 2.70 eV, demonstrating the great photoresponsive ability of g-C3N4. An optimized g-C3N4 content of 0.10 g in immobilized P. chrysosporium and an optimized immobilized P. chrysosporium dosage of 1.0 g were suitable for organic matters removal. The removal efficiency of total organic carbon (TOC) reached 74.99% in 72 h with the initial TOC concentration of 100 mg L-1. In addition, the gas chromatography coupled with mass spectrometry (GC-MS) measurements showed that immobilized P. chrysosporium presented an outstanding removal performance for almost all organic compounds in landfill leachate, especially for the volatile fatty acids and long-chain hydrocarbons. The overall results indicate that the combination P. chrysosporium with photocatalyst g-C3N4 for organic matters removal from landfill leachate may provide a more comprehensive potential for the landfill leachate treatment.

Self-Optimization of the Active Site of Molybdenum Disulfide by an Irreversible Phase Transition during Photocatalytic Hydrogen Evolution.

The metallic 1T-MoS2 has attracted considerable attention as an effective catalyst for hydrogen evolution reactions (HERs). However, the fundamental mechanism about the catalytic activity of 1T-MoS2 and the associated phase evolution remain elusive and controversial. Herein, we prepared the most stable 1T-MoS2 by hydrothermal exfoliation of MoS2 nanosheets vertically rooted into rigid one-dimensional TiO2 nanofibers. The 1T-MoS2 can keep highly stable over one year, presenting an ideal model system for investigating the HER catalytic activities as a function of the phase evolution. Both experimental studies and theoretical calculations suggest that 1T phase can be irreversibly transformed into a more active 1T' phase as true active sites in photocatalytic HERs, resulting in a "catalytic site self-optimization". Hydrogen atom adsorption is the major driving force for this phase transition.

A bamboo-inspired hierarchical nanoarchitecture of Ag/CuO/TiO(2) nanotube array for highly photocatalytic degradation of 2,4-dinitrophenol.

The optimized geometrical configuration of muitiple active materials into hierarchical nanoarchitecture is essential for the creation of photocatalytic degradation system that can mimic natural photosynthesis. A bamboo-like architecture, CuO nanosheets and Ag nanoparticles co-decorated TiO2 nanotube arrays (Ag/CuO/TiO2), was fabricated by using simple solution-immersion and electrodeposition process. Under simulated solar light irradiation, the 2,4-dinitrophenol (2,4-DNP) photocatalytic degradation rate over Ag/CuO/TiO2 was about 2.0, 1.5 and 1.2 times that over TiO2 nanotubes, CuO/TiO2 and Ag/TiO2, respectively. The enhanced photocatalytic activity of ternary Ag/CuO/TiO2 photocatalyst was ascribed to improved light absorption, reduced carrier recombination and more exposed active sites. Moreover, the excellent stability and reliability of the Ag/CuO/TiO2 photocatalyst demonstrated a promising application for organic pollutant removal from water.