Ultrathin cobalt-based nanosheets containing surface oxygen promoted near-complete nitrate removal.

Electrocatalytic nitrate removal offers a sustainable approach to alleviate nitrate pollution and to boost the anthropogenic nitrogen cycle, but it still suffers from limited removal efficiency at high rates, especially at low levels of nitrate. Herein, we report the near-complete removal of low-level nitrate (10-200 ppm) within 2 h using ultrathin cobalt-based nanosheets (CoNS) containing surface oxygen, which was fabricated from in-situ electrochemical reconstruction of conventional nanosheets. The average nitrate removal of 99.7 % with ammonia selectivity of 98.2 % in 9 cyclic runs ranked in the best of reported catalysts. Powered by a solar cell under the winter sun, the full-cell nitrate electrolysis system, equipped with ultrathin CoNS, achieved 100 % nitrogen gas selectivity and 99.6 % total nitrogen removal. The in-situ Fourier Transform Infrared included experiments and theoretical computations revealed that in-situ electrochemical reconstruction not only increased electrochemical active surface area but also constructed surface oxygen in active sites, leading to enhanced stabilization of nitrate adsorption in a symmetry breaking configuration and charge transfer, contributing to near-complete nitrate removal on ultrathin CoNS. This work provides a strategy to design ultrathin nanocatalysts for nitrate removal.

Activating nickel foam with trace titanium oxide for enhanced water oxidation.

Nickel-based electrocatalysts for water oxidation suffer from low activity and poor stability. In this work, 0.015 mg cm-2 TiO2 nanosheets anchored on Ni foam addressed these problems after electrochemical activation. In situ investigations, including Raman spectra, corroborated the enhanced generation of highly active Ni(III)-O-O species on Ni foam in the presence of trace TiO2.

Solar utilization beyond photosynthesis.

Natural photosynthesis is an efficient biochemical process which converts solar energy into energy-rich carbohydrates. By understanding the key photoelectrochemical processes and mechanisms that underpin natural photosynthesis, advanced solar utilization technologies have been developed that may be used to provide sustainable energy to help address climate change. The processes of light harvesting, catalysis and energy storage in natural photosynthesis have inspired photovoltaics, photoelectrocatalysis and photo-rechargeable battery technologies. In this Review, we describe how advanced solar utilization technologies have drawn inspiration from natural photosynthesis, to find sustainable solutions to the challenges faced by modern society. We summarize the uses of advanced solar utilization technologies, such as converting solar energy to electrical and chemical energy, electrochemical storage and conversion, and associated thermal tandem technologies. Both the foundational mechanisms and typical materials and devices are reported. Finally, potential future solar utilization technologies are presented that may mimic, and even outperform, natural photosynthesis.

An electrochemical gram-scale protocol for pyridylation of inert N-heterocycles with cyanopyridines.

Here, we present a protocol to decyanopyridate inert N-heterocycles access to N-fused heterocycles via the mechanism of dual proton-coupled electron transfer (PCET). We describe a detailed guide to performing an electrochemical gram-scale protocol for decyanopyridation of inert N-heterocycles. The desired pyridylated quinolone is synthesized in a 5.0 mmol scale with a yield of 76%. The protocol is limited to cyanopyridines. For complete details on the use and execution of this protocol, please refer to Niu et al. (2022).

Electrochemical ammonium-cation-assisted pyridylation of inert N-heterocycles via dual-proton-coupled electron transfer.

A straightforward and practical strategy for pyridylation of inert N-heterocycles, enabled by ammonium cation and electrochemical, has been described. This protocol gives access to various N-fused heterocycles and bidentate nitrogen ligand compounds, through dual-proton-coupled electron transfer (PCET) and radical cross-coupling in the absence of exogenous metal and redox reagent. It features broad substrate scope, wide functional group tolerance, and easy gram-scale synthesis. Various experiments and density functional theory (DFT) calculation results show the mechanism of dual PCET followed by radical cross-coupling is the preferred pathway. Moreover, ammonium salt plays the dual role of protonation reagent and electrolyte in this conversion, and the resulting product 9-(pyridin-4-yl)acridine compound can be used for fluorescence recognition of Fe2+ and Pd2+ with high sensitivity.

Photoelectrochemical energy storage materials: design principles and functional devices towards direct solar to electrochemical energy storage.

Advanced solar energy utilization technologies have been booming for carbon-neutral and renewable society development. Photovoltaic cells now hold the highest potential for widespread sustainable electricity production and photo(electro)catalytic cells could supply various chemicals. However, both of them require the connection of energy storage devices or matter to compensate for intermittent sunlight, suffering from complicated structures and external energy loss. Newly developed photoelectrochemical energy storage (PES) devices can effectively convert and store solar energy in one two-electrode battery, simplifying the configuration and decreasing the external energy loss. Based on PES materials, the PES devices could realize direct solar-to-electrochemical energy storage, which is fundamentally different from photo(electro)catalytic cells (solar-to-chemical energy conversion) and photovoltaic cells (solar-to-electricity energy conversion). This review summarizes a critically selected overview of advanced PES materials, the key to direct solar to electrochemical energy storage technology, with the focus on the research progress in PES processes and design principles. Based on the specific discussions of the performance metrics, the bottlenecks of PES devices, including low efficiency and deteriorative stability, are also discussed. Finally, several perspectives of potential strategies to overcome the bottlenecks and realize practical photoelectrochemical energy storage devices are presented.

Asymmetric Oxo-Bridged ZnPb Bimetallic Electrocatalysis Boosting CO2 -to-HCOOH Reduction.

Electrochemical CO2 reduction (ECR) is one of the promising CO2 recycling technologies sustaining the natural carbon cycle and offering more sustainable higher-energy chemicals. Zn- and Pb-based catalysts have improved formate selectivity, but they suffer from relatively low current activities considering the competitive CO selectivity on Zn. Here, lead-doped zinc (Zn(Pb)) electrocatalyst is optimized to efficiently reduce CO2 to formate, while CO evolution selectivity is largely controlled. Selective formate is detected with Faradaic efficiency (FEHCOOH ) of ≈95% at an outstanding partial current density of 47 mA cm-2 in a conventional H-Cell. Zn(Pb) is further investigated in an electrolyte-fed device achieving a superior conversion rate of ≈100 mA cm-2 representing a step closer to practical electrocatalysis. The in situ analysis demonstrates that the Pb incorporation plays a crucial role in CO suppression stem from the generation of the Pb-O-C-O-Zn structure rather than the CO-boosted Pb-O-C-Zn. Density functional theory (DFT) calculations reveal that the alloying effect tunes the adsorption energetics and consequently modifies the electronic structure of the system for an optimized asymmetric oxo-bridged intermediate. The alloying effect between Zn and Pb controls CO selectivity and achieves a superior activity for a selective CO2 -to-formate reduction.

The early response expression profiles of miRNA-mRNA in farmed yellow catfish (Pelteobagrus fulvidraco) challenged with Edwardsiella tarda infection.

Edwardsiella tarda, the bacterial pathogen that causes ascites disease and red-head disease, poses a serious threat to yellow catfish (Pelteobagrus fulvidraco) aquaculture. In this study, the spleens of E. tarda-infected and non-infected yellow catfish were sequenced to obtain the microRNA (miRNA) and mRNA expression profiles. We obtained 657 differentially expressed (DE) miRNAs and 6867 DE mRNAs between two groups and annotated them using the KEGG database. In addition, the 43 negatively correlated miRNA-mRNA pairs were identified using integrated miRNA-mRNA analysis, which including immune-related miRNAs and target genes such as miR-144, miR-1260, miR-1388, miR-33, miR-338, miR-181b, miR-34c, miR-135 and CLEC4E, LITR, PIKfyve, NCF4, IL-12ß, IP6K2, TNFRSF9, IL-4Rα, IRF2, Mx2. We verified 8 DE miRNAs pairs and 10 DE mRNAs by quantitative real-time PCR. Finally, the CLEC4E and Mx2 mRNAs were selected for further verification using in situ hybridization. Together, our results provide valuable information for further analyses of the mechanisms of yellow catfish defense against E. tarda infection.

Reversible Hybrid Aqueous Li-CO2 Batteries with High Energy Density and Formic Acid Production.

Metal-CO2 batteries, an attractive technology for both energy storage and CO2 utilization, are typically classified into organic Li(Na)-CO2 batteries with a high energy density/output voltage and aqueous Zn-CO2 batteries with flexible chemical production. However, achieving both high-efficiency energy storage and flexible chemical production is still challenging. In this study, a reversible hybrid aqueous Li-CO2 battery is developed, integrating Li with an aqueous phase, which exhibits not only a high operating voltage and energy density but also highly selective formic acid production. Based on a Li plate as the anode, NaCl solution as the aqueous electrolyte, solid electrolyte Li1.5 Al0.5 Ge1.5 P3 O12 (LAGP) as a separator and Li+ transporter, and a bifunctional Pd-based electrocatalyst as the cathode, the resulting battery shows a high discharge voltage of up to 2.6 V, an outstanding energy conversion efficiency of above 80 %, and remarkable selectivity of CO2 -to-HCOOH conversion of up to 97 %. The related reaction mechanism is proposed as CO2 +2 Li+2 H+ ⇌HCOOH+2 Li+ .

Recent Development of CO2 Electrochemistry from Li-CO2 Batteries to Zn-CO2 Batteries.

Metal-CO2 batteries with CO2 as cathode active species give rise to opportunities to deal with energy and environmental issues simultaneously. This technology is more appealing when CO2 is flexibly reduced to chemicals and fuels driven by surplus electricity because it represents a low-cost and controllable approach to maximized electricity utilization and value-added CO2 utilization. Nonaqueous metal-CO2 batteries exhibited high discharge voltage and capacity with carbon and oxalate as reduction products from CO2 electrochemistry that lacks proton. In contrast, aqueous Zn-CO2 batteries implemented flexible CO2 electrochemistry for more value-added products accompanied by energy storage based on a proton-coupled electron transfer mechanism. In this Account, we have exemplified our recent results in the development of CO2 electrochemistry from nonaqueous Li-CO2 batteries to aqueous Zn-CO2 batteries toward practical value-added CO2 conversion. Aimed at the challengingly limited CO2 electrochemistry and high cost of nonaqueous Li-CO2 batteries, we proposed aqueous Zn-CO2 batteries. Our previous works on nonaqueous Li-CO2 batteries, aqueous Zn-air batteries, and aqueous CO2 reduction electrocatalysts further shed light on battery mechanism, device construction, and electrocatalyst design. For example, bipolar membranes maintain the stability of the basic anolyte and neutral catholyte, as well as the kinetics of ion transport at the same time, forming the device base for aqueous Zn-CO2 batteries. Moreover, in terms of the electrocatalyst catalyzing both discharge and charge reactions on the cathode, the design of multifunctional electrocatalysts is of great importance for not only CO2 electrochemistry but also spontaneous discharge and energy efficiency of aqueous Zn-CO2 batteries. We have explored a series of multifunctional electrocatalyst cathodes, including noble metal, transition metal, and metal-free materials, all of which facilitated CO2 electrochemistry in aqueous Zn-CO2 batteries with value-added carbon-based products. Meanwhile, several operating models for practical complicated situations are presented, such as rechargeable, reversible, dual-model, and solid-state batteries. Zn-CO2 batteries with different models require different design mechanisms for electrocatalyst cathodes. Reversible aqueous Zn-CO2 batteries with HCOOH generation were enabled by electrocatalysts capable of catalyzing the interconversion of CO2 and HCOOH at low overpotentials, rechargeable aqueous Zn-CO2 batteries were allowed by electrocatalysts capable of catalyzing efficient CO2 reduction and O2 evolution, and dual-model aqueous Zn-CO2 batteries were realized by electrocatalysts capable of catalyzing CO2 reduction, water oxidation, and oxygen reduction. Concluding remarks include a summary of recent CO2 electrochemistry in metal-CO2 batteries and a brief discussion of future challenges and opportunities for practical aqueous Zn-CO2 batteries, such as highly reduced products and high production rate.

Rechargeable Zn-CO2 Electrochemical Cells Mimicking Two-Step Photosynthesis.

Metal-CO2 batteries represent a promising priority for sustainable energy and the environment. However, CO2 utilization in nonaqueous electrolytes mostly involves difficult CO2 electrochemistry, leading to poor selectivity and limited cycle performance. Herein, an aqueous rechargeable Zn-CO2 electrochemical cell that tunably produced CO fuel gas (90% Faradaic efficiency) during cell discharge (cathodic reaction: CO2 + 2e- + 2H+ → CO + H2 O) and O2 during cell charge at ≈2 V (cathodic reaction: H2 O → 1/2O2 + 2e- + 2H+ ), mimicking the separate steps of CO2 fixation and water oxidation during photosynthesis while exhibiting the advantages of high efficiency, tunable products, and operation independent of sunlight is proposed and realized. The cell achieves a remarkable energy efficiency of 68% with fuel generation, providing an alternative for the green, efficient, and safe utilization of CO2 by metal-CO2 batteries.

Reversible Aqueous Zinc-CO2 Batteries Based on CO2 -HCOOH Interconversion.

As a promising technique for CO2 fixation/utilization and energy conversion/storage, the metal-CO2 battery has been studied to improve its interconversion between CO2 and carbonates/oxalates. Herein, we propose and realize a reversible aqueous Zn-CO2 battery based on the reversible conversion between CO2 and liquid HCOOH on a bifunctional Pd cathode. The 3D porous Pd interconnected nanosheet with enriched edge and pore structure, has a highly electrochemical active surface to facilitate simultaneous selective CO2 reduction and HCOOH oxidation at low overpotentials. The resulting battery has a 1 V charge voltage, a cycling durability over 100 cycles, and a high energy efficiency of 81.2 %. The battery mechanism is proposed as Zn+CO2 +2 H+ +2 OH- ↔ ZnO+HCOOH+H2 O, through which the reversible conversion between CO2 and liquid HCOOH was realized.

CO2 Overall Splitting by a Bifunctional Metal-Free Electrocatalyst.

Photo/electrochemical CO2 splitting is impeded by the low cost-effective catalysts for key reactions: CO2 reduction (CDRR) and water oxidation. A porous silicon and nitrogen co-doped carbon (SiNC) nanomaterial by a facile pyrolyzation was developed as a metal-free bifunctional electrocatalyst. CO2 -to-CO and oxygen evolution (OER) partial current density under neutral conditions were enhanced by two orders of magnitude in the Tafel regime on SiNC relative to single-doped comparisons beyond their specific area gap. The photovoltaic-driven CO2 splitting device with SiNC electrodes imitating photosynthesis yielded an overall solar-to-chemical efficiency of advanced 12.5 % (by multiplying energy efficiency of CO2 splitting cell and photovoltaic device) at only 650 mV overpotential. Mechanism studies suggested the elastic electron structure of -Si(O)-C-N- unit in SiNC as the highly active site for CDRR and OER simultaneously by lowering the free energy of CDRR and OER intermediates adsorption.

Direct Solar-to-Electrochemical Energy Storage in a Functionalized Covalent Organic Framework.

A covalent organic framework integrating naphthalenediimide and triphenylamine units (NT-COF) is presented. Two-dimensional porous nanosheets are packed with a high specific surface area of 1276 m2 g-1 . Photo/electrochemical measurements reveal the ultrahigh efficient intramolecular charge transfer from the TPA to the NDI and the highly reversible electrochemical reaction in NT-COF. There is a synergetic effect in NT-COF between the reversible electrochemical reaction and intramolecular charge transfer with enhanced solar energy efficiency and an accelerated electrochemical reaction. This synergetic mechanism provides the key basis for direct solar-to-electrochemical energy conversion/storage. With the NT-COF as the cathode materials, a solar Li-ion battery is realized with decreased charge voltage (by 0.5 V), increased discharge voltage (by 0.5 V), and extra 38.7 % battery efficiency.

Metal-Free Fluorine-Doped Carbon Electrocatalyst for CO2 Reduction Outcompeting Hydrogen Evolution.

The electrochemical CO2 reduction (ECDRR), as a key reaction in artificial photosynthesis to implement renewable energy conversion/storage, has been inhibited by the low efficiency and high costs of the electrocatalysts. Herein, we synthesize a fluorine-doped carbon (FC) catalyst by pyrolyzing commercial BP 2000 with a fluorine source, enabling a highly selective CO2 -to-CO conversion with a maximum Faradaic efficiency of 90 % at a low overpotential of 510 mV and a small Tafel slope of 81 mV dec-1 , outcompeting current metal-free catalysts. Moreover, the higher partial current density of CO and lower partial current density of H2 on FC relative to pristine carbon suggest an enhanced inherent activity towards ECDRR as well as a suppressed hydrogen evolution by fluorine doping. Fluorine doping activates the neighbor carbon atoms and facilitates the stabilization of the key intermediate COOH* on the fluorine-doped carbon material, which are also blocked for competing hydrogen evolution, resulting in superior CO2 -to-CO conversion.

Highly exposed Fe-N4 active sites in porous poly-iron-phthalocyanine based oxygen reduction electrocatalyst with ultrahigh performance for air cathode.

Progress in the development of efficient electrocatalysts for oxygen reduction reactions is imperative for various energy systems such as metal-air batteries and fuel cells. In this paper, an innovative porous two-dimensional (2D) poly-iron-phthalocyanine (PFe-Pc) based oxygen reduction electrocatalyst created with a simple solid-state chemical reaction without pyrolysis is reported. In this strategy, silicon dioxide nanoparticles play a pivotal role in preserving the Fe-N4 structure during the polymerization process and thereby assist in the development of a porous structure. The new polymerized phthalocyanine electrocatalyst with tuned porous structure, improved specific surface area and more exposed catalytic active sites via the 2D structure shows an excellent performance towards an oxygen reduction reaction in alkaline media. The onset potential (E = 1.033 V) and limiting current density (I = 5.58 mA cm-2) are much better than those obtained with the commercial 20% platinum/carbon electrocatalyst (1.046 V and 4.89 mA cm-2) and also show better stability and tolerance to methanol crossover. For practical applications, a zinc-air (Zn-air) battery and methanol fuel cell equipped with the PFe-Pc electrocatalyst as an air cathode reveal a high open circuit voltage and maximum power output (1.0 V and 23.6 mW cm-2 for a methanol fuel cell, and 1.6 V and 192 mW cm-2 for the liquid Zn-air battery). In addition, using the PFe-Pc electrocatalyst as an air cathode in a flexible cable-type Zn-air battery exhibits excellent performance with an open-circuit voltage of 1.409 V. This novel porous 2D PFe-Pc has been designed logically using a new, simple strategy with ultrahigh electrochemical performances in Zn-air batteries and methanol fuel cell applications.

Prevalence, Antibiotic Susceptibility and Diversity of Vibrio parahaemolyticus Isolates in Seafood from South China.

Vibrio parahaemolyticus is a leading cause of foodborne infections in China and a threat to human health worldwide. The main objective of this study is to determine the prevalence and characteristic of V. parahaemolyticus isolates in fish, oyster and shrimp samples from the South China domestic consumer market. To accomplish this, we examined 504 seafood samples from 11 provinces of China. The prevalence rates were 9.38, 30.36, and 25.60%, respectively. In summer (33.33%), the prevalence of V. parahaemolyticus was more common than that detected in the winter (14.01%). In addition, we identified 98 V. parahaemolyticus strains. The antimicrobial resistance trends of our seafood isolates to 15 antimicrobial agents revealed that major isolates were resistant to ampicillin (79.59%). Furthermore, 68.38% of the isolates were identified as being multidrug resistance. The prevalence of tdh or trh genes among the isolates was 8.16 and 12.24%, respectively. ERIC-PCR and multilocus sequence typing (MLST) results enabled classification of the isolates (n = 98) into different clusters, revealing genetic variation and relatedness among the isolates. Thus, our findings demonstrate the prevalence of V. parahaemolyticus in a variety of common seafood consumed domestically in China and provides insights into the dissemination of antibiotic-resistant strains, which should improve our microbiological risk assessment knowledge associated with V. parahaemolyticus in seafoods.

Reduced graphene oxide supported palladium nanoparticles via photoassisted citrate reduction for enhanced electrocatalytic activities.

Reduced graphene oxide (rGO) supported palladium nanoparticles (Pd NPs) with a size of ∼3 nm were synthesized using one-pot photoassisted citrate reduction. This synthetic approach allows for the formation and assembly of Pd NPs onto the rGO surface with a desired size and can be readily used for other metal NP preparation. The prepared rGO-Pd exhibited 5.2 times higher mass activity for ethanol oxidation reaction than the commercial platinum/carbon (Pt/C). In the oxygen reduction reaction tests, rGO-Pd exhibited comparable activity compared with Pt/C and maintained its high performance after 4000 cycles of potential sweep. These results demonstrate that our synthetic approach is effective for preparing graphene-supported metal NPs with excellent activity and stability in ethanol oxidation and oxygen reduction reactions.