Steering lithium and potassium storage mechanism in covalent organic frameworks by incorporating transition metal single atoms.

Organic electrodes mainly consisting of C, O, H, and N are promising candidates for advanced batteries. However, the sluggish ionic and electronic conductivity limit the full play of their high theoretical capacities. Here, we integrate the idea of metal-support interaction in single-atom catalysts with π-d hybridization into the design of organic electrode materials for the applications of lithium (LIBs) and potassium-ion batteries (PIBs). Several types of transition metal single atoms (e.g., Co, Ni, Fe) with π-d hybridization are incorporated into the semiconducting covalent organic framework (COF) composite. Single atoms favorably modify the energy band structure and improve the electronic conductivity of COF. More importantly, the electronic interaction between single atoms and COF adjusts the binding affinity and modifies ion traffic between Li/K ions and the active organic units of COFs as evidenced by extensive in situ and ex situ characterizations and theoretical calculations. The corresponding LIB achieves a high reversible capacity of 1,023.0 mA h g-1 after 100 cycles at 100 mA g-1 and 501.1 mA h g-1 after 500 cycles at 1,000 mA g-1. The corresponding PIB delivers a high reversible capacity of 449.0 mA h g-1 at 100 mA g-1 after 150 cycles and stably cycled over 500 cycles at 1,000 mA g-1. This work provides a promising route to engineering organic electrodes.

Robust Ru-VO2 Bifunctional Catalysts for All-pH Overall Water Splitting.

Designing robust bifunctional catalysts for oxygen evolution reaction (OER) and hydrogen evolution reaction in all-pH conditions for overall water splitting (OWS) is an effective way to achieve sustainable development. Herein, a composite Ru-VO2 containing Ru-doped VO2 and Ru nanoparticles (NPs) is synthesized, and it shows a high OWS performance in full-pH range due to their synergist effect. In particular, the OER mass activities of Ru-VO2 at 1.53 V (vs RHE) in acidic, alkaline, and PBS solutions are ≈65, 36, and 235 times of commercial RuO2 in the same conditions. The "Ru-VO2 || Ru-VO2 " two-electrode electrolyzer only needs a voltage of 1.515 V (at 10 mA cm-2 ) in acidic water splitting, which can operate stably for 125 h at 10 mA cm-2 without significant voltage decay. In situ Raman spectra and in situ differential electrochemical mass spectrometry prove that the OER of Ru-VO2 in acid follows the adsorption evolution mechanism. Density functional theory calculations further reveal the synergistic effect between Ru NP and Ru-doped VO2 , which breaks the hydrogen bond network formed by *OH adsorbed on the Ru single-atom site, and thereby significantly enhances the OER activity. This work provides new insights into the design of novel bifunctional pH-universal catalysts for OWS.

Construction of Single-Atom Catalysts for N, O Synergistic Coordination and Application to Electrocatalytic O2 Reduction.

Replacing expensive platinum oxygen reduction reaction (ORR) catalysts with atomically dispersed single-atom catalysts is an effective way to improve the energy conversion efficiency of fuel cells. Herein, a series of single-atom catalysts, TM-N2O2Cx (TM=Sc-Zn) with TM-N2O2 active units, were designed, and their catalytic performance for electrocatalytic O2 reduction was investigated based on density functional theory. The results show that TM-N2O2Cx exhibits excellent catalytic activity and stability in acidic media. The eight catalysts (TM=Sc, Ti, V, Cr, Mn, Fe, Co, and Ni) are all 4e- reaction paths, among which Sc-N2O2Cx, Ti-N2O2Cx, and V-N2O2Cx follow dissociative mechanisms and the rest are consistent with associative mechanisms. In particular, Co-N2O2Cx and Ni-N2O2Cx enable a smooth reduction in O2 at small overpotentials (0.44 V and 0.49 V, respectively). Furthermore, a linear relationship between the adsorption free energies of the ORR oxygen-containing intermediates was evident, leading to the development of a volcano plot for the purpose of screening exceptional catalysts for ORR. This research will offer a novel strategy for the design and fabrication of exceptionally efficient non-precious metal catalysts on an atomic scale.

Facile Chemical Vapor Modification Strategy to Construct Surface Cyano-Rich Polymer Carbon Nitrides for Highly Efficient Photocatalytic H2 Evolution.

The surface grafting of electro-negative cyano groups on polymer carbon nitrides (PCNs) is an effective way to tail their electronic structure. Despite the significant progress in the synthesis of cyano group-enriched PCN, developing a simple and efficient method remains challenging. Here, a facile strategy was developed for fabricating surface cyano-rich PCN (PCN-DM) with a porous structure via chemical vapor modification using diaminomaleonitrile. The cyano groups of diaminomaleonitrile substituted the amino groups on PCN surface via a deamination. The hydrogen production rate of the PCN-DM was approximately 17 times higher than that of pristine PCN. This significant increase in photocatalytic performance could be assigned to the fusion of cyano groups in the surface of PCN, forming new gap states that broadened the visible-light harvesting and accelerated charge separation for photoredox reactions. This study unveils a promising approach for incorporating functional units in the design of novel photocatalysts for efficient hydrogen production.

Bipolar fluorinated covalent triazine framework cathode with high lithium storage and long cycling capability.

Organic materials with adjustable structures and wide sources are expected to become potential candidates for commercial cathodes of lithium-ion batteries (LIBs). However, most organic materials have unstable structures, poor conductivity, and are easily soluble in electrolytes, resulting in unsatisfactory lithium storage performance. Covalent-organic frameworks have attracted extensive attention due to their stable frame structures, adjustable pore structures and functionalized official groups. Herein, a fluorinated covalent triazine framework (FCTF) is synthesized by a simple ion-thermal method. Compared with the fluorine-free covalent triazine frameworks (CTFs), the introduction of fluorine improves the lithium storage performance of CTF. When used as a cathode for lithium ion batteries, FCTF can retain a reversible capacity of 125.6 mA h g-1 after 200 cycles at a current density of 100 mA g-1. Besides, it also delivers 106.3 mA h g-1 after 400 cycles at a current density of 200 mA g-1 with 0.03% decrease per cycle (from 40 to 400 cycles).

Porous organic polymers as a platform for sensing applications.

Sensing analysis is significantly important for human health and environmental safety, and has gained increasing concern. As a promising material, porous organic polymers (POPs) have drawn widespread attention due to the availability of plentiful building blocks and their tunable structures, porosity and functions. Moreover, the permanent porous nature could provide a micro-environment to interact with guest molecules, rendering POPs attractive for application in the sensing field. In this review, we give a comprehensive overview of POPs as a platform for sensing applications. POP-based sensors are mainly divided into five categories, including fluorescence turn-on sensors, fluorescence turn-off sensors, ratiometric fluorescent sensors, colorimetric sensors and chemiresistive sensors, and their various sensing applications in detecting explosives, metal ions, anions, small molecules, biological molecules, pH changes, enantiomers, latent fingerprints and thermosensation are summarized. The different structure-based POPs and their corresponding synthetic strategies as well as the related sensing mechanisms mainly including energy transfer, donor-acceptor electron transfer, absorption competition quenching and inner filter effect are also involved in the discussion. Finally, the future outlook and perspective are addressed briefly.

LncRNA RP11-248E9.5 and RP11-456D7.1 are Valuable for the Diagnosis of Childhood Pneumonia.

BACKGROUND: Pneumonia is a common infection of the lung parenchyma in children, and early and accurate diagnosis of childhood pneumonia (CP) is important for implementing appropriate preventive and treatment strategies. This study aimed to evaluate the diagnostic value of the combination of long non-coding RNA (lncRNA) RP11-248E9.5, RP11-456D7.1, c-reactive protein (CRP), neutrophil-to-lymphocyte ratio (NLR), and platelet-to-lymphocyte ratio (PLR) in CP. PATIENTS AND METHODS: A total of 50 healthy children (HC) and 100 CP patients were enrolled. The serum expression of RP11-248e9.5 and RP11-456d7.1 was detected by qRT-PCR. The white blood cell (WBC), hemoglobin (HB), platelet (PLT), neutrophil, and lymphocyte were analyzed by automated hematology analyzer. The serum levels of CRP and procalcitonin (PCT) were analyzed by automatic biochemical analyzer. The receiver operating characteristic (ROC) curves were applied to evaluate the diagnostic value in CP. RESULTS: The NLR and PLR, expression of RP11-248E9.5 and RP11-456D7.1, and serum levels of CRP and PCT were significantly higher in the CP group than those in the HC group. Both RP11-248E9.5 (AUC, 0.86; sensitivity, 84%; specificity, 78%) and RP11-456D7.1 (AUC, 0.89; sensitivity, 79%; specificity, 92%) exhibited certain diagnostic value in CP. The diagnostic values of PCT, CRP, NLR and PLR in CP were limited by low sensitivity (≤ 71%). The combination of multiple indicators improved the diagnostic value. The combination of RP11-248E9.5, RP11-456D7.1, CRP, NLR, and PLR had the best diagnostic value in CP (AUC, 0.992; Sensitivity, 0.97; Specificity, 0.99). CONCLUSION: The combination of RP11-248E9.5, RP11-456D7.1, CRP, NLR, and PLR was a potential diagnostic strategy for CP.

Few-Layered Fluorinated Triazine-Based Covalent Organic Nanosheets for High-Performance Alkali Organic Batteries.

In order to fulfill the increasing demand for renewable energy, besides the lithium-ion batteries, other alkali (Na, K)-ion batteries are extensively investigated. However, the difficulty to find universal and environmentally benign electrodes for these alkali (Na, K)-ion batteries still severely restricts their development. Promising characteristics, including molecular diversity, low cost, and operation safety, endow the organic electrodes more advantages for applications in alkali-ion batteries. However, organic electrodes usually deliver a reversible capacity smaller than that of their inorganic counterparts due to sluggish ion/electron diffusion and possible dissolution in organic electrolytes. This work introduces fluorine atoms into the covalent triazine frameworks (CTF) to obtain two-dimensional layered fluorinated CTF (FCTF) and its exfoliated few-layered product (E-FCTF) and uses them as anodes of Li, Na, and K organic batteries. Exfoliated E-FCTF electrode delivers high reversible capacities, as well as excellent cycle life for alkali organic batteries (1035 mAh g-1 at 100 mA g-1 after 300 cycles and 581 mAh g-1 at 2 A g-1 after 1000 cycles for lithium organic batteries). In view of the experimental probing and the theoretical calculation, the Li storage mechanism for the E-FCTF can be determined to be an intriguing multielectronic redox reaction originated from lithium storage on the benzene ring and triazine ring units.

High-Lithium-Affinity Chemically Exfoliated 2D Covalent Organic Frameworks.

Covalent organic frameworks (COFs) with reversible redox behaviors are potential electrode materials for lithium-ion batteries (LIBs). However, the sluggish lithium diffusion kinetics, poor electronic conductivity, low reversible capacities, and poor rate performance for most reported COF materials limit their further application. Herein, a new 2D COF (TFPB-COF) with six unsaturated benzene rings per repeating unit and ordered mesoporous pores (≈2.1 nm) is designed. A chemical stripping strategy is developed to obtain exfoliated few-layered COF nanosheets (E-TFPB-COF), whose restacking is prevented by the in situ formed MnO2 nanoparticles. Compared with the bulk TFPB-COF, the exfoliated TFPB-COF exhibits new active Li-storage sites associated with conjugated aromatic π electrons by facilitating faster ion/electron kinetics. The E-TFPB-COF/MnO2 and E-TFPB-COF electrodes exhibit large reversible capacities of 1359 and 968 mAh g-1 after 300 cycles with good high-rate capability.

Few-Layered Boronic Ester Based Covalent Organic Frameworks/Carbon Nanotube Composites for High-Performance K-Organic Batteries.

Organic electrodes for low-cost potassium ion batteries (PIBs) are attracting more interest by virtue of their molecular diversity, environmental friendliness, and operation safety. But the sluggish potassium diffusion kinetics, dissolution in organic electrolyte, poor electronic conductivity, and low reversible capacities are several drawbacks compared with inorganic counterparts. Herein, the boronic ester based covalent organic framework (COF) material is successfully prepared on the exterior surface of carbon nanotubes (CNTs) via rational design of the organic condensation reaction and used as an anode material for PIBs. The few-layered structure of COF-10@CNT can provide more exposed active sites and fast K+ kinetics. It exhibits ultrahigh potassium storage performances (large reversible capacities of 288 mAh g-1 after 500 cycles at 0.1 A g-1 and 161 mAh g-1 after 4000 cycles at 1 A g-1), which is superior to previous organic electrodes and most inorganic electrodes. Moreover, the K-storage mechanism is proposed to be π-cation interaction between K+ and conjugated π-electrons of benzene rings.