Engineering organic polymers as emerging sustainable materials for powerful electrocatalysts.

Cost-effective and high-efficiency catalysts play a central role in various sustainable electrochemical energy conversion technologies that are being developed to generate clean energy while reducing carbon emissions, such as fuel cells, metal-air batteries, water electrolyzers, and carbon dioxide conversion. In this context, a recent climax in the exploitation of advanced earth-abundant catalysts has been witnessed for diverse electrochemical reactions involved in the above mentioned sustainable pathways. In particular, polymer catalysts have garnered considerable interest and achieved substantial progress very recently, mainly owing to their pyrolysis-free synthesis, highly tunable molecular composition and microarchitecture, readily adjustable electrical conductivity, and high stability. In this review, we present a timely and comprehensive overview of the latest advances in organic polymers as emerging materials for powerful electrocatalysts. First, we present the general principles for the design of polymer catalysts in terms of catalytic activity, electrical conductivity, mass transfer, and stability. Then, the state-of-the-art engineering strategies to tailor the polymer catalysts at both molecular (i.e., heteroatom and metal atom engineering) and macromolecular (i.e., chain, topology, and composition engineering) levels are introduced. Particular attention is paid to the insightful understanding of structure-performance correlations and electrocatalytic mechanisms. The fundamentals behind these critical electrochemical reactions, including the oxygen reduction reaction, hydrogen evolution reaction, CO2 reduction reaction, oxygen evolution reaction, and hydrogen oxidation reaction, as well as breakthroughs in polymer catalysts, are outlined as well. Finally, we further discuss the current challenges and suggest new opportunities for the rational design of advanced polymer catalysts. By presenting the progress, engineering strategies, insightful understandings, challenges, and perspectives, we hope this review can provide valuable guidelines for the future development of polymer catalysts.

Recent Functionalized Strategies of Metal-Organic Frameworks for Anode Protection of Aqueous Zinc-Ion Battery.

The inherent benefits of aqueous Zn-ion batteries (ZIBs), such as environmental friendliness, affordability, and high theoretical capacity, render them promising candidates for energy storage systems. Nevertheless, the Zn anodes of ZIBs encounter severe challenges, including dendrite formation, hydrogen evolution reaction, corrosion, and surface passivation. These would result in the infeasibility of ZIBs in practical situations. To this end, artificial interfaces with functionalized materials are crafted to protect the Zn anode. They have the capability to modulate the zinc ion flux in proximity to the electrode surface and shield it from aqueous electrolytes by leveraging either size effects or charge effects. Considering metal-organic frameworks (MOFs) with tunable pore size, chemical composition, and stable framework structures, they have emerged as effective materials for building artificial interfaces, prolonging the lifespan, and improving the unitization of Zn anode. In this review, the contributions of MOFs for protecting Zn anode, which mainly involves facilitating homogeneous nucleation, manipulating selective deposition, regulating ion and charge flux, accelerating Zn desolvation, and shielding against free water and anions are comprehensively summarized. Importantly, the future research trajectories of MOFs for the protection of the Zn anode are underscored, which may propose new perspectives on the practical Zn anode and endow the MOFs with high-value applications.

Molecule and Microstructure Modulations of Cyano-Containing Electrodes for High-Performance Fully Organic Batteries.

Cyano-containing electrodes usually promise high theoretical potentials while suffering from uncontrollable self-dissolution and sluggish reaction kinetics. Herein, to remedy their limitations, an unprecedented core-shell heterostructured electrode of carbon nanotubes encapsulated in poly(1,4-dicyanoperfluorobenzene sulfide) (CNT@PFDCB) is rationally crafted via molecule and microstructure modulations. Specifically, the linkage of sulfide bridges of PFDCB prevents the active cyano groups from dissolving, resulting in a robust structure. The fluorinations modulate the electronic configurations in frontier orbitals, allowing higher electrical conductivity and elevated output voltage. Combined with the core-shell architecture to unlock the sluggish diffusion kinetics for both electrons and guest ions, the CNT@PFDCB exhibits an impressive capacity (203.5 mAh g-1), remarkable rate ability (127.6 mAh g-1 at 3.0 A g-1), and exceptional cycling stability (retaining 81.1 % capacity after 3000 cycles at 1.0 A g-1). Additionally, the Li-storage mechanisms regarding PFDCB are thoroughly revealed by in situ attenuated total reflection infrared spectroscopy, in situ Raman spectroscopy, and theoretical simulations, which involve the coordination interaction between Li ions and cyano groups and the electron delocalization along the conjugated skeleton. More importantly, a practical fully organic cell based on the CNT@PFDCB is well-validated that demonstrates a tremendous potential of cyanopolymer as the cathode to replace its inorganic counterparts.

Reconfiguring the Hydrogen Networks of Aqueous Electrolyte to Stabilize Iron Hexacyanoferrate for High-Voltage pH-Decoupled Cell.

Prussian blue analogs (PBAs) are promising insertion-type cathode materials for different types of aqueous batteries, capable of accommodating metal or non-metal ions. However, their practical application is hindered by their susceptibility to dissolution, which leads to a shortened lifespan. Herein, we have revealed that the dissolution of PBAs primarily originates from the locally elevated pH of electrolytes, which is caused by the proton co-insertion during discharge. To address this issue, the water-locking strategy has been implemented, which interrupts the generation and Grotthuss diffusion of protons by breaking the well-connected hydrogen bonding network in aqueous electrolytes. As a result, the hybrid electrolyte enables the iron hexacyanoferrate to endure over 1000 cycles at a 1 C rate and supports a high-voltage pH-decoupled cell with an average voltage of 1.95 V. These findings provide insights for mitigating the dissolution of electrode materials, thereby enhancing the viability and performance of aqueous batteries.

Hydronium Ion Batteries: A Sustainable Energy Storage Solution.

Hydronium ions have been reversibly stored for the first time in an electrode of crystalline 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA). A highly reversible discharge-charge behavior of PTCDA was observed in an aqueous acidic electrolyte of 1 m H2 SO4 . The capacity and the operation potentials are comparable to that of Na-ion storage in the same electrode.

Transformation of Rusty Stainless-Steel Meshes into Stable, Low-Cost, and Binder-Free Cathodes for High-Performance Potassium-Ion Batteries.

To recycle rusty stainless-steel meshes (RSSM) and meet the urgent requirement of developing high-performance cathodes for potassium-ion batteries (KIB), we demonstrate a new strategy to fabricate flexible binder-free KIB electrodes via transformation of the corrosion layer of RSSM into compact stack-layers of Prussian blue (PB) nanocubes (PB@SSM). When further coated with reduced graphite oxide (RGO) to enhance electric conductivity and structural stability, the low-cost, stable, and binder-free RGO@PB@SSM cathode exhibits excellent electrochemical performances for KIB, including high capacity (96.8 mAh g-1 ), high discharge voltage (3.3 V), high rate capability (1000 mA g-1 ; 42 % capacity retention), and outstanding cycle stability (305 cycles; 75.1 % capacity retention).

Crafting Core-Shell Heterostructures with Enriched Active Centers for High-Energy-Density Symmetric Lithium-Ion Batteries.

Current research strives to create sustainable and ecofriendly organic electrode materials (OEMs) due to the rising concerns about traditional inorganic electrode materials that call for substantial resource consumption in battery manufacturing. However, OEMs often exhibit unbalanced performance, with high capacity conflicting with a long lifespan. Herein, a 2D fully conjugated covalent organic framework featuring abundant C═O and C═N groups (HTPT-COF) was strategically synthesized by coupling 2,3,7,8-tetraamino-1,4,6,9-tetraketone with hexaketocyclohexane octahydrate. It stabilizes the enriched active centers by an extended π-conjugated skeleton, thereby affording a high theoretical capacity in conjunction with potential structure stability. To further unlock the barriers of fast charge, the HTPT-COF was interwoven around highly conductive carbon nanotubes, creating a robust core-sheath heterostructure (HTPT-COF@CNT). Consequently, the crafted HTPT-COF@CNT achieves large reversible capacities of 507.7 mA h g-1, high-rate performance (247.8 mA h g-1 at 20.0 A g-1), and long-term durability (1000 cycles). Aiming to streamline the process and cut the cost of battery manufacturing, all-organic symmetric batteries were well fabricated using HTPT-COF@CNT as both cathode and anode, demonstrating high energy/power density (up to 191.7 W h kg-1 and 3800.3 W kg-1, respectively) and long-term stability over 1000 cycles. Such HTPT-COF@CNT represents a promising sustainable electrode that effectively addresses irreconcilable contradictions encountered by OEMs, boosting the development of advanced organic batteries with high capacity and cycling stability.

Correlation of the Degree of Hydronephrosis and Computed Tomography Value of Calculi with Efficacy of Ureteroscopic Lithotripsy in Patients with Upper Urinary Tract Infectious Calculi.

OBJECTIVE: The correlation of the degree of hydronephrosis and computed tomography (CT) value of calculi with the efficacy of ureteroscopic lithotripsy (URSL) in patients with upper urinary tract infectious calculi was explored. METHODS: The clinical data of 152 patients with upper urinary tract infectious calculi and on URSL in Shanghai Baoshan District Wusong Central Hospital from November 2019 to November 2021 were collected for retrospective analysis. All patients received CT examination before surgery. According to the therapeutic effect of URSL, all patients were divided into the non-calculi group (NCG, n = 101) and residual calculi group (RCG, n = 51), which were compared in terms of the degree of hydronephrosis and CT value of calculi. Then, the correlation of the degree of hydronephrosis and CT value of calculi with the efficacy of URSL in patients was analysed. RESULTS: No significant difference in clinical data was found between the groups (p > 0.05). Patients in the NCG group had lower degree of hydronephrosis than those in the RCG group (p < 0.05), and the NCG had lower CT value of calculi (p < 0.001). Spearman rank correlation analysis showed that the degree of hydronephrosis in patients with upper urinary tract infectious calculi was negatively correlated with the efficacy of URSL (r = -0.676, p < 0.001), and the CT value of calculi in such patients was negatively correlated with the efficacy of URSL (r = -0.795, p < 0.001). CONCLUSIONS: The degree of hydronephrosis and CT value of calculi were negatively correlated with the efficacy of URSL. Both can be used to predict clinical efficacy and have clinical guiding value for the formulation of treatment plans in patients with urinary tract infectious calculi.

A dendrite-free and anticaustic Zn anode enabled by high current-induced reconstruction of the electrical double layer.

Aqueous Zn-based batteries deliver thousands of cycles at high rates but poor recyclability at low rates. Herein, we reveal that this illogical phenomenon is attributed to the reconstructed electrode/electrolyte interface at high rates, wherein the condensed electrical double layer (EDL) and the tightly absorbed Zn2+ ions on the Zn electrode surface afford compact and corrosion-resistant Zn deposits.

Decoupled aqueous batteries using pH-decoupling electrolytes.

Aqueous batteries have been considered as the most promising alternatives to the dominant lithium-based battery technologies because of their low cost, abundant resources and high safety. The output voltage of aqueous batteries is limited by the narrow stable voltage window of 1.23 V for water, which theoretically impedes further improvement of their energy density. However, the pH-decoupling electrolyte with an acidic catholyte and an alkaline anolyte has been verified to broaden the operating voltage window of the aqueous electrolyte to over 3 V, which goes beyond the voltage limitations of the aqueous batteries, making high-energy aqueous batteries possible. In this Review, we summarize the latest decoupled aqueous batteries based on pH-decoupling electrolytes from the perspective of ion-selective membranes, competitive redox couples and potential battery prototypes. The inherent defects and problems of these decoupled aqueous batteries are systematically analysed, and the critical scientific issues of this battery technology for future applications are discussed.

High-Energy and Long-Lived Zn-MnO2 Battery Enabled by a Hydrophobic-Ion-Conducting Membrane.

Alkaline Zn-MnO2 batteries feature high security, low cost, and environmental friendliness while suffering from severe electrochemical irreversibility for both the Zn anode and MnO2 cathode. Although neutral electrolytes are supposed to improve the reversibility of the Zn anode, the MnO2 cathode indeed experiences a capacity degradation caused by the Jahn-Teller effect of the Mn3+ ion, thus shortening the lifespan of the neutral Zn-MnO2 batteries. Theoretically, the MnO2 cathode undergoes a highly reversible two-electron redox reaction of the MnO2/Mn2+ couple in strongly acidic electrolytes. However, acidic electrolytes would inevitably accelerate the corrosion of the Zn anode, making long-lived acidic Zn-MnO2 batteries impossible. Herein, to overcome the challenges faced by Zn-MnO2 batteries, we propose a hybrid Zn-MnO2 battery (HZMB) by coupling the neutral Zn anode with the acidic MnO2 cathode, wherein the neutral anode and acidic cathode are separated by a proton-shuttle-shielding and hydrophobic-ion-conducting membrane. Benefiting from the optimized reaction conditions for both the MnO2 cathode and Zn anode as well as the well-designed membrane, the HZMB exhibits a high working voltage of 2.05 V and a long lifespan of 2275 h (2000 cycles), breaking through the limitations of Zn-MnO2 batteries in terms of voltage and cycle life.

Flexible 1D Batteries: Recent Progress and Prospects.

With the rapid development of wearable and portable electronics, flexible and stretchable energy storage devices to power them are rapidly emerging. Among numerous flexible energy storage technologies, flexible batteries are considered as the most favorable candidate due to their high energy density and long cycle life. In particular, flexible 1D batteries with the unique advantages of miniaturization, adaptability, and weavability are expected to be a part of such applications. The development of 1D batteries, including lithium-ion batteries, zinc-ion batteries, zinc-air batteries, and lithium-air batteries, is comprehensively summarized, with particular emphasis on electrode preparation, battery design, and battery properties. In addition, the remaining challenges to the commercialization of current 1D batteries and prospective opportunities in the field are discussed.

A Water-/Fireproof Flexible Lithium-Oxygen Battery Achieved by Synergy of Novel Architecture and Multifunctional Separator.

To meet the increasing demands for portable and flexible devices in a rapidly developing society, it is urgently required to develop highly safe and flexible electrochemical energy-storage systems. Flexible lithium-oxygen batteries with high theoretical specific energy density are promising candidates; however, the conventional half-open structure design prevents it from working properly under water or fire conditions. Herein, as a proof-of-concept experiment, a highly safe flexible lithium-oxygen battery achieved by the synergy of a vital multifunctional structure design and a unique composite separator is proposed and fabricated. The structure can effectively prevent the invasion of water from the environment and combustion, which is further significantly consolidated with the help of a polyimide and poly(vinylidene fluoride-co-hexafluoropropylene) composite separator, which holds good water resistance, thermal stability, and ionic conductivity. Unexpectedly, the obtained lithium-oxygen battery exhibits superior flexibility, water resistance, thermal resistance, and cycling stability (up to 218 cycles; at a high current of 1 mA and capacity of 4 mA h). This novel water/fireproof, flexible lithium-oxygen battery is a promising candidate to power underwater flexible electronics.

Surfactant-Free Aqueous Synthesis of Pure Single-Crystalline SnSe Nanosheet Clusters as Anode for High Energy- and Power-Density Sodium-Ion Batteries.

SnSe with 3D hierarchical nanostructure composed of interconnected single-crystal SnSe nanosheets is synthesized via a fast and effective strategy. Unexpectedly, when used as the anode material for Na-ion batteries (NIBs), the SnSe exhibits a high capacity (738 mA h g-1 ), superior rate capability (40 A g-1 ), and high energy density in a full cell. These results provide the possibility of SnSe use as NIBs anodes.

Decorating Waste Cloth via Industrial Wastewater for Tube-Type Flexible and Wearable Sodium-Ion Batteries.

To turn waste into treasure, a facile and cost-effective strategy is developed to revive electroless nickel plating wastewater and cotton-textile waste toward a novel electrode substrate. Based on the substrate, a binder-free PB@GO@NTC electrode is obtained, which exhibits superior electrochemical performance. Moreover, for the first time, a novel tube-type flexible and wearable sodium-ion battery is successfully fabricated.

Complete mitochondrial genome of the giant croaker Nibea japonica (Perciformes, Sciaenidae) and phylogenetic analysis of the Sciaenidae.

The giant croaker Nibea japonica (Perciformes, Sciaenidae) is an important economic fish distributing in the East China Sea, South China Sea, and Japan southern coast. In this study, the complete mitochondrial genome of N. japonica was firstly determined. It is 16 496 bp-length and consists of 22 tRNA genes, 13 protein-coding genes, two rRNA genes, and a control region. Except for eight tRNA and ND6 genes, all other mitochondrial genes are encoded on the heavy strand. Phylogenetic analysis revealed that N. japonica, A. amoyensis, and other seven fish first clustered into the Argyrosominae clade. It is consistent with the taxonomic status. Then, the Argyrosominae, Pseudosciaeninae, and Sciaeniae formed the sister group, while the Johniinae became a separate clade, which is inconsistent with the previous phenotypic report. It is suggested that the researches of single gene and taxionomic might lose some significant evolutionary characters. This study will contribute to phyogenetic analysis of the Sciaenidae and the natural resources conservation.

Integrating 3D Flower-Like Hierarchical Cu2NiSnS4 with Reduced Graphene Oxide as Advanced Anode Materials for Na-Ion Batteries.

Development of an anode material with high performance and low cost is crucial for implementation of next-generation Na-ion batteries (NIBs) electrode, which is proposed to meet the challenges of large scale renewable energy storage. Metal chalcogenides are considered as promising anode materials for NIBs due to their high theoretical capacity, low cost, and abundant sources. Unfortunately, their practical application in NIBs is still hindered because of low conductivity and morphological collapse caused by their volume expansion and shrinkage during Na(+) intercalation/deintercalation. To solve the daunting challenges, herein, we fabricated novel three-dimensional (3D) Cu2NiSnS4 nanoflowers (CNTSNs) as a proof-of-concept experiment using a facile and low-cost method. Furthermore, homogeneous integration with reduced graphene oxide nanosheets (RGNs) endows intrinsically insulated CNTSNs with superior electrochemical performances, including high specific capacity (up to 837 mAh g(-1)), good rate capability, and long cycling stability, which could be attributed to the unique 3D hierarchical structure providing fast ion diffusion pathway and high contact area at the electrode/electrolyte interface.

Prognostic Risk Factors Associated with Recurrence and Metastasis After Radical Resection in Patients with Hepatolithiasis Complicated by Intrahepatic Cholangiocarcinoma.

The objective of this study was to analyze the predictive significance of different prognostic factors associated with recurrence and metastasis after the radical resection in patients with hepatolithiasis complicated by intrahepatic cholangiocarcinoma (HLA/IHCC). A total of 138 patients with HLA/IHCC admitted during April 2006-April 2009 were selected for this study and they were divided into two groups, with and without recurrence/metastasis. After a radical resection surgery, the patients were followed up for 5 years to monitor the recurrence and/or metastasis. The general and clinical data of the two groups were analyzed to evaluate the relevant risk factors. The study showed that recurrence/metastasis occurred in 48 patients with a rate of 34.8 %. Recurrence in liver accounted for 85.4 % (41 cases), whereas in lung and bone metastases occurred at rates of 8.3 % (4 cases) and 6.3 % (3 cases), respectively. Univariate analysis revealed that CA19-9, tumor diameter, tumor amount, lymphatic metastasis, and AJCC stage of the recurrence/metastasis group were significantly different from those of the non-recurrence/metastasis patients (p < 0.05). The multivariate analysis showed that CA19-9 > 200 U/mL, tumor diameter >5 cm, presence of multiple tumors, lymphatic metastasis, and III-IV AJCC stages were independent risk factors of tumor recurrence and metastasis after the radical surgery (p < 0.05). During the 5 years of follow-up, 65 patients (47.1 %) died, including 31 in the recurrence/metastasis and 34 in the non-recurrence/metastasis groups, accounting for 64.5 % (31/48) and 37.8 % (34/90) of mortality in the two groups, respectively. Thus, the 5-year mortality in the recurrence/metastasis group was significantly higher than that in the non-recurrence/metastasis group (p < 0.05). The CA19-9 antigen, tumor diameter, tumor amount, lymphatic metastasis, and AJCC stage were significantly associated with increased risk of post-resection recurrence and metastasis of HLA/IHCC. The massive lymphadenectomy during the surgery and perioperative control of inflammation decreased the risk of recurrence/metastasis and further improved the disease prognosis.

Correlation of the Degree of Hydronephrosis and Computed Tomography Value of Calculi with Efficacy of Ureteroscopic Lithotripsy in Patients with Upper Urinary Tract Infectious Calculi

Objective: The correlation of the degree of hydronephrosis and computed tomography (CT) value of calculi with the efficacy of ureteroscopic lithotripsy (URSL) in patients with upper urinary tract infectious calculi was explored. Methods: The clinical data of 152 patients with upper urinary tract infectious calculi and on URSL in Shanghai Baoshan District Wusong Central Hospital from November 2019 to November 2021 were collected for retrospective analysis. All patients received CT examination before surgery. According to the therapeutic effect of URSL, all patients were divided into the non-calculi group (NCG, n = 101) and residual calculi group (RCG, n = 51), which were compared in terms of the degree of hydronephrosis and CT value of calculi. Then, the correlation of the degree of hydronephrosis and CT value of calculi with the efficacy of URSL in patients was analysed. Results: No significant difference in clinical data was found between the groups (p > 0.05). Patients in the NCG group had lower degree of hydronephrosis than those in the RCG group (p < 0.05), and the NCG had lower CT value of calculi (p < 0.001). Spearman rank correlation analysis showed that the degree of hydronephrosis in patients with upper urinary tract infectious calculi was negatively correlated with the efficacy of URSL (r = −0.676, p < 0.001), and the CT value of calculi in such patients was negatively correlated with the efficacy of URSL (r = −0.795, p < 0.001). Conclusions: The degree of hydronephrosis and CT value of calculi were negatively correlated with the efficacy of URSL. Both can be used to predict clinical efficacy and have clinical guiding value for the formulation of treatment plans in patients with urinary tract infectious calculi (AU)

[Residual level and ecological risk assessment of OCPs and PCBs in sediments of mudflat shellfish culturing areas in Ningbo, Zhejiang Province of East China].

GC-ECD methods were adopted to determine the residual level of OCPs (including HCHs and DDTs) and PCBs in the surface sediments collected from mudflat shellfish culturing areas in Ningbo, with the sources of the OCPs and PCBs analyzed and the ecological risks of the residual OCPs and PCBs evaluated. The residual level of OCPs was 0.80-32.40 ng X g(-1), and that of PCBs was 3.20-33.33 ng X g(-1). The HCHs mainly came from long distance atmospheric transportation and historical residues, while the DDTs had new input at some sites, possibly coming from the application of dicofol. At most sites, there existed potential ecological risks of p, p'-DDT and DDTs, with strong indications in Qiangtou and Xidian where the residual level of p, p'-DDT was higher than the effect rang median (ERM), suggesting an ecological menace to the benthos. The residual PCBs at most sites were in low level ecological risk.