Recent Advances in Catalyst Design and Performance Optimization of Nanostructured Cathode Materials in Zinc-Air Batteries.

This review focuses on the advanced design and optimization of nanostructured zinc-air batteries (ZABs), with the aim of boosting their energy storage and conversion capabilities. The findings show that ZABs favor porous nanostructures owing to their large surface area, and this enhances the battery capacity, catalytic activity, and life cycle. In addition, the nanomaterials improve the electrical conductivity, ion transport, and overall battery stability, which crucially reduces dendrite growth on the zinc anodes and improves cycle life and energy efficiency. To obtain a superior performance, the importance of controlling the operational conditions and using custom nanostructural designs, optimal electrode materials, and carefully adjusted electrolytes is highlighted. In conclusion, porous nanostructures and nanoscale materials significantly boost the energy density, longevity, and efficiency of Zn-air batteries. It is suggested that future research should focus on the fundamental design principles of these materials to further enhance the battery performance and drive sustainable energy solutions.

Easily constructed porous silver films for efficient catalytic CO2 reduction and Zn-CO2 batteries.

For the electroreduction of carbon dioxide into high value-added chemicals, highly active and selective catalysts are crucial, and metallic silver is one of the most intriguing candidate materials available at a reasonable cost. Herein, through a novel two-step operation of Ag paste/SBA-15 coating and HF etching, porous silver films on a commercial carbon paper with a waterproofer (p-Ag/CP) could be easily fabricated on a large scale as highly efficient carbon dioxide reduction reaction (CO2RR) electrocatalysts with a CO Faraday efficiency (FECO) as high as 96.7% at -1.0 V vs. the reversible hydrogen electrode (RHE), and it still reaches up to 90% FECO over applied potentials ranging from -0.8 to -1.1 V vs. the RHE. Meanwhile, the membrane electrode assembly (MEA) utilizing the p-Ag/CP catalyst has achieved a current density, FECO, and stability of ∼60 mA cm-2, >91%, and 11 h, respectively. Furthermore, the assembled aqueous Zn-CO2 battery using p-Ag/CP cathode yielded a peak power density of 0.34 mW cm-2, 75 charge-discharge cycles for 25 h, and 64% FECO at 2.5 mA cm-2. Compared with flat Ag/CP, the significant enhancement in the CO2RR activity of p-Ag/CP was mainly attributed to the distinctive porous structure and an improved three-phase boundary, which is capable of inducing the stabilization of *COOH intermediates, increased active specific surface areas, fast electron transfer kinetic and mass transportation. Further, theoretical calculations revealed that p-Ag/CP possessed an optimized energy barrier for *COOH intermediates.

Target volumes comparison between postoperative simulation magnetic resonance imaging and preoperative diagnostic magnetic resonance imaging for prone breast radiotherapy after breast-conserving surgery.

BACKGROUND: This study investigated the differences in target volumes between preoperative magnetic resonance imaging (MRIpre) and postoperative MRI (MRIpost) for breast radiotherapy after breast-conserving surgery (BCS) using deformable image registration (DIR). METHODS AND MATERIALS: Seventeen eligible patients who underwent whole-breast irradiation in the prone position after BCS were enrolled. On MRIpre, the gross tumor volume (GTV) was delineated as GTVpre, which was then expanded by 10 mm to represent the preoperative lumpectomy cavity (LC), denoted as LCpre. The LC was expanded to the clinical target volume (CTV) and planning target volume (PTV) on the MRIpre and MRIpost, denoted as CTVpre, CTVpost, PTVpre, and PTVpost, respectively. The MIM software system was used to register the MRIpre and MRIpost using DIR. Differences were evaluated regarding target volume, distance between the centers of mass (dCOM), conformity index (CI), and degree of inclusion (DI). The relationship between CILC /CIPTV and the clinical factors was also assessed. RESULTS: Significant differences were observed in LC and PTV volumes between MRIpre and MRIpost (p < 0.0001). LCpre was 0.85 cm3 larger than LCpost, while PTVpre was 29.38 cm3 smaller than PTVpost. The dCOM between LCpre and LCpost was 1.371 cm, while that between PTVpre and PTVpost reduced to 1.348 cm. There were statistically significant increases in CI and DI for LCpost-LCpre and PTVpost-PTVpre (CI = 0.221, 0.470; DI = 0.472, 0.635). No obvious linear correlations (p > 0.05) were found between CI and GTV, primary tumor volume-to-breast volume ratio, distance from the primary tumor to the nipple and chest wall, and body mass index. CONCLUSIONS: Despite using DIR technology, the spatial correspondence of target volumes between MRIpre and MRIpost was suboptimal. Therefore, relying solely on preoperative diagnostic MRI with DIR for postoperative LC delineation is not recommended.

Pd1Cu Single-Atom Alloys for High-Current-Density and Durable NO-to-NH3 Electroreduction.

Electrochemical reduction of NO to NH3 (NORR) offers a prospective method for efficient NH3 electrosynthesis. Herein, we first design single-atom Pd-alloyed Cu (Pd1Cu) as an efficient and robust NORR catalyst at industrial-level current densities (>0.2 A cm-2). Operando spectroscopic characterizations and theoretical computations unveil that Pd1 strongly electronically couples its adjacent two Cu atoms (Pd1Cu2) to enhance the NO activation while promoting the NO-to-NH3 protonation energetics and suppressing the competitive hydrogen evolution. Consequently, the flow cell assembled with Pd1Cu exhibits an unprecedented NH3 yield rate of 1341.3 µmol h-1 cm-2 and NH3-Faradaic efficiency of 85.5% at an industrial-level current density of 210.3 mA cm-2, together with an excellent long-term durability for 200 h of electrolysis, representing one of the highest NORR performances on record.

Efficient and Stable pH-Universal Water Electrolysis Catalyzed by N-Doped Hollow Carbon Confined RuIrOx Nanocrystals.

A facile strategy is developed to fabricate 3 nm RuIrOx nanocrystals anchored onto N-doped hollow carbon for highly efficient and pH-universal overall water splitting and alkaline seawater electrolysis. The designed catalyst exhibits much lower overpotential and superior stability than most previously reported Ru- and Ir-based electrocatalysts for hydrogen/oxygen evolution reactions. It also manifests excellent overall water splitting activities and maintains ≈100% Faradic efficiency with a cell voltage of 1.53, 1.51, and 1.54 V at 10 mA cm-2 for 140, 255, and 200 h in acid, alkaline, and alkaline seawater electrolytes, respectively. The excellent electrocatalytic performance can be attributed to solid bonding between RuIrOx and the hollow carbon skeleton, and effective electronic coupling between Ru and Ir, thus inducing its remarkable electrocatalytic activities and long-lasting stability.

Nb2AlC MAX Nanosheets Supported Ru Nanocrystals as Efficient Catalysts for Boosting pH-Universal Hydrogen Production.

MAX phase combines both ceramic and metallic properties, which exhibits widespread application prospects. 2D MAX nanosheets have more abundant surface-active sites, being anticipated to improve the performance of surface-related applications. Herein, for the first time, 2D Nb2AlC nanosheets (NSs) as novel supports anchored with Ru catalysts for overall water splitting are developed. The optimized catalyst of Ru@Nb2AlC NSs exhibit Pt-comparable kinetics and superior catalytic activity toward hydrogen evolution reaction (HER) (low overpotentials of 61 and 169 mV at 10 and 100 mA cm-2, respectively) with excellent durability (5000 cycles or 80 h) in alkaline media. In particular, Ru@Nb2AlC NSs achieve a mass activity of ≈4.8 times larger than the commercial Pt/C (20 wt.%) catalyst. The post-oxidation resultant catalyst of RuO2@Nb2AlC NSs also exhibit boosting HER and oxygen evolution reaction activities and ≈100% Faraday efficiency for overall water splitting with a cell voltage of 1.61 V to achieve 10 mA cm-2. Therefore, the novel category of 2D MAX supports anchored with Ru nanocrystals offers a novel strategy for designing a wide range of MAX-supported metal catalysts for the renewable energy field.

Electrocatalytic nitrate-to-ammonia conversion on CoO/CuO nanoarrays using Zn-nitrate batteries.

Zn-NO3- batteries can generate electricity while producing NH3 in an environmentally friendly manner, making them a very promising device. However, the conversion of NO3- to NH3 involves a proton-assisted 8-electron (8e-) transfer process with a high kinetic barrier, requiring high-performance catalysts to realize the potential applications of this technology. Herein, we propose a heterostructured CoO/CuO nanoarray electrocatalyst prepared on a copper foam (CoO/CuO-NA/CF) that can electrocatalytically and efficiently convert NO3- to NH3 at low potential and achieves a maximum NH3 yield of 296.9 µmol h-1 cm-2 and the Faraday efficiency (FE) of 92.9% at the -0.2 V vs. reversible hydrogen electrode (RHE). Impressively, Zn-NO3- battery based on the monolithic CoO/CuO-NA/CF electrode delivers a high NH3 yield of 60.3 µmol h-1 cm-2, FENH3 of 82.0%, and a power density of 4.3 mW cm-2. This study provides a paradigm for heterostructured catalyst preparation for the energy-efficient production of NH3 and simultaneously generating electrical energy.

MOF-on-MOF-Derived Ultrafine Fe2P-Co2P Heterostructures for High-Efficiency and Durable Anion Exchange Membrane Water Electrolyzers.

The alkaline hydrogen evolution reaction (HER) in an anion exchange membrane water electrolyzer (AEMWE) is considered to be a promising approach for large-scale industrial hydrogen production. Nevertheless, it is severely hampered by the inability to operate tolerable HER catalysts consistently under low overpotentials at ampere-level current densities. Here, we develop a universal ligand-exchange (MOF-on-MOF) modulation strategy to synthesize ultrafine Fe2P and Co2P nanoparticles, which are well anchored on N and P dual-doped carbon porous nanosheets (Fe2P-Co2P/NPC). In addition, benefiting from the downshift of the d-band center and the interfacial Co-P-Fe bridging, the electron-rich P site is triggered, which induces the redistribution of electron density and the swapping of active centers, lowering the energy barrier of the HER. As a result, the Fe2P-Co2P/NPC catalyst only requires a low overpotential of 175 mV to achieve a current density of 1000 mA cm-2. The solar-driven water electrolysis system presents a record-setting and stable solar-to-hydrogen conversion efficiency of 20.36%. Crucially, the catalyst could stably operate at 1000 mA cm-2 over 1000 h in a practical AEMWE at an estimated cost of US$0.79 per kilogram of H2, which achieves the target (US$2 per kg of H2) set by the U.S. Department of Energy (DOE).

LINC00921 reduces lung cancer radiosensitivity by destabilizing NUDT21 and driving aberrant MED23 alternative polyadenylation.

Alternative polyadenylation (APA) plays a major role in controlling transcriptome diversity and therapeutic resistance of cancers. However, long non-coding RNAs (lncRNAs) involved in pathological APA remain poorly defined. Here, we functionally characterize LINC00921, a MED13L/P300-induced oncogenic lncRNA, and show that it is required for global regulation of APA in non-small cell lung cancer (NSCLC). LINC00921 shows significant potential for reducing NSCLC radiosensitivity, and high LINC00921 levels are associated with a poor prognosis for patients with NSCLC treated with radiotherapy. LINC00921 controls NUDT21 stability by facilitating binding of NUDT21 with the E3 ligase TRIP12. LINC00921-induced destabilization of NUDT21 promotes 3' UTR shortening of MED23 mRNA via APA, which, in turn, leads to elevated MED23 protein levels in cancer cells and nuclear translocation of ß-catenin and thereby activates expression of multiple ß-catenin/T cell factor (TCF)/lymphoid enhancer-binding factor (LEF)-regulated core oncogenes (c-Myc, CCND1, and BMP4). These findings highlight the importance of functionally annotating lncRNAs controlling APA and suggest the clinical potential of therapeutics for advanced NSCLC.

Ampere-Level Nitrate Electroreduction to Ammonia over Monodispersed Bi-Doped FeS2.

Electrochemical conversion of NO3- into NH3 (NO3RR) holds an enormous prospect to simultaneously yield valuable NH3 and alleviate NO3- pollution. Herein, we report monodispersed Bi-doped FeS2 (Bi-FeS2) as a highly effective NO3RR catalyst. Atomic coordination characterizations of Bi-FeS2 disclose that the isolated Bi dopant coordinates with its adjacent Fe atom to create the unconventional p-d hybridized Bi-Fe dinuclear sites. Operando spectroscopic measurements combined with theoretical calculations disclose that Bi-Fe dinuclear sites can synergistically enhance the hydrogenation energetics of NO3--to-NH3 pathway, while suppressing the competitive hydrogen evolution, leading to a high NO3RR selectivity and activity. Consequently, the specially designed flow cell equipped with Bi-FeS2 exhibits a high NH3 yield rate of 83.7 mg h-1 cm-2 with a near-100% NO3--to-NH3 Faradaic efficiency at an ampere-level current density of 1023.2 mA cm-2, together with an excellent long-term stability for 100 h of electrolysis, ranking almost the highest performance among all reported NO3RR catalysts.

Co doping promotes the alkaline overall seawater electrolysis performance over MnPSe3 nanosheets.

Herein, two-dimensional cobalt-doped MnPSe3 nanosheets (CMPS) were constructed, which served as an outstanding bifunctional catalyst for alkaline seawater splitting, i.e., offering the current density of 10 mA cm-2 with applied overpotentials of 59 and 300 mV for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), respectively. The assembled two-electrode system of CMPS//CMPS also demonstrated excellent catalytic activity (10 mA cm-2, 1.59 V) and can remain stable for more than 100 h. Moreover, the theoretical calculations showed that CMPS features a suitable H* adsorption beneficial for the HER, as well as a lower free energy barrier favorable for the OER.

Metal Phosphorous Chalcogenide: A Promising Material for Advanced Energy Storage Systems.

The development of efficient and affordable electrode materials is crucial for clean energy storage systems, which are considered a promising strategy for addressing energy crises and environmental issues. Metal phosphorous chalcogenides (MPX3 ) are a fascinating class of two-dimensional materials with a tunable layered structure and high ion conductivity, making them particularly attractive for energy storage applications. This review article aims to comprehensively summarize the latest research progress on MPX3 materials, with a focus on their preparation methods and modulation strategies. Additionally, the diverse applications of these novel materials in alkali metal ion batteries, metal-air batteries, and all-solid-state batteries are highlighted. Finally, the challenges and opportunities of MPX3 materials are presented to inspire their better potential in energy storage applications. This review provides valuable insights into the promising future of MPX3 materials in clean energy storage systems.

Acupuncture at ST36 ameliorates experimental autoimmune encephalomyelitis via affecting the function of B cells.

Acupuncture at ST36 can alleviate a variety of autoimmune diseases, including experimental autoimmune encephalomyelitis (EAE), while the specific mechanism for the treatment of EAE is not clear. In this study, we found that acupuncture at ST36 can significantly increase the excitability of splenic sympathetic nerve, and promote the differentiation of peripheral B and CD4+T cells in the anti-inflammatory direction. After blocking the splenic sympathetic nerve with 6-OHDA, this anti-inflammatory effect of acupuncture is partially reversed. In addition, the results of western blot and qPCR showed that acupuncture at ST36 simultaneously activated the ß2-AR-cAMP signaling pathway in the splenic B and CD4+T cells, and this activation was more significant in B cells. In vitro, when CD4+T cells were cultured alone, norepinephrine (NE) had no significant effect on their differentiation. While in the presence of B cells, NE significantly promotes the anti-inflammatory differentiation of B and CD4+T cells. Therefore, the above results reveal that acupuncture can relieve EAE by stimulating the sympathetic nerves of spleen, mainly through acting on B cells to mediate anti-inflammatory effects, and indirectly affecting the function of CD4+T cells.

Bifunctional bimetallic oxide nanowires for high-efficiency electrosynthesis of 2,5-furandicarboxylic acid and ammonia.

It is an appealing avenue for electrosyntheis of high-valued chemicals at both anode and cathode by coupling 5-hydroxymethylfurfural (HMF) oxidation and nitrate reduction reactions simultaneously, while the development such bifunctional electrocatalysts is still in its infancy with dissatisfied selectivity and low yield rate. Here, we first report that Zn-doped Co3O4 nanowires array can be served as an efficient and robust dual-functional catalyst for HMF oxidation and nitrate reduction at ambient conditions. Specifically, the catalyst shows a faradaic efficiency of 91 % and a yield rate of 241.2 µmol h-1 cm-2 for 2,5-furandicarboxylic acid formation together with a high conversion of nearly 100 % at a potential of 1.40 V. It also displays good cycling stability. Besides, the catalyst is capable of catalyzing the reduction of nitrate to NH3, giving a maximal faradaic efficiency of 92 % and a peak NH3 yield rate of 4.65 mg h-1 cm-2 at a potential of -0.70 V. These results surpass those obtained using pristine Co3O4 and are comparable to those of state-of-the-art electrocatalysts. Moreover, the catalyst is further employed as the cathode catalyst to assemble a Zn-nitrate battery, giving a peak power density of 5.24 mW cm-2 and a high yield rate of 0.72 mg h-1 cm-2. Theoretical simulations further reveal that Zn-doping favors the adsorption and dissociation of nitrate and HMF species and reduces the energy barrier as well. Our work demonstrates the potential interest of Co3O4-based materials for the highly selective production of valuable feedstocks via ambient electrolysis.

Electroacupuncture at ST36 acupoint regulates stem cells during experimental autoimmune encephalomyelitis.

BACKGROUND: Electroacupuncture (EA) is given to assist in the treatment of MS, which is an effective therapeutic method. However, the therapy mechanism of EA related to stem cells in the treatment of MS is not yet known. In this study, we used a classic animal model of multiple sclerosis: experimental autoimmune encephalomyelitis (EAE) to evaluate the therapeutic effect of EA at Zusanli (ST36) acupoint in EAE and shed light on its potential roles in the effects of stem cells in vivo. METHODS: The EAE animal models were established. From the first day after immunization, EAE model mice received EA at ST36 acupoint, named the EA group. The weight and clinical score of the three groups were recorded for 28 days. The demyelination, inflammatory cell infiltration, and markers of neural stem cells (NSCs), hematopoietic stem cells (HSCs), and mesenchymal stem cells (MSCs) were compared. RESULTS: We showed that EAE mice treated with EA at ST36 acupoint, were suppressed in demyelination and inflammatory cell infiltration, and thus decreased clinical score and weight loss and mitigated the development of EAE when compared with the EAE group. Moreover, our data revealed that the proportions of NSCs, HSCs, and MSCs increased in the EA group compared with the EAE group. CONCLUSIONS: Our study suggested that EA at ST36 acupoint was an effective nonpharmacological therapeutic protocol that not only reduced the CNS demyelination and inflammatory cell infiltration in EAE disease but also increased the proportions of various stem cells. Further study is necessary to better understand how EA at the ST36 acupoint affects EAE.

Amorphous Fe-Co oxide as an active and durable bifunctional catalyst for the urea-assisted H2 evolution reaction in seawater.

In this study, we prepared amorphous iron-cobalt oxide through the dealloying of trimetallic FeCoAl, showing excellent performance in both urea oxidation and hydrogen evolution reactions (UOR and HER) in alkaline seawater. The catalyst demonstrated stable UOR and HER activity during long-term operations due to the abundant active sites and oxygen vacancies. The catalyst required applied potentials of 1.52 and -0.185 V to yield 100 mA cm-2 for the UOR and HER, respectively. Moreover, when used as both the cathode and anode, the electrolyzer required a working voltage of 1.68 V to yield 100 mA cm-2 for urea-assisted hydrogen production.

Copper Phosphide Nanowires as High-Performance Catalysts for Urea-Assisted Hydrogen Evolution in Alkaline Medium.

Water electrolysis represented a promising avenue for the large-scale production of high-purity hydrogen. However, the high overpotential and sluggish reaction rates associated with the anodic oxygen evolution reaction (OER) posed significant obstacles to efficient water splitting. To tackle these challenges, the urea oxidation reaction (UOR) emerged as a more favorable thermodynamic alternative to OER, offering both the energy-efficient hydrogen evolution reaction (HER) and the potential for the treating of urea-rich wastewater. In this work, a two-step methodology comprising nanowire growth and phosphating treatment was employed to fabricate Cu3P nanowires on Cu foam (Cu3P-NW/CF) catalysts. These novel catalytic architectures exhibited notable efficiencies in facilitating both the UOR and HER in alkaline solutions. Specifically, within urea-containing electrolytes, the UOR manifested desirable operational potentials of 1.43 V and 1.65 V versus the reversible hydrogen electrode (vs. RHE) to reach the current densities of 10 and 100 mA cm-2, respectively. Concurrently, the catalyst displayed a meager overpotential of 60 mV for the HER at a current density of 10 mA cm-2. Remarkably, the two-electrode urea electrolysis system, exploiting the designed catalyst as both the cathode and anode, demonstrated an outstanding performance, attaining a low cell voltage of 1.79 V to achieve a current density of 100 mA cm-2. Importantly, this voltage is preferable to the conventional water electrolysis threshold in the absence of urea molecules. Moreover, our study shed light on the potential of innovative Cu-based materials for the scalable fabrication of electrocatalysts, energy-efficient hydrogen generation, and the treatment of urea-rich wastewater.

Dense Crystalline/Amorphous Phosphides/Oxides Interfacial Sites for Enhanced Industrial-Level Large Current Density Seawater Oxidation.

Designing high-efficiency and low-cost catalysts with high current densities for the oxygen evolution reaction (OER) is critical for commercial seawater electrolysis. Here, we present a heterophase synthetic strategy for constructing an electrocatalyst with dense heterogeneous interfacial sites among crystalline Ni2P, Fe2P, CeO2, and amorphous NiFeCe oxides on nickel foam (NF). The synergistic effect of high-density crystalline and amorphous heterogeneous interfaces effectively promotes the redistribution of the charge density and optimizes the adsorbed oxygen intermediates, lowering the energy barrier and promoting the O2 desorption, thus enhancing the OER performance. The obtained NiFeO-CeO2/NF catalyst exhibited outstanding OER catalytic activity, with low overpotentials of 338 and 408 mV required to attain high current densities of 500 and 1000 mA cm-2, respectively, in alkaline natural seawater electrolytes. The solar-driven seawater electrolysis system presents a record-setting and stable solar-to-hydrogen conversion efficiency of 20.10%. This work provides directives for developing highly effective and stable catalysts for large-scale clean energy production.

High entropy alloy nanoparticles as efficient catalysts for alkaline overall seawater splitting and Zn-air batteries.

High entropy alloys (HEAs) are those metallic materials that consist of five or more elements. Compared with conventional alloys, they have much more catalytic active sites due to unique structural characteristics such as high entropy effect and lattice distortion, endowing them with promising applications in the region of hydrolysis catalysts. Herein, we successfully loaded high-entropy alloys onto carbon nanotubes (FeNiCoMnRu@CNT) by hydrothermal means. It exhibits excellent HER and OER properties in alkaline seawater. To accomplish two-electrode total water splitting when constructed into Zn air cells, it only needed 1.6 V, and the timing voltage curve showed a steady current density of 10 mA cm-2 during constant electrolysis for more than 30 h in alkaline seawater. The remarkably high HER and OER activity of FeNiCoMnRu@CNT HEAs NPS indicates the potentially broad application prospect of HEAs for Zn air battery.

Tunable Heterogeneous FeCo Alloy-Mo0.82N Bifunctional Electrocatalysts for Temperature-Adapted Zn-Air Batteries.

The practical applications of temperature-tolerant Zn-air batteries (ZABs) rely on highly active and stable bifunctional catalysts that accelerate cathodic oxygen reduction (ORR) and oxygen evolution (OER) reactions. Herein, we successfully integrated fascinating transition metal nitrides and FeCo alloys through a simple coordination assembly and pyrolysis process. Importantly, the alloy-to-nitride ratio in the heterogeneous catalyst can be carefully regulated through the subsequent etching process. Moreover, the composition-dependent ORR/OER performance of the FeCo-Mo0.82N catalysts was revealed. Aqueous ZABs using the optimized FeCo-Mo0.82N-60 as a cathode exhibit a high peak power density of 149.7 mW cm-2 and an impressive stability of 600 h with a low charge-discharge voltage gap decay rate of 0.025 mV h-1, which exceeds those of most of recent reports. Furthermore, the FeCo-Mo0.82N-60-based flexible ZABs display a small specific capacity degradation (3%) from 40 to -10 °C, demonstrating excellent temperature tolerance.