The design and fabrication of highly active hydrogen evolution reaction (HER) electrocatalysts that can outperform Pt/C are extremely desirable but remain challenging. Herein, S-doped hollow mesoporous carbon-anchored Ru nanoclusters (Ru NCs/S-HMCs) are fabricated as a novel and highly active HER electrocatalyst through a modified Stöber process and subsequent hydrothermal treatment, in which Ru NCs (1.64 nm in size) are uniformly anchored onto S-HMCs channels. Benefiting from the unique electronic structure induced by S doping and the spatial confinement effect of the mesoporous carbon, the Ru NCs/S-HMCs catalyst exhibits excellent pH-universal HER activity, requiring overpotentials of only 3.5, 61.0, and 63.5 mV to achieve a current density of 10 mA cm-2 in alkaline, neutral, and acidic electrolytes, respectively. In 1 M KOH, 0.5 M H2SO4, and 0.5 M PBS solutions, Ru NCs/S0.5-HMCs exhibits high mass activities of 21542, 2998 and 7088 mA mgRu-1, respectively, at an overpotential of -50 mV. The excellent activity stems from (1) the pore confinement effect, which promotes the formation of ultrasmall Ru NCs (1.64 nm) and suppresses metal leaching; (2) the S doping, which modulates the electronic structure of Ru and reduces the water dissociation barrier; and (3) the hollow mesoporous architecture, which accelerates mass and electron transport. This work provides insights for designing high-efficiency pH-universal electrocatalysts.
ABSTRACT Direct synthesis of urea through photocatalytic N 2 and CO 2 reduction (PNCR) offers a sustainable approach to mitigate CO 2 emissions and reduce energy consumption from urea production for industry and agriculture. However, achieving high yield of urea is limited by the high energy barrier for co‐reduction of N 2 and CO 2 with subsequent C–N coupling. Herein, we propose that the spin polarization of chiral mesostructured Mo doped Bi 2 WO 6 (CMMB) can facilitate the formation of triplet 3 NOH by regulating the parallel electron spin alignment and promote the separation and transfer of photogenerated carriers, leading to enhanced C–N formation. The incorporation of Mo sites into Bi 2 WO 6 promotes the adsorption and activation of N 2 . A state‐of‐the‐art urea yield was achieved without additives via PNCR on CMMB, surpassing the best‐reported inorganic catalyst by a significant margin. This study provides an effective strategy for designing catalyst structures for the green synthesis of organonitrogen compounds.
The abuse of antibiotics has posed severe threats to the ecological environment and human health. Therefore, it is of great significance to develop efficient and convenient methods for the detection of trace antibiotic residues in water . Herein, we report a multifunctional sensing material {[Zn(H3L)(1,4-bib)]·H₂O}ₙ (Zn-CP) (H5L = 6-(3′,4′-dicarboxyphenoxy)-1,2,4-benzenetricarboxylic acid, 1,4-bib = 1,4-bis(1-imidazolyl)benzene) synthesized via a convenient hydrothermal method. Zn-CP exhibits distinct fluorescence responses toward kanamycin (KAN), tetracycline (TC), chlortetracycline (CTC), and norfloxacin (NFX): fluorescence enhancement for KAN, significant fluorescence quenching for TC and CTC, and a ratiometric response for NFX, with the corresponding detection limits of 147.16 nM, 178.28 nM, 186.92 nM, and 62.59 nM, respectively. Notably, the sensing mechanism is further elucidated by combining multiple experiments and density functional theory (DFT) calculations. More importantly, this fluorescent detection method is successfully applied to the sensitive determination of KAN, TC, CTC, and NFX in tap water and river water samples. This work demonstrates the advantages of fluorescent sensing materials based on coordination polymer and provides a promising strategy for the detection of antibiotic residues in aqueous environments.
Solid polymer electrolytes (SPEs) fabricated via in situ polymerization have garnered significant attention due to their excellent interfacial compatibility. Nonetheless, critical challenges, including low ionic conductivity, sluggish Li+ transport kinetics, and electrolyte flammability continue to hinder their widespread application. Herein, we introduce a multifunctional tri-arm crosslinker, triallyl isocyanurate (TAIC), to engineer an ultrathin, hypercrosslinked solid polymer electrolyte (TAIC-SPE) through in situ copolymerization with polyethylene glycol diacrylate (PEGDA). TAIC can act as rigid anchoring junctions, effectively avoiding the formation of long polymer chains, thereby enhancing ionic conductivity, and the electron-withdrawing carbonyl and triazine groups promote LiTFSI dissociation via anion coordination, enhancing the Li+ transference number. Besides, N-rich, structurally stable triazine ring can endow SPEs with high flame resistance and promote the formation of Li3N-enriched SEI during electrochemical cycling. The in situ-formed hypercrosslinked network ensures seamless interfacial adhesion and yields an only ~28-μm-thick membrane that provides short ion diffusion pathways. Thus, the optimized TAIC-SPE delivers a remarkable room-temperature ionic conductivity of 1.03 mS cm−1, a high Li+ transference number of 0.62, a wide electrochemical window (>4.8 V) and high temperature tolerance. Consequently, the symmetric cells can achieve stable cycling for over 2000 h, and full cells with LiFePO4 cathode and high-voltage NCM cathode can run stably with a high-capacity retention. This work underscores the viability of hypercrosslinked SPEs toward the practical realization of safe, high-performance solid-state Li metal batteries.
Direct synthesis of urea through photocatalytic N2 and CO2 reduction (PNCR) offers a sustainable approach to mitigate CO2 emissions and reduce energy consumption from urea production for industry and agriculture. However, achieving high yield of urea is limited by the high energy barrier for co-reduction of N2 and CO2 with subsequent C-N coupling. Herein, we propose that the spin polarization of chiral mesostructured Mo doped Bi2WO6 (CMMB) can facilitate the formation of triplet 3NOH by regulating the parallel electron spin alignment and promote the separation and transfer of photogenerated carriers, leading to enhanced C-N formation. The incorporation of Mo sites into Bi2WO6 promotes the adsorption and activation of N2. A state-of-the-art urea yield was achieved without additives via PNCR on CMMB, surpassing the best-reported inorganic catalyst by a significant margin. This study provides an effective strategy for designing catalyst structures for the green synthesis of organonitrogen compounds.
Ammonia decomposition is an appealing method for on-site hydrogen production, enabling ease of transportation and storage of H2. However, the high-temperature and hydrogen-rich environment present a challenge in developing highly efficient and stable catalysts. Hence, this study outlines an exsolution strategy for synthesizing a Ni-based catalyst in intimate contact with CeO2. The Ce10/NiAl2O4 catalyst exhibits competitive catalytic performance for ammonia decomposition reaction, and achieves a hydrogen production rate of 78.3 mmol gcat−1 min−1 at 550 °C. Importantly, the robust structure of the Ce10/NiAl2O4 catalyst ensures that no significant deactivation is observed during the 200-h stability test. HRTEM, XRD, TPD and kinetic studies reveals that the presence of CeO2 enhances the dispersion of exsolved Ni nanoparticles, modulates the surface basicity of catalyst, reduce the reaction activation energy, promote the desorption of nitrogen/hydrogen species, and subsequently promotes NH3 adsorption/activation capacity·NH3-TPD-MS in combination with in-situ DRIFTS demonstrate that CeO2 could accelerate the recombination and desorption of N* adatoms, which is the rate limiting step, thereby significantly boosting catalytic performance. Furthermore, the DFT calculations reveal that the interaction between CeO2 and Ni species facilitates electron transfer toward Ni, lowering the barrier for both N–H dissociation and N* recombination and desorption. This work not only presents an efficient and stable noble-metal-free catalyst for ammonia decomposition to generate hydrogen, but also provide a general strategy to engineer high-performance catalysts applicable to harsh catalytic environments.
INTRODUCTION:Intrahepatic splenosis is an extremely rare intrahepatic mass, which is easily misdiagnosed and mistreated. There are a few reports in the literature that intrahepatic splenosis mimicking hepatocellular carcinoma in a patient with elevated AFP. This study aims to analyze the diagnosis and treatment strategies of intrahepatic splenosis. MATERIALS AND METHODS:The clinical data of eleven patients with intrahepatic splenosis, diagnosed and treated at Wuhan Asia General Hospital and Union Hospital (Wuhan, China) between March 2012 and November 2024, were retrospectively analyzed. Enhanced CT imaging and enhanced MRI were used for the screening and diagnosis of liver lesions. RESULTS:Of the eleven patients with intrahepatic splenosis, six cases were pure intrahepatic splenosis, and five cases included extrahepatic splenosis. Enhanced CT imaging or enhanced MRI showed intrahepatic splenosis lesions with uneven enhancement in the form of fast in and fast out. Two patients were misdiagnosed with hepatocellular carcinoma due to elevated AFP, but biopsy revealed intrahepatic splenosis, thus avoiding unnecessary resection. The size of the intrahepatic splenosis lesions ranged from 1.0 to 4.2 cm. None of the nine patients who underwent surgical resection had splenosis recurrences, and the patients with intrahepatic splenosis confirmed by liver biopsy did not show lesion progression during the active examination period. DISCUSSION:Splenosis refers to the autotransplantation of viable splenic tissue into different anatomic compartments following splenic injury. The enhanced CT or MRI features of intrahepatic splenosis are similar to those of HCC. Selective hepatic arteriography may help differentiate intrahepatic splenosis from HCC. Percutaneous liver biopsy helps diagnose intrahepatic splenosis. CONCLUSION:In patients who have previously undergone splenectomy due to splenic trauma, it is important to consider the potential occurrence of intrahepatic splenosis upon the identification of intrahepatic lesions, and percutaneous liver biopsy is recommended. For individuals without clinical symptoms following a confirmed diagnosis of intrahepatic splenosis, no specific treatment is required.
Photodynamic therapy (PDT) is a promising treatment for cholangiocarcinoma (CCA), but its efficacy is limited by robust tumor antioxidant defenses and immunosuppressive microenvironment. Disrupting the expression of SLC6A6, a taurine transporter critical for redox homeostasis, represents a promising strategy for sensitizing CCA cells to PDT by disrupting taurine-mediated antioxidant protection. A first-in-class antibody-based PROTAC (AbTAC) specifically targeting SLC6A6 degradation was developed, followed by the engineering of biomimetic, ROS-responsive nanoparticles cloaked with CCA cell membranes (CM-TAC@Ce@PEG) for tumor-targeted co-delivery of the AbTAC and the photosensitizer chlorin e6 (Ce6). Comprehensive nanoparticle characterization covered size, drug loading, spectral properties, ROS production, and drug release kinetics. And the CM-TAC@Ce@PEG was evaluated for targeted fluorescence imaging and therapeutic efficacy in vitro and in vivo, with further investigation of its synergy with anti-PD-1 immunotherapy. Preclinical studies demonstrated that light-induced ROS triggers nanoparticle depolymerization. SLC6A6 degradation depletes taurine in tumor cells, disrupting antioxidant defenses and inducing ferroptosis. Crucially, CM-TAC@Ce@PEG simultaneously induces tumor cells to secrete colony-stimulating factor 2 (CSF2), driving M1 macrophage polarization and restoring CD8⁺ T cell cytotoxicity. This dual action powerfully activates innate and adaptive immunity, significantly inhibiting CCA growth. Furthermore, as a combination therapy with anti-PD-1 immunotherapy, CM-TAC@Ce@PEG markedly enhances therapeutic efficacy and effectively prevents tumor recurrence. This work unveils an integrated strategy that integrating PDT with metabolic reprogramming and immune activation. Targeting SLC6A6-mediated redox dysregulation not only overcomes PDT resistance but also synergizes with immune checkpoint blockade, establishing a promising therapeutic strategy for CCA.
Proton ceramic fuel cells (PCFCs) are favored for their excellent performance under medium-temperature conditions. However, their advancement is limited by sluggish oxygen kinetics and the lack of highly compatible cathodes. Nanocatalysts produced via in situ exsolution have emerged as a promising solution to overcome the limitations of conventional PCFC cathode catalysts. A novel three-phase composite cathode, synthesized via in situ ion topology engineering, achieves enhanced performance in PCFCs. By introducing the transition metal V into BaCe0.25Fe0.75O3-delta (BCF), BaFe2O4 nanoparticles are formed on the cathode surface through Fe-Ba-V ion exchange, simultaneously creating a BaCeO3-BaFe1-xVxO3 co-catalyzed interface. This composite cathode exhibits superior oxygen adsorption-dissociation capabilities and serves as an efficient proton conduction carrier. The self-assembled BaFe2O4, with its low thermal expansion coefficient, reduces the material's overall thermal expansion and improves cathode-electrolyte compatibility. Additionally, the cathode's stability and catalytic activity are significantly enhanced. PCFCs utilizing BCF-V as the cathode achieved an impressive power density of 1.73 W cm-2 at 650 degrees C and maintained stable operation for over 200 h at 600 degrees C.
Alkaline-earth segregation and low electronic conductivity restrict the practical applications of high-performance cathodes in solid oxide fuel cells (SOFCs) and protonic ceramic fuel cells (PCFCs). To address these issues, a unique electrode structure with a sintered active backbone coated with an in situ-formed porous net-like PrCoO3 (PCO) layer is developed. The effectiveness of this strategy is demonstrated using Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF), known for unprecedented oxygen reduction activity but with a great tendency to cause segregation and low electrical conductivity. This design leverages the beneficial characteristics of BSCF and PCO: the BSCF backbone provides high oxygen reduction activity, while the porous net-like PCO layer generated in situ offers high electrical conductivity. More importantly, this approach has the ability to eliminate potential surface segregation and even utilize the segregation by element interdiffusion to form a coating layer with high oxygen reduction activity. Therefore, the PCO-coated BSCF cathode (BSCF-PCO) offers impressive cell performance with a low area-specific polarization resistance of 0.02 Ω cm2 at 600 °C using a symmetric cell and a maximum power density of 1835 mW cm-2 at 600 °C using an anode-supported fuel cell, which are superior to the cells with the state-of-the-art BSCF (i.e., 0.04 Ω cm2 and 987 mW cm-2). Furthermore, this strategy significantly boosts the activity of other cathode materials such as Ba0.5Sr0.5Fe0.8Zn0.2O3-δ, a typical cathode for PCFCs. This study thus provides a facile, universal in situ strategy for constructing high-performance cathodes by removing and transforming surface segregation for SOFCs and PCFCs.
Resorbable devices for fracture fixation have gained extensive interest owing to their ability to avoid secondary surgery. Silk, as a biomaterial, is considered a promising candidate for fixation systems due to its biocompatibility, remarkable mechanical properties, and controllable degradation. However, the current methods for preparing silk fixation devices are complex and time-consuming, involving multiple processes, including dissolution, dialysis, lyophilization, etc. Here, we report a novel approach for fabricating silk fixation devices directly from a silk-LiBr solution through bidirectional dialysis. As the concentration of lithium bromide decreases and the ethanol concentration increases, the silk-LiBr solution undergoes a structural transition to beta-sheet, resulting in hydrogel formation. The hydrogel is further processed into a robust silk fixation system through drying and machining. The obtained silk screw demonstrated a maximum compression modulus of 1.47 GPa. In vivo experiments demonstrated that the silk fixation system exhibits good biocompatibility and maintains fixation stability for up to 4 months. Notably, the silk-based screw retained 94.8 % of its weight after four months in rats. The significance of this study lies in the development of a fabrication technique that enables the direct processing of silk-LiBr solution into diverse material formats with tunable structures and properties.
As an important ingredient, propylene is well converted into different industrial products, especially for C3 oxygen-containing compounds. However, traditional thermal catalysis not only increases the cost due to operation conditions of high temperature and high pressure, but also results in production of carbon dioxide via complete oxidation. Benefitting from mild operation condition and clean electric energy, electrocatalysis heaves in sight. Voltage regulation is used to enhance the selectivity of products and prevent excessive electrocatalytic oxidation of propylene (EOP) into carbon dioxide. Moreover, Pd, Ag, Pt-based materials have been constructed to promote kinetic rate and reduce the overpotential. This mini review summarizes influence of structure regulation on activity and stability of EOP, including adsorption-activation, reaction mechanism, structure-activity relationship, etc. Moreover, the challenges such as controlling selective electrocatalysis, simplifying the synthesis process and advanced techniques for characterizations are proposed. This review will inspire more researchers to design superior electrocatalysts to optimize their EOP performance.
Carbon-based metal-free materials are emerging as leading candidates to replace noble-metal catalysts in the oxygen reduction reaction (ORR). Herein, we introduce a facile secondary carbonation technique for fabricating Se and N co-doped metal-free catalysts using a zeolite imidazole framework (ZIF-8) as the precursor. The optimal electrocatalyst, designated SeNC-900, exhibited good ORR performance under both alkaline and acidic conditions, with half-wave potentials of 0.864 V and 0.731 V (vs. RHE), respectively. Density functional theory (DFT) calculations reveal that the enhanced activity of SeNC-900 originates from Se doping, which triggers an increase in the intrinsic defects of sp3-hybridized C. Concurrently, the sp3-hybridized C, in concert with Se dopant, modulates the electronic structure of the active C atoms. This work not only underscores the significance of tuning the electronic structure to boost catalytic performance by enriching intrinsic defects but also presents a fresh insight into the effect of heteroatom doping on carbon-based materials for electrocatalysis.
K+ desolvation in moderately concentrated ester electrolytes becomes easier with a longer alkyl chain of the linear ester. An electrolyte of 2.4 M KFSI in an ethylene carbonate + butyl methyl carbonate mixture renders a graphite anode with a high capacity of 261 mA h g-1 and 93% capacity retention after 500 cycles at 2C.
Enhancing the oxygen reduction kinetics at the cathode surface is crucial in the design optimization efforts for protonic ceramic fuel cells (PCFCs). Our study introduces a surface engineering strategy based on acid oxide- induced self-assembly to precisely control atomic arrangements on the surface of praseodymium-barium- cobalt ferrite (Pr 0.5 Ba 0.5 Co 0.7 Fe 0.3 O 3-delta , PBCF). This method enables the preparation of a "sandwich" type core- shell structure composed of three components: PBCF @Bavac(Barium Vacancies)@BaVO3. The lattice oxygen redox activity of cathode was accordingly fine-tuned to enhance the cathode performance of PCFCs. The synergistic integration of surface BaVO3 nanoparticles and Ba vac enhanced the PCFC's power density by over 50 %, achieving 1.68 W cm-2 at 650 degrees C. Furthermore, the formation of a barium vanadate second phase on the surface of PBCF not only aids in the redox reaction of the cathode but also significantly improves the stability of the cathode, thereby extending its lifetime. This research has broad applicability for surface modification of structurally stable perovskite cathodes.
To address the issue of suboptimal performance in solid oxide fuel cells, which are known for their exceptional energy transformation potential, numerous researchers are focused on enhancing the reaction kinetics and longterm stability of materials. This study presents the development of a perovskite material with a high concentration of surface proton acid sites, achieved through Cs doping with the formula Ba 0.95 Cs 0.05 Ce 0.3 Fe 0.7 O 3+delta (BCCF). The BCCF air electrode delivers a power density of 1.62 W cm- 2 at 700 degrees C in fuel cell (FC) mode. Additionally, it demonstrates a current density of-2.73 A cm- 2 at 1.3 V in electrolysis cell (EC) mode at 650 degrees C under 20 % H2O. The elevated electrocatalytic capability of the BCCF air electrode was ascribed to its substantial proton acid content. Density Functional Theory (DFT) calculations indicate that the inclusion of Cs promotes hydration formation and hence increases electrocatalytic activity.
Fiber materials have demonstrated significant competitive advantages in the field of electrocatalytic water splitting. Their unique characteristics-including high specific surface area, robust conductive networks, customizable properties, and the potential for hybridization with metal materials-make them prime candidates for catalytic applications. This review begins by exploring the fundamental principles of electrocatalytic water splitting, then categorizes the various types of fibers currently employed in this domain, and finally highlights the diverse roles that fiber materials play. In summary, the article outlines future research trajectories, potential applications, and anticipated challenges of fiber materials in electrocatalytic water splitting. This comprehensive review aims to foster a deeper understanding of this critical field and ultimately advance clean energy technologies.
Clean energy hydrogen is a promising substitute for traditional fossil fuels. Hydrogen production via electrocatalytic and photocatalytic water splitting is attracting much attention due to its environmental friendliness. Platinum-based materials are used to promote the kinetic rate for hydrogen evolution reaction (HER). However, the Pt usage is limited by their high price and low content. Much efforts have been put to replace them by non-precious metals. With low melting point and widest liquid temperature range, gallium is easily coupled with other metals or non-metals for constructing composite material for HER, However, systematic research on constructing gallium-based materials for HER is rare and this review could fill in certain gaps of related field. In this work, the preparation method and HER performance of gallium-based materials including gallium alloy, gallium phosphide and their composites, are summarized systematically. This review provides a comprehensive understanding of the structure influences of these gallium-based materials on electrocatalytic and photocatalytic HER performance. Moreover, possible challenges and prospects are also proposed for inspiring people to design excellent gallium-based materials for HER.
One of the current research directions in proton-conducting solid oxide fuel cells (H-SOFCs) is the development of triple-phase conducting cathodes. To enhance the proton conductivity and catalytic activity of barium ferrate cathode materials, the ratio of cerium to zinc is optimized, and the phase composition is carefully adjusted. This optimization results in significantly improved power density in single cells utilizing BaCe0.26Fe0.64Zn0.1O3-delta (BCFZ10) as the cathode, reaching a peak power density of 998.6 mW cm-2 at 600 degrees C. The remarkable performance of BCFZ10 cells can be attributed to their heightened proton conductivity and diminished hydration energy, as validated by thermogravimetric (TG) experiments. Density functional theory (DFT) calculations have further substantiated that the incorporation of zinc through doping effectively lowers the energy barrier for proton transition, consequently amplifying the proton absorption capability and electrochemical reactivity. The Zn-doped BCF36 cathode boosts proton conductivity, lowers hydration energy and achieves a peak power density of 998.6 mW cm-2 at 600 degrees C with a polarization resistance of 0.151 Omega cm2 for a single cell with the BCFZ10 cathode.
In-based catalysts offer an attractive approach for electrocatalytic reduction of CO2 (eCO2RR) into formate. However, precisely controlling the adsorption of competitive intermediates (*COOH and *OCHO) on In-based catalysts remains a tremendous challenge. Based on that, Ga is introduced for optimizing the electronic structure of In and adsorption of competitive intermediates. Here the indium-gallium metal organic framework (InGaMOF) with rich In-Ga bimetal sites is synthesized by a simple two-step method. The best InGaMOF(5 : 1) catalyst exhibits an excellent formate faradaic efficiency of 93% at -0.5 V (vs. RHE). The structure-activity relationship is revealed by in situ electrochemical Fourier transform infrared spectroscopy and other techniques. The characterization data indicate that the generated In-Ga bimetal sites in InGaMOF(5 : 1) provide co-adsorbed sites for CO2 molecules, facilitating their initial adsorption and activation into *CO2-. Moreover, the atomic bridging of Ga with In atoms efficiently optimizes the electronic structure of In, which results in weaker In-C hybridization of competitive *COOH (for CO) and stronger In-O hybridization of *OCHO (for formate). This study provides a new insight for understanding the important role of Ga in Ga-based bimetal electrocatalysts towards the eCO2RR. In-Ga bimetal sites facilitate the initial adsorption and activation to *CO2- and adjust the surface electronic features, thus significantly promoting the favorable conversion of the adsorbed *OCHO intermediate toward formate.