bluuebunny/crossref_metadata_2025_split huggingface dataset:
Porous Carbon‐Supported Catalysts for Proton Exchange Membrane Fuel Cells
Authors: Song Pengyu , Chen Jiajun , Yin Zicheng , Yang Ziyi , Wang Lu 
Published: October 2024

AbstractProton exchange membrane fuel cells (PEMFCs) are crucial for the efficient utilization of hydrogen. Currently, their efficiency is mainly limited by the slow kinetics of the cathode oxygen reduction reaction (ORR) and the poisoning effect between ionomers and catalytic sites, particularly with Pt‐based catalysts. Recent works suggest that the emerging porous carbon‐supported catalysts hold promise in mitigating these challenges by ensuring fast kinetics while alleviating the poisoning. This review examines porous carbon‐supported catalysts for PEMFC cathodes, covering synthesis methods, structure and performance evaluation, and future prospects, with an emphasis on the influence of porous carbon support on PEMFC performance. On one hand, the rational design of pore structure in carbon support can help optimize the location of the active sites and enhance mass transfer. On the other hand, diverse pore structures provide a platform for gaining a deeper understanding of the mechanisms behind microscale mass transfer and reaction at the three‐phase boundaries. This review aims to inspire innovative strategies for the precise synthesis of porous carbon‐supported catalysts with various pore structures to further boost PEMFC performance.
Organic Compound Modified Cu‐Based Catalysts for the Hydrogenation of Esters
Authors: Cui Kai , Jing Yuli , Li Xiaohong 
Published: October 2024

AbstractCu/SiO2 catalysts are widely applied to the hydrogenation of dimethyl oxalate and ethylene carbonate to the corresponding ethylene glycol and methanol simultaneously, whereas ethylene glycol and methanol are important bulk commodities and raw materials for the production of oxygen‐containing chemicals and fuels. However, Cu particles usually aggregate or sinter to deactivate and the ratio of surface Cu0/Cu+ species is also difficult to control under the reaction conditions, so that the catalyst activity and stability is still a big challenge. It was found that modification of Cu‐based catalysts with certain organic compound inhibited the agglomeration of Cu particles, regulated the ratio of surface Cu0/Cu+ species, and even generated carbon layers to protect the Cu particles, which definitely improved the stability of the catalyst along with the enhanced catalytic performance. In this review, recent developments in ester hydrogenation over organic compound‐modified Cu/SiO2 catalysts were summarized and the issues to be further clarified are discussed as well.
Extractive Distillation of Isobutyl Alcohol and Isobutyl Acetate Using Dimethyl Sulfoxide: Process Design and Intensification
Authors: Yildirim Rumeysa , Unlusu Betul 
Published: October 2024

AbstractWe have designed a separation process of isobutyl alcohol (52.0 mol%) and isobutyl acetate (48.0 mol%) mixture using conventional extractive distillation (ED) and extractive dividing‐wall column (E‐DWC) with the solvent dimethyl sulfoxide (DMSO). The binary mixture exhibits a minimum boiling azeotrope that is sensitive to pressure. Thermodynamic analyses have shown that the vacuum pressures work better compared to the atmospheric pressure when DMSO is the solvent. Based on the separation with a purity of 99.9 mol%, the E‐DWC process has resulted in 9.6 % and 4.8 % reductions in the total annual cost and CO2 emission rates, respectively, in comparison to the conventional method. After further intensification using the heat pump technique, the E‐DWC process with the solvent DMSO has provided more than 40.0 % reduction in energy consumption compared to the ED systems studied in the literature using the solvents butyl propionate and dimethylformamide.
Elucidating the Performance Limitations of a 25 cm2 Pure‐Water‐Fed Non‐Precious Metal Anion Exchange Membrane Electrolyzer Cell
Authors: Lemcke Michelle Sophie , Loos Stefan , Menzel Nadine , Bron Michael 
Published: October 2024

AbstractAnion exchange membrane (AEM) water electrolysis has emerged as a promising technology for producing hydrogen in a carbon‐neutral economy. To advance its industrial application, performance evaluations of non‐precious metal AEM electrolyzers with electrode areas of 25 cm2 were conducted. The focus was on pure water operation, achieving a current density of 0.26 A cm−2 at a voltage of 2.2 V. To gain a better understanding, the AEM electrolyzer was also operated in aqueous KOH, yielding 1.2 A cm−2 at 2.2 V. By adding a liquid electrolyte and by varying cell components, causes of the occurring performance limitations and ways to improve the AEM electrolyzer were identified. Electrochemical impedance analysis showed that the activation loss at the anode due to sluggish OER kinetics was the limiting factor at low current densities. At higher current densities, which is the operating range of interest for industrial application, the ohmic resistance from the membrane was the dominant factor limiting high performance in pure water operation.
Photoelectrochemical Hydrogen Production from Water Using Copper‐based Chalcopyrite Thin Films
Authors: Ikeda Shigeru , Ishizuka Shogo 
Published: October 2024

AbstractCopper (Cu)‐based chalcopyrite compounds are promising photoabsorber materials not only for solar cells but also for photoelectrochemical (PEC) systems for conversion of sunlight energy into chemical energy. PEC water splitting to generate hydrogen (H2) is one of the most advanced technologies in a PEC system for the use of Cu‐based chalcopyrite compounds. In this review, we firstly introduce crystallographic/energetic structures of Cu‐based chalcopyrite compounds in view of their applications to PEC water splitting. Explanations for the operation of PEC water splitting using semiconductor materials are then overviewed. Based on these backgrounds, studies on PEC H2 evolution over photocathodes based on CuInS2 and CuGaSe2 thin films that we have developed are reviewed in detail. For realizing efficient PEC H2 evolution over these thin films, surface modifications with an n‐type layer such as CdS and a catalytic site such as Pt deposit were found to be indispensable. Precise controls of p‐n heterointerfaces formed by introducing an n‐type layer should also be required to enhance PEC performance. Although PEC water splitting has not reached the required efficiency to be useful, effective combinations of appropriate surface and interface modifications should lead to further improvements of properties to be close to practical applications.
A Uniform Conductive Carbon Coating of Nitrogen‐Doped Carbon Improves the Electrochemical Performance of LiMn0.7Fe0.3PO4 Cathode Material for Lithium‐ion Batteries
Authors: Xiong Hesen , Zhang Zongliang , Dai Jiaxin , Zhao Pei , He Kai , Gao Jie , Wu Qiang , Wang Baofeng 
Published: October 2024

AbstractThe practical application of LiMn1−xFexPO4 as a cathode material is hindered considerably by its poor electronic conductivity and slow lithium‐ion diffusion. In the present study, a uniform nitrogen‐doped carbon coating on LiMn0.7Fe0.3PO4 (LiMn0.7Fe0.3PO4@NC) was achieved using ethylene diamine tetraacetic acid (EDTA) as a chelating agent and carbon source. The nitrogen‐doped carbon layer enhanced the electronic conductivity and ionic diffusion of the LiMn0.7Fe0.3PO4 cathode. Furthermore, the uniform carbon layer prevented metal ion dissolution and stabilized the crystal structure. The resulting LiMn0.7Fe0.3PO4@NC‐2 sample demonstrated superior performance with a specific capacity of 152.5 mAh g−1 at 0.1 C and preserved 93.7 % of this capacity over 200 cycles at 1 C. Meanwhile, the LiMn0.7Fe0.3PO4@NC‐2 sample demonstrated a high Li+ diffusion coefficient (3.98×10−11 cm2 s−1) and electrical conductivity (1.47×10−2 S cm−1). This study presents a novel approach to designing high‐performance cathode materials using a cost‐effective and straightforward process.
Ag108(PEt3)24Cl6: A Hexagonal Prismatic Metalloid Cluster
Authors: Kordan Mike Alexander , Schrenk Claudio , Schnepf Andreas 
Published: October 2024

AbstractThe ligands used for the protection of metalloid clusters heavily influence the resulting structure and shape. For silver, thiolate and alkynyl ligands are commonly used, while phosphines usually play a minor role as co‐ligands. Herein, we report the synthesis and structural characterization of Ag108(PEt3)24Cl6 (1), the largest structurally characterized metalloid silver cluster with phosphines and halides as sole ligands. Instead of the frequently observed spherical shape of metalloid clusters, 1’s structure resembles a hexagonal prism. The highly light and temperature sensitive compound features many similarities to its smaller congener Ag64(PnBu3)16Cl6, though there are distinct structural and electronic differences present. Within 1, a Ag64 subunit can be found, which identifies these clusters as molecular seeds for the formation of faceted nanoparticles.
True and false discoveries with independent and sequential e‐values
Authors: Vovk Vladimir , Wang Ruodu 
Published: October 2024

AbstractIn this article, we use e‐values in the context of multiple hypothesis testing, assuming that the base tests produce independent, or sequential, e‐values. Our simulation and empirical studies, as well as theoretical considerations, suggest that, under this assumption, our new algorithms are superior to the known algorithms using independent p‐values and to our recent algorithms designed for e‐values without the assumption of independence.
Biosourced Au(III) Complexes from D‐Xylose: Synthesis and Biological Evaluation
Authors: Pascual Laura M. H. , Devy Jérôme , Colin Marius , Chazée Lise , Guillaneuf Alexandra , Marin Béatrice , Plantier‐Royon Richard , Gatard Sylvain 
Published: October 2024

AbstractA series of xylose‐based ligands was obtained using a convenient approach, in a few steps from D‐xylose. The complexation properties of these ligands towards Au3+ cations have been studied through different methods (multinuclear NMR, mass spectrometry, elemental analysis). The biological properties (antibacterial and anti‐tumoral) of all the isolated xyloside Au(III) complexes were investigated in vitro. The xyloside Au(III) complexes gave the highest activities against E. coli (vs P. aeruginosa, S. aureus and S. epidermidis). The study also revealed that the nature of the sugar may play an important role in determining the selectivity of the antibacterial effect. Preliminary anti‐tumoral evaluations showed that one complex containing a polyamine chain, exhibited interesting anti‐proliferative activities on breast tumor cell lines MDA‐MB‐231 and BT‐20. The anti‐migratory effect of this complex also showed an average 35 % reduction in cell migration on the same two cancer cell lines.
Video Documented Upscaled Synthesis of Salts of the Parent Carbaborate Ion [CB11H12]−, its Undecafluorinated Form [CHB11F11]− and Useful Starting Materials for its Introduction
Authors: Kulenkampff Jan , Armbruster Christian , Drolshagen Johanna , Regnat Celine , Wienold Tina , Spari Luisa , Fix Jana , Sterbak Tabea , Scherer Harald , Krossing Ingo 
Published: October 2024

AbstractIn this work, we present our improved protocols for the single batch syntheses of approximately 32 g of [NHMe3][CB11H12] and 10 g of Na[CHB11F11] as well as salt metathesis reactions, granting access to useful starting materials to introduce the [CHB11F11]− anion. This includes the trityl cation [Ph3C]+ and the bis‐1,2‐difluorobenzene‐silver(I)‐complex [Ag(odfb)2]+, as well as some applications of the shown compounds. The described methodology allows the synthesis of large amounts of both the [CB11H12]− and the [CHB11F11]− anion and therefore making them accessible for further reactions. To facilitate the reproducibility, we present video tutorials of the synthetic steps towards Na[CHB11F11].
Multi‐Layer Kesterite‐Based Photocathodes for NH3 Photosynthesis from N2 Reduction Reaction
Authors: Ferreira de Brito Juliana , Medina Marina , Sousa Santos Hugo Leandro , dos Santos Araujo Mileny , Santana Andrade Marcos Antônio , Helena Mascaro Lucia 
Published: October 2024

AbstractThe necessity of new methods to substitute the Haber‐Bosch process in the NH3 synthesis, generating fewer greenhouse gases, and dispensing less energy, drove the investigation of the photoelectrocatalytic approach in the N2 reduction reaction (N2RR). For that, this work presents the synthesis and characterization of the layered CZTSSe/CdS/TiO2 photocathode decorated with Pt nanoparticles for application in NH3 production using the photoelectrocatalysis technique. The CZTSSe/CdS/TiO2‐Pt characterization showed a well‐designed and stable photocatalyst synthesized layer by layer with an important contribution of the Pt nanoparticles for the catalyst performance, improving the photocurrent density and the charge transfer. The N2RR in a two‐compartment photochemical cell with 0.1 mol L−1 Na2SO3 and 0.05 mol L−1 H2SO4 in the cathodic and anodic chamber, respectively, using CZTSSe/CdS/TiO2‐Pt and under 1 sun of light incidence and applied potential of −0.4 VAg/AgCl reached 0.22 mmol L−1 cm−2 NH3, a value 28 folds higher than using the catalyst without Pt modification. The superiority of N2RR under the photoelectrocatalysis technique was demonstrated compared to photocatalytic and electrocatalytic techniques, together with the investigation of the supporting electrolyte influence in the cathodic compartment. Additionally, that is the first time a kesterite‐based photocathode has been applied to NH3 photosynthesis, showing excellent photoconversion capability.
Sensitivity of Capacity Fade in Vanadium Redox Flow Battery to Electrolyte Impurity Content
Authors: Pichugov Roman , Loktionov Pavel , Verakso Darya , Pustovalova Alla , Chikin Dmitry , Antipov Anatoly 
Published: October 2024

AbstractThe gradual capacity decrease of vanadium redox flow battery (VRFB) over long‐term charge‐discharge cycling is determined by electrolyte degradation. While it was initially believed that this degradation was solely caused by crossover, recent research suggests that oxidative imbalance induced by hydrogen evolution reaction (HER) also plays a significant role. In this work by using vanadium pentoxides with different impurities content, we prepared three grades of vanadium electrolyte. By measuring electrochemical properties on carbon felt electrode in three‐electrode cell and VRFB membrane‐electrode assembly we evaluate the influence of impurity content on battery polarization and rate of side reactions which is indicated by the increase of average oxidation state (AOS) during charge‐discharge tests and varies from 0.061 to 0.027 day−1 for electrolytes made from 99.1 and 99.9 wt % V2O5. We found that increase of AOS correlates with the increase of open‐circuit voltage of VRFB in the discharged state ranging from 9.6 to 14.9 mV day−1 for highest and lowest electrolyte purity levels, respectively. While AOS increase is significant, it does not solely determine capacity fade. It is demonstrated that the presence of vanadium crossover decreases capacity fade, i. e. levels the contribution of side reactions on capacity drop.
High‐Efficiency Deep‐Blue Solution‐Processed Organic Light‐Emitting Diodes Using Carbazole Dendrons Modified Hybridized Local and Charge‐Transfer Emitters
Authors: Chantanop Nuttapong , Saenubol Atthapon , Itsoponpan Teerapat , Prakanpo Nipanan , Wongkaew Praweena , Loythaworn Thidarat , Waengdongbung Wijitra , Sudyodsuk Taweesak , Promarak Vinich 
Published: October 2024

AbstractIn the pursuit of efficient and cost‐effective organic light‐emitting diodes (OLEDs), the development of solution‐processed hybridized local and charge transfer (HLCT) emitters presents a promising approach. HLCT materials uniquely integrate the advantages of both singlet and triplet excitons, surpassing the traditional spin statistical limit of 25 % while offering high photoluminescence efficiency and balanced charge transport properties. Herein, we report the synthesis and characterization of two new deep blue, solution‐processable HLCT fluorophores, G1FTPI and G2FTPI. These compounds incorporate fluorenyl carbazole dendron units into the HLCT luminogenic triphenylamine‐phenanthroimidazole (TPI) molecule. Their HLCT and photoluminescence (PL) properties were experimentally and theoretically investigated using solvation effects and density functional theory (DFT) calculations. The molecules exhibit deep blue emission with a high solid‐state fluorescence quantum yield, good solution‐processed film‐forming quality, and high hole mobility values of 2.18–2.61×10−6 cm2 V−1 s−1. Both compounds were successfully employed as non‐doped emissive layers in solution‐processed OLEDs, demonstrating excellent electroluminescent (EL) performance. Notably, the G2FTPI‐based device emitted a deep blue light at 432 nm with CIE coordinates of (0.158, 0.098) and achieved a maximum current efficiency (CEmax) of 3.13 cd A−1 and a maximum external quantum efficiency (EQEmax) of 5.30 %.
Real‐Time Implementation of Unknown Input Observer‐Based State and Unknown Disturbance Estimation for Series Active Filters
Authors: Kiran Nagulapati , Naidu I. E. S. 
Published: October 2024

ABSTRACTSeries active filter (SAF) is generally utilized in compensating harmonic voltage source‐type loads. In this paper, a combined action of controller and observer is proposed for SAF. Full state feedback (SFB) and linear quadratic regulator (LQR) controllers are posited in order to estimate states, and fault. SFB utilizes the pole placement method, whereas LQR utilizes the tuning of matrices by Bryson's rule. Luenberger observer (LO), proportional–integral observer (PIO), and unknown input observer (UIO) were also designed. The efficacy of this scheme is illustrated through the simulations, in the presence of faults. The state dynamics of SFB‐ and LQR‐based control of SAF with LO, PIO, and UIO in different faulty cases are compared. It can be clearly seen through simulations that the state dynamic response of LQR‐based control of SAF is faster when compared to SFB‐based control of SAF in both cases. Further, LO and PIO established a steady‐state error between the actual state and its estimate, with reference to desired input, in the presence of a fault. UIO perfectly tracked the desired input, even in the presence of various unknown fault, when compared to LO and PIO. Furthermore, UIO also estimates the unknown faults better when compared to PIO. Finally, in a dynamic operating scenario, the effectiveness of the suggested control strategy has been assessed and verified using MATLAB/SIMULINK and the output of a real‐time simulator (OPAL‐RT OP4510).
Heatwave‐Induced Paternal Effects Have Limited Adaptive Benefits in Offspring
Authors: Irish Sara D. , Sutter Andreas , Pinzoni Livia , Sydney Mabel C. , Travers Laura , Murray David , de Coriolis Jean‐Charles , Immler Simone 
Published: October 2024

ABSTRACTAs the threat of climate change and associated heatwaves grows, we need to understand how natural populations will respond. Inter‐generational non‐genetic inheritance may play a key role in rapid adaptation, but whether such mechanisms are truly adaptive and sufficient to protect wild populations is unclear. The contribution of paternal effects in particular is not fully understood, even though the male reproductive system may be highly sensitive to heatwaves. We used the zebrafish Danio rerio to investigate the effects of heatwaves on male fertility and assess potential adaptive benefits to their offspring in a number of large‐scale heatwave experiments. Heatwave conditions had negative effects on male fertility by reducing gamete quality and fertilisation success, and we found indications of an adaptive effect on hatching in offspring produced by heatwave‐exposed males. Our findings highlight the importance of including male and female fertility when determining species ability to cope with extreme conditions and suggest that parental effects provide limited adaptive benefits.
Dinuclear Copper(II) Complex with Intramolecular O−H⋅⋅⋅O Hydrogen Bonding: Magneto‐Structural Correlation for Acylhydrazone‐Based Phenoxido Bridged Copper(II) Complexes
Authors: Böhme Michael , Mohanty Monalisa , Lima Sudhir , Buchholz Axel , Görls Helmar , Dinda Rupam , Plass Winfried 
Published: October 2024

AbstractThe μ‐phenoxido‐bridged dinuclear copper(II) complex, [Cu2(L1)2(dmso)(MeOH)] (1), has been synthesized using N′‐(4‐(diethylamino)‐2‐hydroxybenzylidene)‐1‐naphthohydrazide (H2L1) as ligand. The structural analysis of 1 reveals that the coordination geometry at the copper ions is best described as a square pyramidal with a Cu⋅⋅⋅Cu distance in the dinuclear complex of 303 pm which is supported by hydrogen bonding between the two apical oxygen donor ligands (O⋅⋅⋅O 277 pm). Magnetic studies indicate that 1 exhibits a strong antiferromagnetic interaction between the two copper(II) ions with a coupling constant of J=−450 cm−1 (
). The magnetic exchange is transmitted through the central [Cu2(OR)2]2+ core, a fragment for which different magneto‐structural correlations have been reported depending on the substituent at the bridging oxygen atom. However, the properties of complex 1 cannot be explained by any of the established correlations. Nevertheless, complex 1, together with the series of compounds based on an acylhydrazone ligand framework reported so far, shows a magneto‐structural correlation as a function of the Cu−O−Cu bridging angle that significantly differs from all previously reported.
A Dehydrocoupling Approach Towards Titanocene Iminophosphane Complexes
Authors: Petrov Andrey , Hering‐Junghans Christian 
Published: October 2024

AbstractDehydrocoupling reactions represent a powerful tool for element‐element bond formation upon H2 elimination. It was shown that transition metals (in low oxidation states or in the form of hydrides) can be coupled with two equivalents of primary pnictanes (R–PnH2; Pn=P, Sb) providing direct access to otherwise elusive η2‐dipnictene (R–Pn=Pn–R) complexes. Herein, we report on the reactivity of the common group IV metallocene precursors Cp2Ti(btmsa) and Cp2Zr(btmsa)(pyridine) (btmsa=C2(SiMe3)2) towards primary pnictanes (R–PnH2 (Pn=P or N) and secondary aminophosphanes (R'P(H)–N(H)R). We found that Cp2Ti(btmsa) reacts with secondary aminophosphanes (R'P(H)–N(H)R) to give η2‐iminophosphane titanocene complexes. The molecular and electronic structure of the new compounds were thoroughly investigated spectroscopically, crystallographically and computationally.