bluuebunny/crossref_metadata_2025_split huggingface dataset:
Hardware and Information Security Primitives Based on 2D Materials and Devices
Authors: Wali Akshay , Das Saptarshi 
Published: December 2022

AbstractHardware security is a major concern for the entire semiconductor ecosystem that accounts for billions of dollars in annual losses. Similarly, information security is a critical need for the rapidly proliferating edge devices that continuously collect and communicate a massive volume of data. While silicon‐based complementary metal‐oxide‐semiconductor technology offers security solutions, these are largely inadequate, inefficient, and often inconclusive, as well as resource intensive in time, energy, and cost, leading to tremendous room for innovation in this field. Furthermore, silicon‐based security primitives have shown vulnerability to machine learning (ML) attacks. In recent years, 2D materials such as graphene and transition metal dichalcogenides have been intensely explored to mitigate these security challenges. In this review, 2D‐materials‐based hardware security solutions such as camouflaging, true random number generation, watermarking, anticounterfeiting, physically unclonable functions, and logic locking of integrated circuits (ICs) are summarized with accompanying discussion on their reliability and resilience to ML attacks. In addition, the role of native defects in 2D materials in developing high entropy hardware security primitives is also examined. Finally, the existing challenges for 2D materials, which must be overcome for large‐scale deployment of 2D ICs to meet the security needs of the semiconductor industry, are discussed.
A Pseudocapacitor Diode Based on Ion‐Selective Surface Redox Effect
Authors: Tang Pei , Tan Wuyang , Li Fangzhou , Xue Shan , Ma Yihui , Jing Pengwei , Liu Yanghui , Zhu Jian , Yan Xingbin 
Published: December 2022

AbstractSupercapacitor diode (CAPode) is a novel device that integrates ion diode functionality into a conventional electrical double‐layer capacitor and is expected to have great applications in emerging fields such as signal propagation, microcircuit rectification, logic operations, and neuromorphology. Here, a brand new pseudocapacitor diode is reported that has both high charge storage (50.2 C g−1 at 20 mV s−1) and high rectification (the rectification ratio of 0.79 at 200 mV s−1) properties, which is realized by the ion‐selective surface redox reaction of spinel ZnCo2O4 in aqueous alkaline electrolyte. Furthermore, an application of the integrated device is demonstrated in the logic gate of circuit system to realize the logic operations of “AND” and “OR”. This work not only expands the types of CAPodes, but also provides a train of thought for constructing high‐performance capacitive ionic diodes.
P3ht‐Graphene Device for the Restoration of Visual Properties in a Rat Model of Retinitis Pigmentosa
Authors: Francia Simona , Di Marco Stefano , DiFrancesco Mattia L. , Ferrari Davide V. , Shmal Dmytro , Cavalli Alessio , Pertile Grazia , Attanasio Marcella , Maya‐Vetencourt José Fernando , Manfredi Giovanni , Lanzani Guglielmo , Benfenati Fabio , Colombo Elisabetta 
Published: December 2022

AbstractRetinal degeneration is one of the prevalent causes of blindness worldwide, for which no effective treatment has yet been identified. Inorganic photovoltaic devices have been investigated for visual restoration in advanced stage Retinitis pigmentosa (RP), although lack of implant flexibility and foreign‐object reactions have limited their application. Organic photoactive retinal prostheses may overcome these limitations, being biomimetic and tissue friendly. Inspired by organic photovoltaic strategies involving graphene, a hybrid retinal prosthesis is recently engineered consisting of a dual poly‐3‐hexylthiophene (P3HT) and graphene layer onto a flexible substrate. Here, this hybrid prosthesis is subretinally implanted in vivo in 5‐month‐old Royal College of Surgeons (RCS) rats, a rodent model of RP. Implanted dystrophic rats restored visual performances at both subcortical and cortical levels in response to light stimuli, in the absence of marked inflammatory responses. Moreover, the analysis of the physical‐mechanical properties after prolonged permanence in the eye showed excellent biocompatibility and robustness of the device. Overall, the results demonstrate that graphene‐enhanced organic photovoltaic devices can be suitably employed for the rescue of retinal dystrophies and supports the translation of the organic strategy into medical practice.
Programmable Control of Multiscale Droplets using V‐Valves
Authors: Xue Tian , Jain Ankit , Cao Xiaobao , Hess David , Stavrakis Stavros , de Mello Andrew 
Published: December 2022

AbstractContemporary droplet‐based microfluidic platforms generate large numbers of sub‐nanoliter (<10−9 L) volume droplets on short timescales. The controllable generation of femtoliter (10−15 L) volume droplets is however a far more challenging task. Herein, the design, fabrication, and testing of a valve‐based droplet‐on‐demand generator that enables the robust and controllable production of femtoliter‐volume water‐in‐oil droplets is described, where droplet size is determined by on‐chip pressure. This generator enables the sequential supply of femtoliter droplets to much larger “mother” droplets stored on‐chip, which in turn allows for high‐precision droplet dilution and programmable droplet pairing/merging operations. Such an approach can generate in excess of 700 fL‐volume droplets of variable content and with dilution factors of almost three orders of magnitude. Using the same principle, the microfluidic platform can also perform rapid, low‐volume consumption titrations. Accordingly, the valve‐based droplet‐on‐demand generator allows for a range of automated and multi‐step droplet‐based manipulations.
Organic Light‐Emitting Diodes Based on Silandiol‐Bay‐Bridged Perylene Bisimides
Authors: Brust Felix , Nagler Oliver , Shoyama Kazutaka , Stolte Matthias , Würthner Frank 
Published: December 2022

AbstractPerylene bisimides (PBIs) are among the best fluorophores but have to be enwrapped for optoelectronic applications by large and heavy substituents to prevent their ππ‐stacking, which is known to accelerate non‐radiative decay processes in the solid state. Here, light‐weight di‐tert‐butylsilyl groups are introduced to bridge 1,12‐dihydroxy and 1,6,7,12‐tetrahydroxy PBIs to afford sublimable dyes for vacuum‐processed optoelectronic devices. For both new compounds, this substitution provides a twisted and shielded perylene π‐core whose, via OSiObridges, rigid structure affords well‐resolved absorption and emission spectra with strong fluorescence in solution, as well as in the solid state. The usefulness of these dyes for vacuum‐processed optoelectronic devices is demonstrated in organic light‐emitting diodes (OLEDs) that show monomer‐like emission spectra and high maximum external quantum efficiency (EQEmax) values of up to 3.1% for the doubly silicon‐bridged PBI.
Regioselective Ortho‐Arylation of Polyhalo‐Substituted (Hetero)Aryl Tosylates Using an Integrated Continuous Flow/Batch Protocol
Authors: Kwon Yong‐Ju , Lee Seungmi , Shin Inji , Kim Won‐Suk 
Published: December 2022

AbstractThe regioselective ortho arylation of polyhalo‐substituted (hetero)aryl tosylates has been investigated employing an integrated continuous flow/batch protocol. The regioselective ortho metalation of (hetero)aryl tosylates using n‐BuLi and ZnCl2 was effectively achieved using continuous flow chemistry in a short residence time of 10.92 s, without removal of the tosyloxy group. The Pd‐catalyzed Negishi coupling reactions of various (hetero)aryl iodides with the resulting arylzinc species proceeded readily at room temperature in 31% to 98% yields. Finally, the method was applied to the synthesis of perampanel in four linear steps, with an overall yield of 43%.magnified image
Plasmon‐Assisted Operando Self‐Healing of Cu2O Photocathodes
Authors: Ross Aaron Michael , Ruiz‐Martinez Debora , Rizzi Gian Andrea , Cianciaruso Francesco , Patelli Alessandro , Salerno Marco , Schmitz Fabian , Napolitani Enrico , Marras Sergio , Prato Mirko , Gross Silvia , Meneghesso Gaudenzio , Marcilla Rebeca , Scotognella Francesco , Gatti Teresa , Lamberti Francesco 
Published: December 2022

AbstractThe ongoing problems in western countries connected to the global energy supply urgently force the research community to strive in finding new methodologies for boosting the functional properties of earth‐abundant raw materials, for example, the largely available cupreous oxide. In this work, the authors focus on the surface sensitization of this metal oxide semiconductor with an argon plasma treatment, that promotes, during photoelectrochemical hydrogen evolution, the formation of metallic copper nanostructures. Interestingly, these copper‐based hierarchical nano‐branches, having inherent plasmonic properties, are at the origin of the improved shelf‐life of the modified Cu2O photocathode, as is demonstrated by advanced structural and photophysical analyses. This proposed photophysical mechanism for an operando electrode stabilization suggests that a self‐healing process can occur within the Cu2O/plasmonic Cu heterostructure. These findings pave the way to the implementation of new, easy‐to‐make strategies to improve the properties of low‐cost, low‐toxicity energy materials.
Bimetallic FeNi Alloy Nanoparticles Grown on Graphene for Efficient Removal of Congo Red From Aqueous Solution
Authors: Zou Qiang , Zhu Zhenghou , Yuan Zhifen 
Published: December 2022

AbstractNano zero‐valent iron (nZVI) is an effective material for dye wastewater treatment, but excessive agglomeration and oxidation greatly limit its application. Herein, graphene (GR) supported FeNi bimetallic nanoparticles (FeNi@GR) are prepared by alloying and carrier supported dispersion for efficient removal of azo dyes from water. Not only can it effectively solve the problem of excessive agglomeration and oxidation of nZVI, but also the synergistic effect of bimetallic coordination formation and the excellent electron transfer ability of graphene are beneficial to enhance the reactivity of FeNi@GR. The optimal FeNi@GR is prepared by adjusting the content of GR and the removal of Congo red (CR) by FeNi@GR‐10% reached 625 mg g−1 within 150 min at pH = 7.0. Higher temperature and lower pH favor the removal of CR azo dye. The action mechanisms of FeNi@GR presumably involve the transfer of active hydrogen atoms and the transfer of electrons generated by Fe0 and Ni0. Besides, the saturation magnetization (Ms) of FeNi@GR is 68.15 emu g−1, which has excellent magnetic response performance. This work not only provides a simple and efficient method to stabilize nZVI, but also reveals that using FeNi@GR is a promising approach for the remediation of water pollution.
Development of In Situ Formed Metal Pyrophosphates (MP2O7, Where M = Sn, Ti, and Zr)/PA/PBI Based Composite Membranes for Fuel Cells
Authors: Wang Zehua , Zhang Jin , Lu Shanfu , Xiang Yan , Shao Zongping , Jiang San Ping 
Published: December 2022

AbstractDevelopment of high temperature polymer electrolyte membrane fuel cells (HT‐PEMFCs) at elevated temperatures is important for the enhancement of tolerance toward CO impurities and for the development of non‐precious metal catalysts. The key challenge in such HT‐PEMFCs is the high temperature polymer electrolyte membranes. Herein, the development of in situ formed metal pyrophosphates (MP2O7, where M = Sn, Ti, and Zr) in phosphoric acid doped polybenzimidazole (PA/PBI) composite membranes for HT‐PEMFCs is reported. The formation mechanism of MP2O7, and characteristics of MP2O7/PA/PBI composite membranes are studied in detail. In contrast to the rapid decay in performance of pristine PA/PBI membrane cells, the in situ formed MP2O7/PA/PBI composite membranes show significantly higher proton conductivity, improved performance, and stability at elevated temperatures of 200–250 °C. The best results are obtained on the in situ formed SnP2O7/PA/PBI composite membrane cells, exhibiting a high peak power density of 476 mW cm−2 and proton conductivity of 51.3 mS cm−1 at 250 °C. The excellent durability of SnP2O7/PA/PBI composite membrane is due to the uniform distribution of in situ formed SnP2O7 nanoparticles in PBI membranes and the formation of a gel‐like region, thin and irregular amorphous layer on the SnP2O7 with the high acid retention ability. This effectively alleviates the PA leaching at elevated temperatures of the new HT‐PEMFCs.
Scalable Direct Recycling of Cathode Black Mass from Spent Lithium‐Ion Batteries
Authors: Gupta Varun , Yu Xiaolu , Gao Hongpeng , Brooks Christopher , Li Weikang , Chen Zheng 
Published: December 2022

AbstractEnd of life (EoL) lithium‐ion batteries (LIBs) are piling up at an intimidating rate, which is alarming for environmental health. With further expected rapid growth of LIB use, the magnitude of spent battery accumulation is also expected to grow. LiNixCoyMnzO2 (NCM) cathode materials are a dominant chemistry in high energy LIBs, and make up a huge portion of this waste accumulation. Direct recycling is one of the most promising ways to turn this waste to wealth, but has been limited to lab‐scale, due to lack of robustness, namely the tedious pretreatment required that involves toxic organic solvents. Herein, a process that integrates the pretreatment and relithiation of the cathode black mass is demonstrated. Cathode material from EoL electric vehicle (EV) batteries is treated in a 100 g per batch operation and the regenerated cathode active material demonstrates 100% electrochemical performance recovery, with 91% yield rate, and shows promise for further scale up. This process has the advantages of integration, scalability, and universality, which clears the barricade for direct recycling to move from lab to industry scale with considerable profitability.
Unexpectedly High Cycling Stability Induced by a High Charge Cut‐Off Voltage of Layered Sodium Oxide Cathodes
Authors: Shen Qiuyu , Liu Yongchang , Zhao Xudong , Jin Junteng , Song Xiaobai , Wang Yao , Qu Xuanhui , Jiao Lifang 
Published: December 2022

AbstractInitiating anionic redox chemistry in layered sodium oxide cathodes is a prevalent method to break the capacity limit set by traditional transition metal redox. However, realizing the “win‐win” scenario of high capacity and high cycling stability is still challenging due to the high‐voltage structural distortion and irreversible oxygen loss. Herein, a Mn activation mechanism is unveiled in a novel P2‐Na0.80Li0.08Ni0.22Mn0.67O2 cathode. By elevating the charge cut‐off voltage to 4.3 V, anionic redox is successfully triggered and partial oxygen loss enables the reduction of Mn upon discharge, thus activating more Mn3+/Mn4+ redox reactions in the following cycles and maintaining the total capacity almost unchanged. In situ X‐ray diffraction reveals a complete solid‐solution reaction with an ultralow volume change of 1.04% upon cycling. Consequently, the P2‐Na0.80Li0.08Ni0.22Mn0.67O2 cathode simultaneously accomplishes a high discharge capacity (134.8 mAh g−1 at 0.1 C) and an unexpectedly long cycling life (capacity retention of 91.5% and 85.2% after 500 and 1000 cycles at 10 C, respectively). Via systematic ex situ characterizations and theoretical computations, the charge compensation mechanism upon Na+ insertion/extraction is elucidated. This work broadens the horizons of current oxygen redox chemistry and provides a new path to design high‐performance layered oxide cathode materials for sodium‐ion batteries.
A Smart Polymeric Sol‐Binder for Building Healthy Active‐Material Microenvironment in High‐Energy‐Density Electrodes
Authors: He Yan , Jing Lei , Feng Lanxiang , Yang Sifan , Yang Jiarui , Fu Xuewei , Yang Wei , Wang Yu 
Published: December 2022

AbstractSimilar to the cell microenvironment in biology, the active material microenvironment (ME@AM) in battery electrodes determines the charge flux into/out the individual AM particles, and the overall device performance thereby. However, it is very challenging to understand and regulate the ME@AM structures due to the lack of advanced binders and their links to electrode microstructures. Here, to address this challenge, a high‐performance sol‐binder based on propylene carbonate (PC) and poly(vinylidene fluoride) is designed and the ME@AM structural evolution during its electrode fabrication is investigated. First, a pen‐ink‐like uniform slurry is successfully prepared in minutes with the PC solvent. Second, the sol‐to‐gel transition of the sol‐binder during high‐temperature drying suppresses the uncontrollable component aggregation/separation as generally found in conventional solution‐based slurries. Third, it helps to build robust and healthy ME@AM with a high mechanical state‐of‐health (97%) and 800% improvement in peeling strength, because of an optimized enriched binder distribution. Finally, thick lean‐binder electrodes are demonstrated with much improved overall electrochemical performance. This study not only uncovers the potential of polymer sols or colloids as advanced binders, but also reshapes the understanding of electrode microstructures and their links to binder systems through the concept of ME@AM.
Visualizing the Chemical Incompatibility of Halide and Sulfide‐Based Electrolytes in Solid‐State Batteries
Authors: Rosenbach Carolin , Walther Felix , Ruhl Justine , Hartmann Matthias , Hendriks Theodoor Anton , Ohno Saneyuki , Janek Jürgen , Zeier Wolfgang G. 
Published: December 2022

AbstractHalide‐based solid electrolytes are currently growing in interest in solid‐state batteries due to their high electrochemical stability window compared to sulfide electrolytes. However, often a bilayer separator of a sulfide and a halide is used and it is unclear why such setup is necessary, besides the instability of the halides against lithium metal. It is shown that an electrolyte bilayer improves the capacity retention as it suppresses interfacial resistance growth monitored by impedance spectroscopy. By using in‐depth analytical characterization of buried interphases by time‐of‐flight secondary ion mass spectrometry and focused ion beam scanning electron microscopy analyses, an indium‐sulfide rich region is detected at the halide and sulfide contact area, visualizing the chemical incompatibility of these two electrolytes. The results highlight the need to consider more than just the electrochemical stability of electrolyte materials, showing that chemical compatibility of all components may be paramount when using halide‐based solid electrolytes in solid‐state batteries.
Spatially Distributed Lithiophilic Gradient in Low‐Tortuosity 3D Hosts via Capillary Action for High‐Performance Li Metal Anodes
Authors: Zhu Zixuan , Liu Bo , Qian Yong , Fang Yanyan , Lei Xin , Liu Xinmiao , Zhou Jianbin , Qian Yitai , Wang Gongming 
Published: December 2022

AbstractRegulating lithium deposition/stripping behavior in 3D hosts is critical for the development of stable lithium metal batteries. Herein, a low‐tortuosity wood derived carbon (WDC) with gradient‐distributed lithiophilic sites is rationally constructed via biomimetic capillary action, as an efficient scaffold for lithium deposition/stripping. Due to the merits of excellent spatial controllability, the gradient Ag particles modified WDC (WDC‐GDAg) displays favorable bottom‐up Li plating behavior with high columbic efficiency and long cycling stability. Finite element simulation reveals that gradient‐distributed Ag sites enable high lithium flux distribution at the bottom and homogeneous electric field distribution on the top of the WDC electrode. Moreover, the full cells with a WDC‐GDAg anode and a LiFePO4 cathode demonstrate high capacity retention of ≈78.9% after 2000 cycles at 10 C and remarkable rate performance even at 40 C, presenting great potential for practical applications.
Boosting the Performance on Scale‐Level of Triboelectric Nanogenerators by Controllable Self‐Triggering
Authors: Wang Qianwang , Yu Xin , Wang Jianlong , Yu Yang , Wang Zhenjie , Wang Zhong Lin , Cheng Tinghai 
Published: December 2022

AbstractThe characteristics of low current and high output impedance of triboelectric nanogenerators (TENGs) constrain their development and application. Recently, corresponding energy management methods have been proposed to solve the problems. Among them, the switch plays an important role in energy management to improve output performance and reduce output impedance. Therefore, a self‐triggering switch controlled by TENGs is proposed for power management to achieve high‐performance output. It is comprised of an electronic logic switch and the triggering TENG to release the energy stored by the energy‐TENG. The experimental results demonstrate that the self‐triggering switch can adjust the duty cycle with the assistance of the inherent load characteristics of the TENG. In addition, the coupling output of the two TENGs increases the single‐cycle peak current by 137 times (from 32 µA to 4.32 mA) in the vertical contact‐separation mode and 5284 times (from 1.3 µA to 6.87 mA) in the horizontal contact mode. In application, the commercial sensor can be powered, and six 100 W lamps in parallel can be lit. The coupling output method of switch‐TENGs and energy‐TENGs provides important guidance for the development of power management and a new approach toward practical applications.
A novel CHD3 variant in a patient with central precocious puberty: Expanded phenotype of Snijders Blok‐Campeau syndrome?
Authors: LeBreton Laure , Allain Eric P. , Parscan Radu Christian , Crapoulet Nicolas , Almaghraby Abdullah , Ben Amor Mouna 
Published: December 2022

AbstractSnijders Blok‐Campeau syndrome is an autosomal dominant genetic disorder first described in 2018, mostly associated with de novo variants in the CHD3 gene that affects chromatin remodeling. This syndrome is characterized by developmental delay, speech delay, and intellectual disability, but only about 60 affected individuals have been reported to date. We report a de novo likely pathogenic CHD3 variant (c.5609G > A; p. (Arg1870Gln)) in a young female presenting with features of Snijders Blok‐Campeau syndrome including speech delay, autism spectrum disorder, learning difficulties, characteristic facial dysmorphisms, and a feature not previously described in this syndrome, idiopathic central precocious puberty. Her puberty was controlled with monthly injections of a GnRH analogue. Targeted exome sequencing was negative for genes known to be responsible for central precocious puberty. Our case raises the possibility that variants in CHD3 gene may also result in central precocious puberty. Strengthening this association could expand the phenotypic spectrum of the Snijders Blok‐Campeau syndrome and should be included in multigene panels for precocious puberty.