bluuebunny/crossref_metadata_2025_split huggingface dataset:
Tailoring Ultrafast and High‐Capacity Sodium Storage via Binding‐Energy‐Driven Atomic Scissors
Authors: Peng Baixin , Lv Zhuoran , Xu Shumao , Pan Jun , Zhao Wei , Dong Chenlong , Huang Fuqiang 
Published: May 2022

AbstractControllably tailoring alloying anode materials to achieve fast charging and enhanced structural stability is crucial for sodium‐ion batteries with high rate and high capacity performance, yet remains a significant challenge owing to the huge volume change and sluggish sodiation kinetics. Here, a chemical tailoring tool is proposed and developed by atomically dispersing high‐capacity Ge metal into the rigid and conductive sulfide framework for controllable reconstruction of GeS bonds to synergistically realize high capacity and high rate performance for sodium storage. The integrated GeTiS3 material with stable Ti–S framework and weak GeS bonding delivers high specific capacities of 678 mA h g−1 at 0.3 C over 100 cycles and 209 mA h g−1 at 32 C over 10 000 cycles, outperforming most of the reported alloying type anode materials for sodium storage. Interestingly, in situ Raman, X‐ray diffraction (XRD), and ex situ transmission electron microscopy (TEM) characterizations reveal the formation of well‐dispersed NaxGe confined in the rigid Ti–S matrix with suppressed volume change after discharge. The synergistically coupled alloying‐conversion and surface‐dominated redox reactions with enhanced capacitive contribution and high reaction reversibility by a binding‐energy‐driven atomic scissors method would break new ground on designing a high‐rate and high‐capacity sodium‐ion batteries.
Slip‐Line‐Guided Growth of Graphene
Authors: Li Yanglizhi , Liu Haiyang , Chang Zhenghua , Li Haoxiang , Wang Shenxing , Lin Li , Peng Hailin , Wei Yujie , Sun Luzhao , Liu Zhongfan 
Published: May 2022

AbstractManipulating the crystal orientation of emerging 2D materials via chemical vapor deposition (CVD) is a key premise for obtaining single‐crystalline films and designing specific grain‐boundary (GB) structures. Herein, the controllable crystal orientation of graphene during the CVD process is demonstrated on a single‐crystal metal surface with preexisting atomic‐scale stair steps resulting from dislocation slip lines. The slip‐line‐guided growth principle is established to explain and predict the crystal orientation distribution of graphene on a variety of metal facets, especially for the multidirectional growth cases on Cu(hk0) and Cu(hkl) substrates. Not only large‐area single‐crystal graphene, but also bicrystal graphene with controllable GB misorientations, are successfully synthesized by rationally employing tailored metal substrate facets. As a demonstration, bicrystal graphenes with misorientations of ≈21° and ≈11° are constructed on Cu(410) and Cu(430) foils, respectively. This guideline builds a bridge linking the crystal orientation of graphene and the substrate facet, thereby opening a new avenue for constructing bicrystals with the desired GB structures or manipulating 2D superlattice twist angles in a bottom‐up manner.
A Light‐Hole Germanium Quantum Well on Silicon
Authors: Assali Simone , Attiaoui Anis , Vecchio Patrick Del , Mukherjee Samik , Nicolas Jérôme , Moutanabbir Oussama 
Published: May 2022

AbstractThe quiet quantum environment of holes in solid‐state devices is at the core of increasingly reliable architectures for quantum processors and memories. However, due to the lack of scalable materials to properly tailor the valence band character and its energy offsets, the precise engineering of light‐hole (LH) states remains a serious obstacle toward coherent optical photon–spin interfaces needed for a direct mapping of the quantum information encoded in photon flying qubits to stationary spin processors. Herein, to alleviate this long‐standing limitation, an all‐group‐IV low‐dimensional system is demonstrated, consisting of a highly tensile strained germanium quantum well grown on silicon allowing new degrees of freedom to control and manipulate the hole states. Wafer‐level, high bi‐isotropic in‐plane tensile strain (<1%) is achieved using strain‐engineered, metastable germanium–tin alloyed buffer layers yielding quantum wells with LH ground state, high g‐factor anisotropy, and a tunable splitting of the hole sub‐bands. The epitaxial heterostructures display sharp interfaces with sub‐nanometer broadening and show room‐temperature excitonic transitions that are modulated and extended to the mid‐wave infrared by controlling strain and thickness. This ability to engineer quantum structures with LH selective confinement and controllable optical response enables manufacturable silicon‐compatible platforms relevant to integrated quantum communication and sensing technologies.
Nonideality‐Aware Training for Accurate and Robust Low‐Power Memristive Neural Networks
Authors: Joksas Dovydas , Wang Erwei , Barmpatsalos Nikolaos , Ng Wing H. , Kenyon Anthony J. , Constantinides George A. , Mehonic Adnan 
Published: May 2022

AbstractRecent years have seen a rapid rise of artificial neural networks being employed in a number of cognitive tasks. The ever‐increasing computing requirements of these structures have contributed to a desire for novel technologies and paradigms, including memristor‐based hardware accelerators. Solutions based on memristive crossbars and analog data processing promise to improve the overall energy efficiency. However, memristor nonidealities can lead to the degradation of neural network accuracy, while the attempts to mitigate these negative effects often introduce design trade‐offs, such as those between power and reliability. In this work, authors design nonideality‐aware training of memristor‐based neural networks capable of dealing with the most common device nonidealities. The feasibility of using high‐resistance devices that exhibit high I‐V nonlinearity is demonstrated—by analyzing experimental data and employing nonideality‐aware training, it is estimated that the energy efficiency of memristive vector‐matrix multipliers is improved by almost three orders of magnitude (0.715 TOPs−1W−1 to 381 TOPs−1W−1) while maintaining similar accuracy. It is shown that associating the parameters of neural networks with individual memristors allows to bias these devices toward less conductive states through regularization of the corresponding optimization problem, while modifying the validation procedure leads to more reliable estimates of performance. The authors demonstrate the universality and robustness of this approach when dealing with a wide range of nonidealities.
Prospecting Cellular Gold Nanoparticle Biomineralization as a Viable Alternative to Prefabricated Gold Nanoparticles
Authors: Schwartz‐Duval Aaron S. , Sokolov Konstantin V. 
Published: May 2022

AbstractGold nanoparticles (GNPs) have shown considerable potential in a vast number of biomedical applications. However, currently there are no clinically approved injectable GNP formulations. Conversely, gold salts have been used in the clinic for nearly a century. Further, there is evidence of GNP formation in patients treated with gold salts (i.e., chrysiasis). Recent reports evaluating this phenomenon in human cells and in murine models indicate that the use of gold ions for in situ formation of theranostic GNPs could greatly improve the delivery within dense biological tissues, increase efficiency of intracellular gold uptake, and specificity of GNP formation within cancer cells. These attributes in combination with safe clinical application of gold salts make this process a viable strategy for clinical translation. Here, the first summary of the current knowledge related to GNP biomineralization in mammalian cells is provided along with critical assessment of potential biomedical applications of this newly emergent field.
Microcrystalline Hybridization Enhanced Coal‐Based Carbon Anode for Advanced Sodium‐Ion Batteries
Authors: Chen He , Sun Ning , Zhu Qizhen , Soomro Razium Ali , Xu Bin 
Published: May 2022

AbstractSodium‐ion batteries (SIBs) are regarded as a kind of promising candidate for large‐scale energy storage technology. The development of advanced carbon anodes with high Na‐storage capacity and initial Coulombic efficiency (ICE) from low cost, resources abundant precursors is critical for SIBs. Here, a carbon microcrystalline hybridization route to synthesize hard carbons with extensive pseudo‐graphitic regions from lignite coal with the assistance of sucrose is proposed. Employing the cross‐linked interaction between sucrose and lignite coal to generate carbon‐based hybrid microcrystalline states, the obtained hard carbons possess pseudo‐graphitic dominant phases with large interlayer spaces that facilitate Na ion's storage and transportation, as well as fewer surface defects that guarantee high ICE. The LCS‐73 with an optimum cross‐link demonstrates the highest Na‐storage capacity of 356 mAh g−1 and an ICE of 82.9%. The corresponding full‐cell delivers a high energy density of 240 Wh kg−1 (based on the mass of anode and cathode materials) and excellent rate capability of 106 mAh g−1 at 10 C in addition to outstanding cycle performance with 80% retention over 500 cycles at 2 C. The proposed work offers an efficient route to develop high‐performance, low‐cost carbon‐based anode materials with potential application for advanced SIBs.
Separator‐Wetted, Acid‐ and Water‐Scavenged Electrolyte with Optimized Li‐Ion Solvation to Form Dual Efficient Electrode Electrolyte Interphases via Hexa‐Functional Additive
Authors: Li Xin , Liu Jiandong , He Jian , Qi Shihan , Wu Mingguang , Wang Huaping , Jiang Gaoxue , Huang Junda , Wu Daxiong , Li Fang , Ma Jianmin 
Published: May 2022

AbstractThe performance of lithium metal batteries (LMBs) is determined by many factors from the bulk electrolyte to the electrode‐electrolyte interphases, which are crucially affected by electrolyte additives. Herein, the authors develop the heptafluorobutyrylimidazole (HFBMZ) as a hexa‐functional additive to inhibit the dendrite growth on the surface of lithium (Li) anode, and then improve the cycling performance and rate capabilities of Li||LiNi0.6Co0.2Mn0.2O2 (NCM622). The HFBMZ can remove the trace H2O and HF from the electrolyte, reducing the by‐products on the surface of solid electrolyte interphase (SEI) and inhibiting the dissolution of metal ions from NCM622. Also, the HFBMZ can enhance the wettability of the separator to promote uniform Li deposition. HFBMZ can make Li+ easy to be desolvated, resulting in the increase of Li+ flux on Li anode surface. Moreover, the HFBMZ can optimize the composition and structure of SEI. Therefore, the Li||Li symmetrical cells with 1 wt% HFBMZ‐contained electrolyte can achieve stable cycling for more than 1200 h at 0.5 mA cm–2. In addition, the capacity retention rate of the Li||NCM622 can reach 92% after 150 cycles at 100 mA g–1.
Consumer willingness to pay for environmentally sustainable meat and a plant‐based meat substitute
Authors: Katare Bhagyashree , Yim Hyejin , Byrne Anne , Wang H. Holly , Wetzstein Michael 
Published: May 2022

AbstractWe investigate consumers' willingness to pay premiums for environmentally sustainably produced meat and plant‐based meat substitutes. We conducted a randomized control study coupled with an incentive‐compatible experimental auction. Treatment consisted of information nudges concerning the environmental and health externalities of meat production and consumption. Results show that demand for sustainably produced beef and a plant‐based meat substitute is inelastic. We elicited participants' time preferences to analyze whether consumer behavior varies with their time preference. Present‐biased treated female participants were willing to pay a significantly lower premium for sustainably produced beef compared to the present‐biased control female participants. Future‐biased treated participants had a higher probability of being willing to pay a premium for a plant‐based meat substitute compared to the control group. We discuss the policy implications and relevance of information nudging, such as labeling, and how the effect of such nudging varies with participant characteristics.
A Silylene Stabilized by a σ‐Donating Nickel(0) Fragment
Authors: Frutos María , Parvin Nasrina , Baceiredo Antoine , Madec David , Saffon‐Merceron Nathalie , Branchadell Vicenç , Kato Tsuyoshi 
Published: May 2022

AbstractA donor‐stabilized silylene 4 featuring a Ni0‐based donating ligand was synthesized. Complex 4 exhibits a pyramidalized and nucleophilic SiII center and shows a peculiar behavior due to the cooperative reactivity of Si and Ni centers. Calculations indicate that the orientation of Ni‐ligands with respect to the silylene moiety is crucial in determining the role of the Ni‐fragment (Lewis acid or Lewis base) towards silylene. Indeed, a simple 90° rotation of the Si−Ni bond, reverses the role of Ni, and transforms a classical silylene→Ni0 complex into an unprecedented Ni0→silylene complex.
Copper‐Catalyzed Radical Enantioselective Carbo‐Esterification of Styrenes Enabled by a Perfluoroalkylated‐PyBox Ligand
Authors: Nie Zaicheng , Chiou Mong‐Feng , Cui Jinfeng , Qu Yanjie , Zhu Xiaotao , Jian Wujun , Xiong Haigen , Li Yajun , Bao Hongli 
Published: May 2022

AbstractChiral lactones are found in many natural products. The reaction of simple alkenes with iodoacetic acid is a powerful method to build lactones, but the enantioselective version of this reaction has not been implemented to date. Herein, we report the efficient catalytic radical enantioselective carbo‐esterification of styrenes enabled by a newly developed CuI‐perfluoroalkylated PyBox system. Simple styrenes have been converted to useful chiral lactones, whose synthetic applications are showcased. Mechanistic studies reveal that this reaction is a rare example of an efficient ligand‐decelerated system, in which the ligand decelerates the reaction, but the reaction is still efficient with reduced amounts of ligand. This uncommon catalytic system may inspire further consideration of the effect of ligands in asymmetric catalysis.
Optochemical Control of Therapeutic Agents through Photocatalyzed Isomerization
Authors: Watson Emma E. , Russo Francesco , Moreau Dimitri , Winssinger Nicolas 
Published: May 2022

AbstractA Ru(bpy)3Cl2 photocatalyst is applied to the rapid trans to cis isomerization of a range of alkene‐containing pharmacological agents, including combretastatin A‐4 (CA‐4), a clinical candidate in oncology, and resveratrol derivatives, switching their configuration from inactive substances to potent cytotoxic agents. Selective in cellulo activation of the CA‐4 analog Res‐3M is demonstrated, along with its potent cytotoxicity and inhibition of microtubule dynamics.
A Cocatalyst Strategy to Enhance Ruthenium‐Mediated Metathesis Reactivity towards Electron‐Deficient Substrates
Authors: Si Guifu , Tan Chen , Chen Min , Chen Changle 
Published: May 2022

AbstractRuthenium‐mediated olefin metathesis has been widely applied for the synthesis of various organic molecules and polymers. Inspired by the cocatalyst strategy for olefin polymerization, here we demonstrate that the abstraction of a chloride ion from various commercially available ruthenium catalysts significantly enhances their reactivity towards electron‐deficient internal olefins. This cocatalyst strategy can be implemented in ethenolysis and cross‐metathesis reactions of FG‐CH=CH‐FG type substrates bearing electron‐withdrawing groups and the synthesis of telechelic polymers that can be converted to polyethylene‐like materials with closed‐loop recycling properties. The copolymerization of cyclic substrate with cycloolefins followed by hydrogenation afforded polyolefin materials with in‐chain break points. Interestingly, switchable catalysis was achieved in the absence and presence of a cocatalyst, which allowed the polymer microstructure and material properties to be fine‐tuned.
Highly Fluorescent Bipyrrole‐Based Tetra‐BF2 Flag‐Hinge Chromophores: Achieving Multicolor and Circularly Polarized Luminescence
Authors: Cui Luxia , Shinjo Hyuga , Ichiki Takafumi , Deyama Koichi , Harada Takunori , Ishibashi Kohei , Ehara Takumi , Miyata Kiyoshi , Onda Ken , Hisaeda Yoshio , Ono Toshikazu 
Published: May 2022

AbstractThis study reports the facile syntheses of tetra‐boron difluoride (tetra‐BF2) complexes, flag‐hinge‐like molecules that exhibit intense green‐to‐orange luminescence in solution and yellow‐to‐red emission in the solid states. Single‐crystal structure analysis and density functional theory calculations suggested a bent structure of this series of compounds. The complexes also exhibited excellent optical properties, with quantum yields reaching 100 % and a large Stokes shift. These properties were attributed to the altered bending angle of the molecule in the S1 excited state. As the rotational motion was suppressed around the 2,2′‐bipyrrole axis, atropisomers with axial chirality were formed, which are optically resolvable into (R) and (S)‐enantiomers through a chiral column. The atropisomers thus function as circularly polarized luminescent (CPL) materials, in which the color (green, green‐yellow, and yellow) can be varied by controlling the aggregation state. This rational design of multi‐BF2 complexes can potentially realize novel photofunctional materials.
Site‐Sensitive Selective CO2 Photoreduction to CO over Gold Nanoparticles
Authors: Huang Haowei , Zhao Jiwu , Weng Bo , Lai Feili , Zhang Menglong , Hofkens Johan , Roeffaers Maarten B. J. , Steele Julian A. , Long Jinlin 
Published: May 2022

AbstractWe demonstrate a new case of materials–gene engineering to precisely design photocatalysts with the prescribed properties. Based on theoretical calculations, a phase‐doping strategy was proposed to regulate the pathways of CO2 conversion over Au nanoparticles (NPs) loaded TiO2 photocatalysts. As a result, the thermodynamic bottleneck of CO2‐to‐CO conversion is successfully unlocked by the incorporation of stable twinning crystal planes into face‐centered cubic (fcc) phase Au NPs. Compared to bare pristine TiO2, the activity results showed that the loading of regular fcc‐Au NPs raised the CO production by 18‐fold but suppressed the selectivity from 84 % to 75 %, whereas Au NPs with twinning (110) and (100) facets boosted the activity by nearly 40‐fold and established near unity CO selectivity. This enhancement is shown to originate from a beneficial shift in the surface reactive site energetics arising at the twinned stacking fault, whereby both the CO reaction energy and desorption energy were significantly reduced.
Maschinelles Lernen zur Vorhersage chemischer Reaktivität: Die Bedeutung “gescheiterter” Experimente
Authors: Strieth‐Kalthoff Felix , Sandfort Frederik , Kühnemund Marius , Schäfer Felix R. , Kuchen Herbert , Glorius Frank 
Published: May 2022

AbstractDie quantitative Vorhersage der Ergebnisse chemischer Reaktionen ist eine zentrale Herausforderung in allen synthetischen Disziplinen. Während die darauf aufbauenden Optimierungsprobleme klassischerweise empirisch adressiert werden, birgt die datengestützte Modellierung ein enormes Potential, diese Prozesse zu beschleunigen. Für solche Vorhersagemodelle werden jedoch große Mengen hochwertiger Daten benötigt, die nur begrenzt verfügbar sind: Zu den Hauptgründen hierfür gehören experimentelle Fehler sowie besonders die menschliche Voreingenommenheit hinsichtlich der Auswahl von Experimenten und der Veröffentlichung von Ergebnissen. In einer Reihe von Fallstudien untersuchen wir die Auswirkungen dieser Verzerrungen auf die Qualität allgemeiner Schlussfolgerungen aus chemischen Reaktionsdaten, wobei die große Bedeutung von “gescheiterten” Beispielen deutlich wird. Schließlich zeigen Fallstudien zu Ansätzen der Datenerweiterung Wege auf, wie diese Einschränkungen umgangen werden können ‐ und demonstrieren somit Perspektiven für eine langfristige Verbesserung der Datenqualität in der Chemie.
Flexible Cuprous Triazolate Frameworks as Highly Stable and Efficient Electrocatalysts for CO2 Reduction with Tunable C2H4/CH4 Selectivity
Authors: Zhuo Lin‐Ling , Chen Pin , Zheng Kai , Zhang Xue‐Wen , Wu Jun‐Xi , Lin Duo‐Yu , Liu Si‐Yang , Wang Zhi‐Shuo , Liu Jin‐Yu , Zhou Dong‐Dong , Zhang Jie‐Peng 
Published: May 2022

AbstractCu‐based metal–organic frameworks have attracted much attention for electrocatalytic CO2 reduction, but they are generally instable and difficult to control the product selectivity. We report flexible Cu(I) triazolate frameworks as efficient, stable, and tunable electrocatalysts for CO2 reduction to C2H4/CH4. By changing the size of ligand side groups, the C2H4/CH4 selectivity ratio can be gradually tuned and inversed from 11.8 : 1 to 1 : 2.6, giving C2H4, CH4, and hydrocarbon selectivities up to 51 %, 56 %, and 77 %, respectively. After long‐term electrocatalysis, they can retain the structures/morphologies without formation of Cu‐based inorganic species. Computational simulations showed that the coordination geometry of Cu(I) changed from triangular to tetrahedral to bind the reaction intermediates, and two adjacent Cu(I) cooperated for C−C coupling to form C2H4. Importantly, the ligand side groups controlled the catalyst flexibility by the steric hindrance mechanism, and the C2H4 pathway is more sensitive than the CH4 one.
Rhodium‐Catalyzed Atroposelective Click Cycloaddition of Azides and Alkynes
Authors: Zeng Linwei , Li Jiaming , Cui Sunliang 
Published: May 2022

AbstractThe cycloaddition of azides and alkynes is the leading click chemistry technology and has been widely used in drug discovery, biology and material sciences. However, the development of a modular and scalable enantioselective click cycloaddition remains a long‐standing challenge. Herein, we report a rhodium‐catalyzed enantioselective click cycloaddition of azides and alkynes for rapid and modular access to atropisomeric triazoles in excellent yields and enantioselectivities. The process is mild, efficient and scalable, and features broad substrate scope.
Hierarchical Hollow Zinc Oxide Nanocomposites Derived from Morphology‐Tunable Coordination Polymers for Enhanced Solar Hydrogen Production
Authors: Zhu Qi , Xu Shuai , Wu Weidong , Qi Yi , Lin Zhan , Li Yuliang , Qin Yanlin 
Published: May 2022

AbstractInfinite coordination‐polymer particles (CPPs) are promising materials for solar energy conversion with high efficiency. However, the range of organic ligands that may be used to create CPPs is limited, as are strategies for modification, thereby hindering the applications of such material. In this paper, competitive evolution–morphological and structural change from Zn‐based crystallites to amorphous particles is described. Controlled contribution of organic linkers selectively derived six Zn‐CPPs with multivariate characters. Based on the diversity of these substructures, hollow zinc oxide particles were initially formed by self‐pyrolysis of CPPs and effectively modified by ultrathin doped nanosheets. The obtained double‐sided heterojunctions offer fully‐covered active sites, bringing together efficient light‐excited charge‐transfer nanochannels, which exhibit an excellent solar H2‐releasing activity (e.g., 4512.5 μmol h−1 g−1) and stable cyclability.