bluuebunny/crossref_metadata_2025_split huggingface dataset:
Artificial Photosynthesis over Tubular In2O3/ZnO Heterojunctions Assisted by Efficient CO2 Activation and S‐Scheme Charge Separation
Authors: Han Gaowei , Liu Chengyuan , Pan Yang , Macyk Wojciech , Wageh Swelm , Al‐Ghamdi Ahmed A. , Xu Feiyan 
Published: November 2022

AbstractSolar‐driven CO2 reduction shows promise in alleviating climate change and energy crises, but it suffers from difficult CO2 activation and rapid electron/hole recombination in current photocatalysts. Here we develop novel metal‐organic frameworks (MOFs)‐derived In2O3/ZnO tubular S‐scheme heterojunction photocatalyst for CO2 photoreduction. Resulting from Fermi level difference and electron transfer, an internal electric field is built at heterojunction interfaces and contributes to the formation of S‐scheme heterojunctions, as unveiled by in situ irradiation X‐ray photoelectron spectroscopy and time‐resolved photoluminescence spectroscopy. CO2 molecules are chemisorbed and activated over the photocatalyst in views of DFT simulations. The CO2 photoreduction follows a *COOH‐intermediate pathway and affords an enhanced CO production rate (12.6 µmol g−1) with nearly 100% selectivity in the absence of any molecular cocatalyst or scavenger. The enhanced performance is ascribed to the efficient charge separation, stronger redox ability, and powerful CO2 activation of In2O3/ZnO S‐scheme heterojunctions.
Adsorption Mechanism and Optical Behaviors of Typical Volatile Organic Compounds on Pristine and Cu/Ni‐Modified C3N Monolayer: A First‐Principles Study
Authors: Ma Kexin , Wang Yanwen , Zheng Yunxin , Xiao Jianrong , Xu Liang , Dai Xueqiong , Wang Zhiyong 
Published: November 2022

AbstractIn this paper, the geometric and electronic structure of four gas molecules, including CH4, CH2O, CH3Cl and C6H6, on pristine and Cu/Ni‐modified C3N monolayer are investigated by using First principles. The calculations show that the Cu/Ni‐doping can effectively strengthen the gas adsorption ability of C3N. Upon gas‐C3N configuration, the adsorption energies are CH2O (0.11 eV) > C6H6 (0.09 eV) > CH3Cl (0.08 eV) > CH4 (0.05 eV). For Cu‐C3N configuration, the adsorption energies are C6H6 (3.26 eV) > CH3Cl (3.24 eV) > CH4 (3.22 eV) > CH2O (3.13 eV). For Ni‐C3N configuration, the adsorption energies are CH2O (1.48 eV) > C6H6 (0.66 eV) > CH3Cl (0.39 eV) > CH4 (0.11 eV). It is worth mentioning that the magnetic moment is reduced to 0 µB when CH2O are adsorbed on Cu/Ni‐C3N, and the maximum charge transfer is 0.71 e, 0.62 e, respectively. Moreover, its optical properties of adsorption of Volatile organic compounds (VOCs) gas molecules are studied. It can be found that the two main absorption peaks locate at 3.0 × 105 cm−1 nm and 2.8 × 105 cm−1 nm at the range of ultraviolet and visible light. The calculated results provide the theoretical reference for Cu‐C3N‐based VOCs sensors.
Hollow Carbon Nanorod Confined Single Atom Rh for Direct Formic Acid Electrooxidation
Authors: Hu Yezhou , Chen Changsheng , Shen Tao , Guo Xuyun , Yang Chen , Wang Deli , Zhu Ye 
Published: November 2022

AbstractNearly theoretical 100% atomic utilization (supposing each atom could serve as independent sites to play a role in catalyz) of single‐atom catalysts (SACs) makes it highly promising for various applications. However, for most SACs, single‐atom sites are trapped in a solid carbon matrix, which makes the inner parts hardly available for reaction. Herein, a hollow N‐doped carbon confined single‐atom Rh (Rh‐SACs/HNCR) is developed via a coordination‐template method. Both aberration‐corrected scanning transmission electron microscopy and energy dispersive X‐ray spectroscopy mapping confirm the uniform distribution of Rh single atoms. Owning to the unique hollow structure and effective carbon confinement, excessive conversion from pyridinic/pyrrolic N to graphic N is hindered. As a proof of concept, Rh‐SACs/HNCR exhibits superior activity, stability, selectivity, and anti‐poisoning capability in formic acid oxidation reaction compared with the counterpart Rh/C, Pd/C, and Pt/C catalysts. This work provides a powerful strategy for synthesizing hollow carbon confined single‐atom catalysts apply in various energy‐related systems.
Benzotriazole‐Based Polymer Acceptor for High‐Efficiency All‐Polymer Solar Cells with High Photocurrent and Low Voltage Loss
Authors: Li Xiaoming , Duan Xiaopeng , Qiao Jiawei , Li Shilin , Cai Yunhao , Zhang Jianqi , Zhang Yuan , Hao Xiaotao , Sun Yanming 
Published: November 2022

AbstractThe power conversion efficiencies (PCEs) of all‐polymer solar cells (all‐PSCs) have already exceeded 17%. However, the limited absorption range of an all‐polymer system results in significantly reduced short‐circuit current density (Jsc), which eventually influences the PCE improvement. To broaden the light absorption of polymer acceptors, herein, benzotriazole is introduced in the core unit of small molecule acceptors and thus two narrow‐bandgap polymer acceptors named PTz‐BO and PTz‐C11 featuring the same molecular backbone and different side‐chain length are synthesized. Compared with PTz‐C11, the PTz‐BO based‐all PSCs deliver a slightly reduced Jsc, a large open‐circuit voltage (Voc) and a low voltage loss below 0.50 V. Moreover, ternary all‐PSCs are constructed by introducing PTz‐C11 as a guest component. Benefiting from the reduced recombination, improved exciton generation and dissociation, and balanced charge transport, a high efficiency of 16.58% is obtained for the ternary all‐PSCs, with a high Jsc over 25 mA cm−2 without sacrificing the Voc. Such result represents the highest efficiency reported for benzotriazole‐based all‐PSCs in the literature thus far. This work demonstrates the great potential of benzotriazole for the synthesis of efficient narrow‐bandgap polymer acceptors.
A Pleistocene assemblage of near‐modern Papio hamadryas from the Middle Awash study area, Afar Rift, Ethiopia
Authors: Brasil Marianne F. , Monson Tesla A. , Taylor Catherine E. , Yohler Ryan M. , Hlusko Leslea J. 
Published: November 2022

AbstractObjectivesThe aim of this study is to assess a new assemblage of papionin fossils (n = 143) recovered from later Pleistocene sediments in the Middle Awash study area in the Afar Rift of Ethiopia.Materials and MethodsWe collected metric and qualitative data to compare the craniodental and postcranial anatomy of the papionin fossils with subspecies of modern Papio hamadryas and with Plio‐Pleistocene African papionins. We also estimated sex and ontogenetic age.ResultsThe new fossils fit well within the range of morphological variation observed for extant P. hamadryas, overlapping most closely in dental size and proportions with the P. h. cynocephalus individuals in our extant samples, and well within the ranges of P. h. anubis and P. h. hamadryas. The considerable overlap in craniodental anatomy with multiple subspecies precludes subspecific diagnosis. We therefore referred 143 individuals to P. hamadryas ssp. The majority of the individuals assessed for ontogenetic age fell into middle‐ and old‐adult age categories based on the degree of dental wear. Males (26%) were better represented than females (12%) among individuals preserving the canine‐premolar honing complex.DiscussionThese new near‐modern P. hamadryas fossils provide a window into population‐level variation in the later Pleistocene. Our findings echo previous suggestions from genomic studies that the papionin family tree may have included a ghost population and provide a basis for future testing of hypotheses regarding hybridization in the recent evolutionary history of this taxon.
Mutability‐Landscape‐Guided Engineering of l‐Threonine Aldolase Revealing the Prelog Rule in Mediating Diastereoselectivity of C−C Bond Formation
Authors: Zheng Wenlong , Pu Zhongji , Xiao Lanxin , Xu Gang , Yang Lirong , Yu Haoran , Wu Jianping 
Published: November 2022

Abstractl‐threonine aldolase (LTA) catalyzes C−C bond synthesis with moderate diastereoselectivity. In this study, with LTA from Cellulosilyticum sp (CpLTA) as an object, a mutability landscape was first constructed by performing saturation mutagenesis at substrate access tunnel amino acids. The combinatorial active‐site saturation test/iterative saturation mutation (CAST/ISM) strategy was then used to tune diastereoselectivity. As a result, the diastereoselectivity of mutant H305L/Y8H/V143R was improved from 37.2 %syn to 99.4 %syn. Furthermore, the diastereoselectivity of mutant H305Y/Y8I/W307E was inverted to 97.2 %anti. Based on insight provided by molecular dynamics simulations and coevolution analysis, the Prelog rule was employed to illustrate the diastereoselectivity regulation mechanism of LTA, holding that the asymmetric formation of the C−C bond was caused by electrons attacking the carbonyl carbon atom of the substrate aldehyde from the re or si face. The study would be useful to expand LTA applications and guide engineering of other C−C bond‐forming enzymes.
Synthesis of α‐Quaternary β‐Lactams via Copper‐Catalyzed Enantioconvergent Radical C(sp3)−C(sp2) Cross‐Coupling with Organoboronate Esters
Authors: Wang Fu‐Li , Liu Lin , Yang Chang‐Jiang , Luan Cheng , Yang Jing , Chen Ji‐Jun , Gu Qiang‐Shuai , Li Zhong‐Liang , Liu Xin‐Yuan 
Published: November 2022

AbstractThe copper‐catalyzed enantioconvergent radical C(sp3)−C(sp2) cross‐coupling of tertiary α‐bromo‐β‐lactams with organoboronate esters could provide the synthetically valuable α‐quaternary β‐lactams. The challenge arises mainly from the construction of sterically congested quaternary stereocenters between the tertiary alkyl radicals and chiral copper(II) species. Herein, we describe our success in achieving such transformations through the utilization of a copper/hemilabile N,N,N‐ligand catalyst to forge the sterically congested chiral C(sp3)−C(sp2) bond via a single‐electron reduction/transmetalation/bond formation catalytic cycle. The synthetic potential of this approach is shown in the straightforward conversion of the corresponding products into many valuable building blocks. We hope that the developed catalytic cycle would open up new vistas for more enantioconvergent cross‐coupling reactions.
Near‐Infrared‐Absorbing Chiral Open [60]Fullerenes
Authors: Hashikawa Yoshifumi , Sadai Shumpei , Okamoto Shu , Murata Yasujiro 
Published: November 2022

AbstractThough [60]fullerene is an achiral molecular nanocarbon with Ih symmetry, it could attain an inherent chirality depending upon a functionalization pattern. The conventional chiral induction of C60 relies mainly upon a multiple addition affording a mixture of achiral and chiral isomers while their chiral function would be largely offset by the existence of pseudo‐mirror plane(s). These are major obstacles to proceed further study on fullerene chirality and yet leave its understanding elusive. Herein, we showcase a carbene‐mediated synthesis of C1‐symmetric chiral open [60]fullerenes showing an intense far‐red to near‐infrared absorption. The large dissymmetry factor of |gabs|=0.12 was achieved at λ=820 nm for circular dichroism in benzonitrile. This is, in general, unachievable by other small chiral organic molecules, demonstrating the potential usage of open [60]fullerenes as novel types of chiral chromophores.
Isolated Electron‐Rich Ruthenium Atoms in Intermetallic Compounds for Boosting Electrochemical Nitric Oxide Reduction to Ammonia
Authors: Zhang Huaifang , Li Yanbo , Cheng Chuanqi , Zhou Jin , Yin Pengfei , Wu Haoming , Liang Zhiqin , Zhang Jiangwei , Yun Qinbai , Wang An‐Liang , Zhu Lijie , Zhang Bin , Cao Wenbin , Meng Xiangmin , Xia Jing , Yu Yifu , Lu Qipeng 
Published: November 2022

AbstractThe direct electrochemical nitric oxide reduction reaction (NORR) is an attractive technique for converting NO into NH3with low power consumption under ambient conditions. Optimizing the electronic structure of the active sites can greatly improve the performance of electrocatalysts. Herein, we prepare body‐centered cubic RuGa intermetallic compounds (i.e.,bccRuGa IMCs) via a substrate‐anchored thermal annealing method. The electrocatalyst exhibits a remarkable NH4+yield rate of 320.6 μmol h−1 mg−1Ruwith the corresponding Faradaic efficiency of 72.3 % at very low potential of −0.2 V vs. reversible hydrogen electrode (RHE) in neutral media. Theoretical calculations reveal that the electron‐rich Ru atoms inbccRuGa IMCs facilitate the adsorption and activation of *HNO intermediate. Hence, the energy barrier of the potential‐determining step in NORR could be greatly reduced.
Nanoporous Films with Oriented Arrays of Molecular Motors for Photoswitching the Guest Adsorption and Diffusion
Authors: Jiang Yunzhe , Danowski Wojciech , Feringa Ben L. , Heinke Lars 
Published: November 2022

AbstractMolecular motors are fascinating nanomachines. However, constructing smart materials from such functional molecules presents a severe challenge in material science. Here, we present a bottom‐up layer‐by‐layer assembly of oriented overcrowded‐alkene molecular motors forming a crystalline metal–organic framework thin film. While all stator parts of the overcrowded‐alkene motors are oriented perpendicular to the substrate, the rotors point into the pores, which are large enough allowing for the light‐induced molecular rotation. Taking advantage of the thin film's transparency, the motor rotation and its activation energy are determined by UV/Vis spectroscopy. As shown by gravimetric uptake experiments, molecular motors in crystalline porous materials are used, for the first time, to control the adsorption and diffusion properties of guest molecules in the pores, here, by switching with light between the (meta‐)stable states. The work demonstrates the potential of designed materials with molecular motors and indicates a path for the future development of smart materials.
Balancing Activity and Stability in Spinel Cobalt Oxides through Geometrical Sites Occupation towards Efficient Electrocatalytic Oxygen Evolution
Authors: An Li , Zhang Hong , Zhu Jiamin , Xi Shibo , Huang Bolong , Sun Mingzi , Peng Yong , Xi Pinxian , Yan Chun‐Hua 
Published: November 2022

AbstractDesigning active and stable oxygen evolution reaction (OER) catalysts are vitally important to various energy conversion devices. Herein, we introduce elements Ni and Mn into (Co)tet(Co2)octO4 nanosheets (NSs) at fixed geometrical sites, including Mnoct, Nioct, and Nitet, to optimize the initial geometrical structure and modulate the CoCo2O4 surface from oxygen‐excess to oxygen‐deficiency. The pristine (Ni,Mn)‐(Co)tet(Co2)octO4 NSs shows excellent OER activity with an overpotential of 281.6 mV at a current density of 10 mA cm−2. Moreover, without damaging their initial activity, the activated (Act)‐(Ni,Mn)‐(Co)tet(Co2)octO4 NSs after surface reconstruction exhibit long‐term stability of 100 h under 10 mA cm−2, 50 mA cm−2, or even 100 mA cm−2. The optimal balance between electroactivity and stability leads to remarkable OER performances, providing a pivotal guideline for designing ideal electrocatalysts and inspiring more works to focus on the dynamic change of each occupation site component.
Synthesis, modification, and adsorption properties of Yb‐MOF: Kinetic and thermodynamic studies
Authors: Yin Lili , Deng Qinsong , Ke Zhilin , Yu Qiaoling , Xiao Yu , Zhang Shuhua 
Published: November 2022

In this paper, a novel Yb metal–organic frameworks {[Yb(L)(DMA)(H2O)]·(3H2O)}n(Yb‐MOF, H3Lis 4‐(N,N′‐bis(4‐carboxylbenzyl)amino)benzenesulfonic acid) was synthesized by solvothermal reaction. ModifiedYb‐MOFwas prepared by the potassium permanganate method for removing the Cu(II) and As(V) from simulated wastewater. The optimal pH value of modifiedYb‐MOFfor Cu(II) and As(V) adsorption was 5, and the optimal dosage of adsorbent was 0.04 mg/10 ml by static adsorption test. Four isothermal adsorption models (Freundlich, Langmuir, Temkin, and Dubinin–Radushkevich models) were fitted and analyzed. The adsorption processes of Cu(II) and As(V) were consistent with Freundlich, Langmuir, and Temkin models. The highest Cu(II) and As(V) adsorption capacity are 59.418 and 81.169 mg/g, respectively. The adsorption kinetic model and thermodynamic analysis of the modifiedYb‐MOFfor Cu(II) and As(V) were studied. The results showed revealed that the pseudo‐second‐order kinetic had a higher correlation association with the Cu(II) and As(V) adsorption process, indicating that chemisorption was dominant in both processes. At 298 and 308 K, the Cu(II) and As(V) adsorption by modifiedYb‐MOFis spontaneous.
Hyaluronan‐coated poly(propylene imine) dendrimers as biomimetic nanocarriers of doxorubicin
Authors: Paolino Marco , Varvarà Paola , Saletti Mario , Reale Annalisa , Gentile Mariangela , Paccagnini Eugenio , Giuliani Germano , Komber Hartmut , Licciardi Mariano , Cappelli Andrea 
Published: November 2022

AbstractA coating technology based on low molecular weight hyaluronic acid (HA) and ferulic acid (FA) was applied to the coating of low generation poly(propylene imine) dendrimers through a biocompatible hexa(ethylene glycol) spacer. The ensuing HA‐FA‐HEG‐PPID dendrimeric materials showed interesting loading capability (between 7.65% and 9.08%) regarding anticancer agent doxorubicin, and their interactions with the drug appeared to hamper the drug release in the physiological environment. Thus, the stable nanostructured loaded delivery systems were able to internalize into cells expressing the HA receptor CD44 and to demonstrate high cytotoxicity comparable to that shown by equivalent amounts of free doxorubicin. Thus, HA‐FA‐HEG‐PPID dendrimeric materials were proposed as biocompatible drug carriers capable of transporting anticancer doxorubicin to tumor cells.
Optimization of high temperature energy storage properties of PEI‐based composite dielectric based on rapid in‐situ growth of inorganic functional layer
Authors: Xu Fuping , Feng Yu , Liu Guang , Zhang Changhai , Li Changming , Chen Qingguo , Chi Qingguo 
Published: November 2022

AbstractThe serious deterioration of the energy density of polymer energy storage dielectrics in high temperature environment is the main reason to curb the in‐depth application of dielectric film capacitors in the field of modern electrical and electronic engineering. Here, aiming at the problem of low dielectric constant of polymer dielectric, a simple, low‐cost method is proposed to grow inorganic polar functional layer on surface of polymer film in situ, which effectively improves the polarization characteristics of polymer dielectric at high temperature. The in situ growth of Ti(OH)4 inorganic polar functional layer on surface of polyetherimide (PEI) film noteworthy to improve the energy storage performance of dielectric film. The energy storage density of 4.59 J/cm2 is obtained at 150°C and 600 MV/m, which is 1.18 times that of PEI film under the same condition. The significant enhancement of high temperature energy storage density can be attributed to introduction of functional layer, which effectively improves the dielectric properties and polarization intensity of dielectric film. Furthermore, the facile preparation method provided in this paper can be applied to various thin films under the premise of controllable cost, which is of great significance to improve the high temperature energy storage characteristics of polymer dielectric.
Infiltration of laponite: An effective approach to improve the mechanical properties and thermostability of collagen hydrogel
Authors: Li Jiao , Tian Zhenhua , Yang Huan , Duan Lian , Liu Yunfei 
Published: November 2022

AbstractRapid aggregate precipitation of collagen and laponite in solution restricted the development of corresponding hybrid materials. Herein, a facile method of immerging collagen hydrogel into laponite dispersion was adopted to prepare hybrid collagen/laponite hydrogel, avoiding the precipitation. Collagen hydrogel shrunk and water content decreased dramatically after laponite solution treatment. According to the images of Scanning electron microscopy and energy dispersive system, the uniformly dispersed laponite in collagen hydrogel was observed, demonstrating infiltration of laponite into collagen hydrogel. X‐ray photoelectron spectroscopy results revealed that coordination bonds generated between magnesium in laponite and collagen. Thermogravimetric analysis and Differential scanning calorimetry results displayed thermal decomposition temperature of collagen hydrogel increased from 321 to 342°C, and denaturation temperature rose from 43.8 to 50.8 °C after laponite infiltration. Rheological and compressive tests showed the elastic modulus, fracture stress, compressive modulus and rupture point of hydrogel treated by 10% laponite were 695.2 Pa, 253.3 kPa, 13.5 kPa and 76.7%, respectively, which were about 3.5, 5.5, 45.0, and 1.4 times larger than those of pristine collagen hydrogel. Besides, enzyme degraded rate of collagen was decelerated, and the hydrogel was still nontoxic with the infiltration of laponite. The promising data demonstrated infiltration of laponite was an effective way to fabricate collagen/laponite hybrid materials with desirable properties.
Spatial–temporal feature extraction based on convolutional neural networks for travel time prediction
Authors: Chen Abel C. H. , Yang Ya‐Ting 
Published: November 2022

AbstractIn recent years, some traffic information prediction methods have been proposed to provide the precise information on travel time, vehicle speed and traffic flow for highways. However, huge errors may be obtained by these methods for urban roads or alternative roads of highways. Therefore, this study proposes a travel time prediction method based on convolutional neural networks to extract important factors for the improvement of traffic information prediction. In practical experimental environments, the travel time records on No. 5 Highway and its alternative roads were collected and used to evaluate the proposed method. The results showed that the mean absolute percentage error of the proposed method was about 5.69%. Therefore, the proposed method based on deep‐learning techniques can improve the accuracy of travel time prediction.
Lowering of Electrostatic Actuator Driving Voltage and Increasing Generated Force Using Spontaneous Polarization of Ferroelectric Nematic Liquid Crystals
Authors: Nishimura Suzushi , Masuyama Satoshi , Shimizu Genichiro , Chen Chun‐Yi , Ichibayashi Taku , Watanabe Junji 
Published: November 2022

AbstractAlthough electrostatic actuators have a simple structure and are lightweight, their range of application is limited because a high applied voltage of more than several kilovolts is required for practical use. Since the force acting between the electrodes of an electrostatic actuator is determined by the electric charge accumulated at the electrode/dielectric interface, the focus is on spontaneous polarization of ferroelectrics to increase the charge. As the ferroelectric material, a nematic liquid crystal material with a spontaneous polarization of 5 µC cm−2 is used. It is demonstrated that a force of 1.3 N is generated at an applied electric field of 0.5 MV m−1. This force is 1200 times higher than that for standard paraelectric materials with a dielectric constant of ten. Further, the generated force responds linearly to the applied voltage, whereas it is proportional to the square of the applied voltage for paraelectric materials. The actuator function of this ferroelectric is examined using a double‐helical coil electrode fabricated using a 3D printer. It can be successfully operated at a voltage of several tens of volts. Under an electric field of 0.25 MV m−1, a remarkable contraction of 6.3 mm occurs, corresponding to 19% of the original length.