bluuebunny/crossref_metadata_2025_split huggingface dataset:
Penta‐Coordinated Y Sites Modulated Single Bi Sites for Promoted Selectivity of Electrochemical CO2 Reduction
Authors: Liang Zhong , Song Lianpeng , Jiang Yong , Liu Jincheng , Zhang Yabin , Zhang Qian , Yan Chun‐Hua , Du Yaping 
Published: November 2023

AbstractAtomically dispersed catalysts with two active sites have attracted attention in recent years. The two different sites may act synergistically in catalytic reactions or one site as active site and another regulates it. In this work, rare earth (RE)‐based single‐atom combo catalyst BiY/CN (with Y penta‐coordinated) is synthesized and characterized carefully for electrochemical reduction of CO2 to formic acid for the first time. The state of active Bi and Y species in the prepared catalyst is proved by the extended X‐ray absorption fine structure spectra and aberration‐corrected high‐angle annular dark field scanning transmission electron microscopy. The comprehensive experimental results and density functional theory calculations show Y sites covered by hydroxyls not only avoid being poisoned by *HCO2 at working conditions, but also serve as a spectator to affect the charge state of Bi sites, promoting performance by facilitating the transformation of *HCO2 intermediate to HCOOH. This work provides a new perspective on RE elements in electrocatalytic carbon dioxide reactions in future studies.
Recent Advances on NIR‐II Light‐Enhanced Chemodynamic Therapy
Authors: Wu Gui‐long , Tan Xiaofeng , Yang Qinglai 
Published: November 2023

AbstractChemodynamic therapy (CDT) is a particular oncological therapeutic strategy by generates the highly toxic hydroxyl radical (•OH) from the dismutation of endogenous hydrogen peroxide (H2O2) via Fenton or Fenton‐like reactions. However, single CDT therapies have been limited by unsatisfactory efficacy. Enhanced chemodynamic therapy (ECDT) triggered by near‐infrared (NIR) is a novel therapeutic modality based on light energy to improve the efficiency of Fenton or Fenton‐like reactions. However, the limited penetration and imaging capability of the visible (400–650 nm) and traditional NIR‐I region (650–900 nm) light‐amplified CDT restrict the prospects for its clinical application. Combined with the high penetration/high precision imaging characteristics of the second near‐infrared (NIR‐II,) nanoplatform, it is expected to kill deep tumors efficiently while imaging the treatment process in real‐time, and more notably, the NIR‐II region radiation with wavelengths above 1000 nm can minimize the irradiation damage to normal tissues. Such NIR‐II ECDT nanoplatforms have greatly improved the effectiveness of CDT therapy and demonstrated extraordinary potential for clinical applications. Accordingly, various strategies have been explored in the past years to improve the efficiency of NIR‐II Enhanced CDT. In this review, the mechanisms and strategies used to improve the performance of NIR‐II‐enhanced CDT are outlined.
UV‐Curing Assisted Direct Ink Writing of Dense, Crack‐Free, and High‐Performance Zirconia‐Based Composites With Aligned Alumina Platelets
Authors: Li Maoyin , Huang Shuigen , Willems Evita , Soete Jeroen , Inokoshi Masanao , Van Meerbeek Bart , Vleugels Jef , Zhang Fei 
Published: November 2023

AbstractAdditive manufacturing (AM) of high‐performance structural ceramic components with comparative strength and toughness as conventionally manufactured ceramics remains challenging. Here, a UV‐curing approach is integrated in direct ink writing (DIW), taking advantage from DIW to enable an easy use of high solid‐loading pastes and multi‐layered materials with compositional changes; while, avoiding drying problems. UV‐curable opaque zirconia‐based slurries with a solid loading of 51 vol% are developed to fabricate dense and crack‐free alumina‐toughened zirconia (ATZ) containing 3 wt% alumina platelets. Importantly, a non‐reactive diluent is added to relieve polymerization‐induced internal stresses, avoid subsequent warping and cracking, and facilitate the de‐binding. For the first time, UV‐curing assisted DIW‐printed ceramic after sintering reveals even better mechanical properties than that processed by a conventional pressing. This is attributed to the aligned alumina platelets, enhancing crack deflection and improving the fracture toughness from 6.8 ± 0.3 MPa m0.5 (compacted) to 7.4 ± 0.3 MPa m0.5 (DIW). The four‐point bending strength of the DIW ATZ (1009 ± 93 MPa) is also higher than that of the conventionally manufactured equivalent (861 ± 68 MPa). Besides homogeneous ceramic, laminate structures are demonstrated. This work provides a valuable hybrid approach to additively manufacture tough and strong ceramic components.
High‐Quality Hybrid Perovskite Thin Films by Post‐Treatment Technologies in Photovoltaic Applications
Authors: Li Mingguang , Zhu Zheng , Wang Zhizhi , Pan Wenjing , Cao Xinxiu , Wu Guangbao , Chen Runfeng 
Published: November 2023

AbstractIncredible progress in photovoltaic devices based on hybrid perovskite materials has been made in the past few decades, and a record‐certified power conversion efficiency (PCE) of over 26% has been achieved in single‐junction perovskite solar cells (PSCs). In the fabrication of high‐efficiency PSCs, the postprocessing procedures toward perovskites are essential for designing high‐quality perovskite thin films; developing efficient and reliable post‐treatment techniques is very important to promote the progress of PSCs. Here, recent post‐treatment technological reforms toward perovskite thin films are summarized, and the principal functions of the post‐treatment strategies on the design of high‐quality perovskite films have been thoroughly analyzed by dividing into two categories in this review: thermal annealing (TA)‐related technique and TA‐free technique. The latest research progress of the above two types of post‐treatment techniques is summarized and discussed, focusing on the optimization of postprocessing conditions, the regulation of perovskite qualities, and the enhancement of device performance. Finally, an outlook of the prospect trends and future challenges for the fabrication of the perovskite layer and the production of highly efficient PSCs is given.
1D Insertion Chains Induced Small‐Polaron Collapse in MoS2 2D Layers Toward Fast‐Charging Sodium‐Ion Batteries
Authors: Lv Zhuoran , Zhao Chendong , Xie Miao , Cai Mingzhi , Peng Baixin , Ren Dayong , Fang Yuqiang , Dong Wujie , Zhao Wei , Lin Tianquan , Lv Ximeng , Zheng Gengfeng , Huang Fuqiang 
Published: November 2023

AbstractMolybdenum disulfide (MoS2) with high theoretical capacity is viewed as a promising anode for sodium‐ion batteries but suffers from inferior rate capability owing to the polaron‐induced slow charge transfer. Herein, a polaron collapse strategy induced by electron‐rich insertions is proposed to effectively solve the above issue. Specifically, 1D [MoS] chains are inserted into MoS2 to break the symmetry states of 2D layers and induce small‐polaron collapse to gain fast charge transfer so that the as‐obtained thermodynamically stable Mo2S3 shows metallic behavior with 107 times larger electrical conductivity than that of MoS2. Theoretical calculations demonstrate that Mo2S3 owns highly delocalized anions, which substantially reduce the interactions of Na−S to efficiently accelerate Na+ diffusion, endowing Mo2S3 lower energy barrier (0.38 vs 0.65 eV of MoS2). The novel Mo2S3 anode exhibits a high capacity of 510 mAh g−1 at 0.5 C and a superior high‐rate stability of 217 mAh g−1 at 40 C over 15 000 cycles. Further in situ and ex situ characterizations reveal the in‐depth reversible redox chemistry in Mo2S3. The proposed polaron collapse strategy for intrinsically facilitating charge transfer can be conducive to electrode design for fast‐charging batteries.
Trisulfide Bond‐Mediated Molecular Phototheranostic Platform for “Activatable” NIR‐II Imaging‐Guided Enhanced Gas/Chemo‐Hypothermal Photothermal Therapy
Authors: Wu Gui‐long , Liu Fen , Li Na , Fu Qian , Wang Cheng‐kun , Yang Sha , Xiao Hao , Tang Li , Wang Feirong , Zhou Wei , Wang Wenjie , Kang Qiang , Li Zelong , Lin Nanyun , Wu Yinyin , Chen Guodong , Tan Xiaofeng , Yang Qinglai 
Published: November 2023

AbstractTumor microenvironment (TME)‐triggered phototheranostic platform offers a feasible strategy to improve cancer diagnosis accuracy and minimize treatment side effects. Developing a stable and biocompatible molecular phototheranostic platform for TME‐activated second near‐infrared (NIR‐II) fluorescence imaging‐guided multimodal cascade therapy is a promising strategy for creating desirable anticancer agents. Herein, a new NIR‐II fluorescence imaging‐guided activatable molecular phototheranostic platform (IR‐FEP‐RGD‐S‐S‐S‐Fc) is presented for actively targeted tumor imaging and hydrogen sulfide (H2S) gas‐enhanced chemodynamic‐hypothermal photothermal combined therapy (CDT/HPTT). It is revealed for the first time that the coupling distance between IR‐FE and ferrocene is proportional to the photoinduced electron transfer (PET), and the aqueous environment is favorable for PET generation. The part of Cyclic‐RGDfK (cRGDfk) peptides can target the tumor and benefit the endocytosis of nanoparticles. The high‐concentration glutathione (GSH) in the TME will separate the fluorescence molecule and ferrocene by the GSH‐sensitive trisulfide bond, realizing light‐up NIR‐II fluorescence imaging and a cascade of trimodal synergistic CDT/HPTT/gas therapy (GT). In addition, the accumulation of hydroxyl radicals (•OH) and down‐regulation of glutathione peroxidase 4 (GPX4) can produce excessive harmful lipid hydroperoxides, ultimately leading to ferroptosis.
Smart Dual‐Exsolved Self‐Assembled Anode Enables Efficient and Robust Methane‐Fueled Solid Oxide Fuel Cells
Authors: Hu Feng , Chen Kongfa , Ling Yihan , Huang Yonglong , Zhao Sunce , Wang Sijiao , Gui Liangqi , He Beibei , Zhao Ling 
Published: November 2023

AbstractPerovskite oxides have emerged as alternative anode materials for hydrocarbon‐fueled solid oxide fuel cells (SOFCs). Nevertheless, the sluggish kinetics for hydrocarbon conversion hinder their commercial applications. Herein, a novel dual‐exsolved self‐assembled anode for CH4‐fueled SOFCs is developed. The designed Ru@Ru‐Sr2Fe1.5Mo0.5O6‐δ(SFM)/Ru‐Gd0.1Ce0.9O2‐δ(GDC) anode exhibits a unique hierarchical structure of nano‐heterointerfaces exsolved on submicron skeletons. As a result, the Ru@Ru‐SFM/Ru‐GDC anode‐based single cell achieves high peak power densities of 1.03 and 0.63 W cm−2 at 800 °C under humidified H2 and CH4, surpassing most reported perovskite‐based anodes. Moreover, this anode demonstrates negligible degradation over 200 h in humidified CH4, indicating high resistance to carbon deposition. Density functional theory calculations reveal that the created metal‐oxide heterointerfaces of Ru@Ru‐SFM and Ru@Ru‐GDC have higher intrinsic activities for CH4 conversion compared to pristine SFM. These findings highlight a viable design of the dual‐exsolved self‐assembled anode for efficient and robust hydrocarbon‐fueled SOFCs.
Palladium‐Catalyzed α‐Selective Halogenation of Triptycene Using Sulfur Directing Group
Authors: Ueno Keisuke , Nishii Yuji , Hirano Koji , Miura Masahiro 
Published: November 2023

AbstractFunctionalized triptycene derivatives have attracted significant research interest because of their potential applications in many research fields. Although the conventional Diels‐Alder reaction of anthracenes with benzynes has been a versatile synthetic tool for functionalized triptycenes, it is hardly possible to control the product regioselectivity. In this report, we demonstrate the selective synthesis of 1,8,13‐trisubstituted triptycenes by Pd‐catalyzed α‐bromination. As for the directing group, SMe group was the most effective to facilitate the halogenation of the proximal three benzene rings. The obtained product was further derivatized through allylation and Rh‐catalyzed hydroboration reactions.
Capturing Doublet Intermediate Emitters by Chemically Crosslinking Confinement towards Spatiotemporal Encryption
Authors: Li Haomin , Lei Huanyu , Ma Shudeng , Song Tianfu , Li Yan , Yu Haifeng 
Published: November 2023

AbstractPhotoluminescence is one of the most meticulous ways to manipulate light energy. Typical photoluminescent emitters are mostly stable substances with a pure photophysical process of spontaneous photon‐emission from their excited states. Intermediate emitters are elusive attributing to their synchronous energy transfer process including photophysical and incomplete photochemical pathways. An intermediate emitter containing radicals is more difficult to be observed due to its inherent chemical reactivity. Here, these challenges are overcome by spontaneously formed space limitations in polymer crosslinking networks meanwhile chemically active intermediates are captured. These doublet intermediates exhibit unique long‐wavelength emissions under chemically crosslinking confinement conditions, and their luminous mechanism provides a novel perspective for designing intermediate emitters with liquid‐crystal character and photoresponsive features towards spatiotemporal encryption, promising for the detection of photochemical reactions and the development of fascinating luminescent systems.
Nickel‐Catalyzed Asymmetric Propargyl‐Aryl Cross‐Electrophile Coupling
Authors: Ding Linlin , Zhao Yue , Lu Hongjian , Shi Zhuangzhi , Wang Minyan 
Published: November 2023

AbstractPerforming asymmetric cross‐coupling reactions between propargylic electrophiles and aryl nucleophiles is a well‐established method to build enantioenriched benzylic alkynes. Here, a catalytic enantioselective propargyl‐aryl cross‐coupling between two electrophiles was achieved for the first time in a stereoconvergent manner. Propargylic chlorides were treated with aryl iodides as well as heteroaryl iodides in the presence of a chiral nickel complex, and manganese metal was used as a stoichiometric reductant, allowing for the construction of a propargyl C‐aryl bond under mild conditions. An alternative dual nickel/photoredox catalytic protocol was also developed for this cross‐electrophile coupling in the absence of a metal reductant. The potential utility of this conversion is demonstrated in the facile construction of stereoenriched bioactive molecule derivatives and medicinal compounds based on the diversity of acetylenic chemistry. Detailed experimental studies have revealed the key mechanistic features of this transformation.
One‐Dimensionally Arranged Quantum‐Dot Superstructures Guided by a Supramolecular Polymer Template
Authors: Yamauchi Mitsuaki , Nakatsukasa Kanako , Kubo Naoki , Yamada Hiroko , Masuo Sadahiro 
Published: November 2023

AbstractColloidal quantum dots (QDs) exhibit important photophysical properties, such as long‐range energy diffusion, miniband formation, and collective photoluminescence, when aggregated into well‐defined superstructures, such as three‐dimensional (3D) and two‐dimensional (2D) superlattices. However, the construction of one‐dimensional (1D) QD superstructures, which have a simpler arrangement, is challenging; therefore, the photophysical properties of 1D‐arranged QDs have not been studied previously. Herein, we report a versatile strategy to obtain 1D‐arranged QDs using a supramolecular polymer (SP) template. The SP is composed of self‐assembling cholesterol derivatives containing two amide groups for hydrogen bonding and a carboxyl group as an adhesion moiety on the QDs. Upon mixing the SP and dispersed QDs in low‐polarity solvents, the QDs self‐adhered to the SP and self‐arranged into 1D superstructures through van der Waals interactions between the surface organic ligands of the QDs, as confirmed by transmission electron microscopy. Furthermore, we revealed efficient photoinduced fluorescence resonance energy transfer between the 1D‐arranged QDs by an in‐depth analysis of the emission spectra and decay curves.
Self‐Assembly of an [M8L24]16+ Intertwined Cube and a Giant [M12L16]24+ Orthobicupola
Authors: Baby Sainaba Arppitha , Venkateswarulu Mangili , Bhandari Pallab , Clegg Jack K. , Sarathi Mukherjee Partha 
Published: November 2023

AbstractThrough coordination‐driven self‐assembly, aesthetically captivating structures can be formed by tuning the length or flexibility of various components. The self‐assembly of an elongated rigid terphenyl‐based tetra‐pyridyl ligand (L1) with a cis‐Pd(II) acceptor produces an [M12L16]24+ triangular orthobicupola structure (1). When flexibility is introduced into the ligand by the incorporation of a ‐CH2‐ group between the dipyridylamine and terphenyl rings in the ligand (L2), anunique [M8L24]16+ water‐soluble ‘intertwined cubic structure’ (2) results. The inherent flexibility of ligand L2 might be the key factor behind the formation of the thermodynamically stable and ′intertwined cubic structure′ in this scenario. This research showcases the ability to design and fabricate novel, topologically distinctive molecular structures by a straightforward and efficient approach.
Room‐Temperature Salt Template Synthesis of Nitrogen‐Doped 3D Porous Carbon for Fast Metal‐Ion Storage
Authors: Chen Bochao , Qi Zijia , Chen Biao , Liu Xin , Li Huan , Han Xiaopeng , Zhou Guangmin , Hu Wenbin , Zhao Naiqin , He Chunnian 
Published: November 2023

AbstractThe water‐soluble salt‐template technique holds great promise for fabricating 3D porous materials. However, an equipment‐free and pore‐size controllable synthetic approach employing salt‐template precursors at room temperature has remained unexplored. Herein, we introduce a green room‐temperature antisolvent precipitation strategy for creating salt‐template self‐assembly precursors to universally produce 3D porous materials with controllable pore size. Through a combination of theoretical simulations and advanced characterization techniques, we unveil the antisolvent precipitation mechanism and provide guidelines for selecting raw materials and controlling the size of precipitated salt. Following the calcination and washing steps, we achieve large‐scale and universal production of 3D porous materials and the recycling of the salt templates and antisolvents. The optimized nitrogen‐doped 3D porous carbon (N‐3DPC) materials demonstrate distinctive structural benefits, facilitating a high capacity for potassium‐ion storage along with exceptional reversibility. This is further supported by in situ electrochemical impedance spectra, in situ Raman spectroscopy, and theoretical calculations. The anode shows a high rate capacity of 181 mAh g−1 at 4 A g−1 in the full cell. This study addresses the knowledge gap concerning the room‐temperature synthesis of salt‐template self‐assembly precursors for the large‐scale production of porous materials, thereby expanding their potential applications for electrochemical energy conversion and storage.
Multiplying Oxygen Permeability of a Ruddlesden‐Popper Oxide by Orientation Control via Magnets
Authors: Zhao Zhijun , Chen Guoxing , Escobar Cano Giamper , Kißling Patrick A. , Stölting Oliver , Breidenstein Bernd , Polarz Sebastian , Bigall Nadja C. , Weidenkaff Anke , Feldhoff Armin 
Published: November 2023

AbstractRuddlesden‐Popper‐type oxides exhibit remarkable chemical stability in comparison to perovskite oxides. However, they display lower oxygen permeability. We present an approach to overcome this trade‐off by leveraging the anisotropic properties of Nd2NiO4+δ. Its (a,b)‐plane, having oxygen diffusion coefficient and surface exchange coefficient several orders of magnitude higher than its c‐axis, can be aligned perpendicular to the gradient of oxygen partial pressure by a magnetic field (0.81 T). A stable and high oxygen flux of 1.40 mL min−1 cm−2 was achieved for at least 120 h at 1223 K by a textured asymmetric disk membrane with 1.0 mm thickness under the pure CO2 sweeping. Its excellent operational stability was also verified even at 1023 K in pure CO2. These findings highlight the significant enhancement in oxygen permeation membrane performance achievable by adjusting the grain orientation. Consequently, Nd2NiO4+δ emerges as a promising candidate for industrial applications in air separation, syngas production, and CO2 capture under harsh conditions.
Diphosphine Ligand‐Enabled Nickel‐Catalyzed Chelate‐Assisted Inner‐Selective Migratory Hydroarylation of Alkenes
Authors: He Hua‐Dong , Chitrakar Ravi , Cao Zhi‐Wei , Wang Dao‐Ming , She Li‐Qin , Zhao Peng‐Gang , Wu Yichen , Xu Yuan‐Qing , Cao Zhong‐Yan , Wang Peng 
Published: November 2023

AbstractThe precise control of the regioselectivity in the transition metal‐catalyzed migratory hydrofunctionalization of alkenes remains a big challenge. With a transient ketimine directing group, the nickel‐catalyzed migratory β‐selective hydroarylation and hydroalkenylation of alkenyl ketones has been realized with aryl boronic acids using alkyl halide as the mild hydride source for the first time. The key to this success is the use of a diphosphine ligand, which is capable of the generation of a Ni(II)‐H species in the presence of alkyl bromide, and enabling the efficient migratory insertion of alkene into Ni(II)‐H species and the sequent rapid chain walking process. The present approach diminishes organosilanes reductant, tolerates a wide array of complex functionalities with excellent regioselective control. Moreover, this catalytic system could also be applied to the migratory hydroarylation of alkenyl azahetereoarenes, thus providing a general approach for the preparation of 1,2‐aryl heteroaryl motifs with wide potential applications in pharmaceutical discovery.
Converting Waste Plastic to Liquid Organic Hydrogen Carriers
Authors: Soltani Mahdokht , Rorrer Julie E. 
Published: November 2023

AbstractThe accumulation of waste plastics in landfills and the environment, as well as the contribution of plastics manufacturing to global warming, call for the development of new technologies that would enable circularity for synthetic polymers. Thus far, emerging approaches for chemical recycling of plastics have largely focused on producing fuels, lubricants, and/or monomers. In a recent study, Junde Wei and colleagues demonstrated a new catalytic system capable of converting oxygen‐containing aromatic plastic waste into liquid organic hydrogen carriers (LOHCs), which can be used for hydrogen storage. The authors utilized Ru−ReOx/SiO2 materials with zeolite HZSM‐5 as a co‐catalyst for the direct hydrodeoxygenation (HDO) of oxygen‐containing aromatic plastic wastes that yield cycloalkanes as LOHCs with a theoretical hydrogen capacity of ≈5.74 wt % under mild reaction conditions. Subsequent efficiency and stability tests of cycloalkane dehydrogenation over Pt/Al2O3 validated that the HDO products can serve as LOHCs to generate H2 gas. Overall, their approach not only opens doors to alleviating the severe burden of plastic waste globally, but also offers a way to generate clean energy and ease the challenges associated with hydrogen storage and transportation.