bluuebunny/crossref_metadata_2025_split huggingface dataset:
Atomic‐Precision Tailoring of Au–Ag Core–Shell Composite Nanoparticles for Direct Electrochemical‐Plasmonic Hydrogen Evolution in Water Splitting
Authors: Mo Jiaying , Barbosa Eduardo C. M. , Wu Simson , Li Yiyang , Sun Yuancheng , Xiang Weikai , Li Tong , Pu Shengda , Robertson Alex , Wu Tai‐sing , Soo Yun‐liang , Alves Tiago V. , Camargo Pedro H. C. , Kuo Winson , Tsang Shik Chi Edman 
Published: May 2021

AbstractTraditionally, bandgap materials are a prerequisite to photocatalysis since they can harness a reasonable range of the solar spectrum. However, the high impedance across the bandgap and the low concentration of intrinsic charge carriers have limited their energy conversion. By contrast, metallic nanoparticles possess a sea of free electrons that can effectively promote the transition to the excited state for reactions. Here, an atomic layer of a bimetallic concoction of silver–gold shells is precisely fabricated onto an Au core via a sonochemical dispersion approach to form a core–shell of Au–Ag that exploits the wide availability of excited states of Ag while maintaining an efficient localized surface plasmon resonance (LSPR) of Au. Catalytic results demonstrate that this mix of Ag and Au can convert solar energy to hydrogen at high efficiency with an increase of 112.5% at an optimized potential of −0.5 V when compared to light‐off conditions under the electrochemical LSPR. This outperforms the commercial Pt catalysts by 62.1% with a hydrogen production rate of 1870 µmol g−1 h−1 at room temperature. This study opens a new route for tuning the range of light capture of hydrogen evolution reaction catalysts using fabricated core–shell material through the combination of LSPR with electrochemical means.
Bioinspired Energy Storage and Harvesting Devices
Authors: Ren Jing , Liu Qiang , Pei Ying , Wang Yang , Yang Shuo , Lin Shihui , Chen Wenshuai , Ling Shengjie , Kaplan David L. 
Published: May 2021

AbstractKnowledge learned from nature demonstrates that system performance can be enhanced and optimized by hierarchical structural design which has dramatically expanded implications for synthetic materials, from design to implementation. In recent years, numerous bioinspired and biomimetic strategies are devoted to design energy storage and harvesting devices. For these devices, efficient and stable electrode/electrolyte interfaces, modified interactions, and new functions are desired, which remain a challenge to fully meet the requirement of the rapidly developed electronic industry. This review, taking lithium batteries, nanogenerators and solar cells as examples, provides a summary and discussion of how the bio‐inspired strategies can influence the electrode/device design and the corresponding interface interactions. By applying and learning from biological materials, natural hierarchical structure, surface topography, and biochemical process, enhanced performance and stability for energy devices can be achieved. Future research expectations in this field and energy management are also discussed.
Printing between the Lines: Intricate Biomaterial Structures Fabricated via Negative Embodied Sacrificial Template 3D (NEST3D) Printing
Authors: Doyle Stephanie E. , Duchi Serena , Onofrillo Carmine , Quigley Anita , Di Bella Claudia , Pirogova Elena , O'Connell Cathal D. 
Published: May 2021

AbstractExtrusion printing techniques are widely used across tissue engineering and related fields for producing 3D structures from biocompatible thermoplastics, however the achievable structural complexity and porosity can be limited by the nozzle‐based, layer‐by‐layer deposition process. Here, how this limitation can be overcome through a new technique termed Negative Embodied Sacrificial Template 3D printing is illustrated. It is demonstrated how the negative pattern within a 3D printed object can easily describe geometries that are extremely challenging to extrusion print directly with biomaterials, and at high resolution. Negative patterns in a water‐soluble sacrificial template can be “developed” by casting in a secondary material and dissolving the template, creating exquisitely complex 3D structures including hyper‐branched dendritic structures and open lattices with stiffnesses tuneable over 3 orders of magnitude. The technique is amenable to a plethora of materials from biodegradable thermoplastics (such as polycaprolactone) to resins (including acrylic and epoxy), silicones (including the Sylgard 184 polydimethylsiloxane formulation), ceramics (including hydroxyapatite composites), hydrogels (including agarose and gelatin methacryloyl), low‐melt temperature metal alloys and others. Using an unmodified, consumer‐grade printer, NEST3D printing achieves high resolution, intricate biomaterial structures with potential applications in biomedical implants and tissue engineering scaffolds.
Recent Progress in Luminous Particle‐Encapsulated Host–Guest Metal‐Organic Frameworks for Optical Applications
Authors: Guo Bing‐Bing , Yin Jia‐Cheng , Li Na , Fu Zi‐Xuan , Han Xiao , Xu Jialiang , Bu Xian‐He 
Published: May 2021

AbstractMetal‐organic frameworks (MOFs) as a unique class of porous crystalline materials have received comprehensive attention in the past decades. Among them, luminescent MOFs (LMOFs) have been a well‐known branch on account of their relevance as optical materials in contemporary era. The establishment of host–guest hybrid LMOF materials has triggered a hot search area owing to the extensive range of applications that can be adjusted by soliciting different functional luminescent guests. Current developments in the thought‐provoking application of host–guest LMOFs have stretched into far‐ranging fields, including light regulation, imaging, sensing, data encryption, etc. This review discusses on the hybridization of MOFs with functional luminescent particles (LPs) as guests for the construction of a series of extraordinary host–guest luminescent composite materials (LP@MOFs). The basic aspects, involving the preconcentration of MOF hosts and luminous guests as well as the comprehensive synthetic strategies of LP@MOFs are introduced. Furthermore, the applications of luminescent LP@MOF materials are highlighted, with a particular emphasis on the present and continuing challenges and the demand trends of such materials that need to be explored.
Enhanced Near‐Infrared Perovskite Light‐Emitting Devices by Introducing Choline Chloride Layer
Authors: Xu Xiaoxiao , Xiao Ke , Hou Guozhi , Zhang Yangyi , Zhu Ting , Xu Ling , Xu Jun , Chen Kunji 
Published: May 2021

AbstractThe existing interface defect states between perovskite and the transport layer is one of the dominant reasons to limit the performance of near‐infrared (NIR) perovskite light‐emitting devices (PeLEDs). Herein, a quaternary ammonium halide choline chloride layer is introduced to improve the wettability of the hole transport layer (HTL) and passivate defect states. As a consequence, the performance of the NIR PeLEDs is obviously enhanced. A maximum output power density of 4.7 mW cm−2 has been achieved by optimizing the concentration of choline chloride. Furthermore, the alternating current (AC) driving mode is introduced to reduce thermal degradation and charge accumulation in the interface region. It is demonstrated that the emission intensity as well as the stability of PeLEDs can be further improved.
Blue LED Induced Manganese (I) Catalysed Direct C2−H Activation of Pyrroles with Aryl Diazoesters
Authors: Sar Saibal , Das Ranajit , Sen Subhabrata 
Published: May 2021

AbstractHerein, we have reported a blue LED mediated manganese pentacarbonyl bromide catalysed incorporation of carbene moieties from aryl diazoesters onto 1H‐pyrroles via their selective C2−H activation. A manganese metal‐carbene has been identified as the active catalyst to facilitate the reaction. Eighteen mono substituted pyrrole derivatives were isolated in good to excellent yields (67→82%) and the disubstituted products were also formed in minor quantities (5 to 8%). HPLC based kinetics study enabled optimization of the reaction. Control experiments, FT‐IR, NMR and GC‐MS based characterization elucidated the putative reaction mechanism.magnified image
Catalyst‐Free Decarbonylative Trifluoromethylthiolation Enabled by Electron Donor‐Acceptor Complex Photoactivation
Authors: Lipp Alexander , Badir Shorouk O. , Dykstra Ryan , Gutierrez Osvaldo , Molander Gary A. 
Published: May 2021

AbstractA catalyst‐ and additive‐free decarbonylative trifluoromethylthiolation of aldehyde feedstocks has been developed. This operationally simple, scalable, and open‐to‐air transformation is driven by the selective photoexcitation of electron donor‐acceptor (EDA) complexes, stemming from the association of 1,4‐dihydropyridines (donor) with N‐(trifluoromethylthio)phthalimide (acceptor), to trigger intermolecular single‐electron transfer events under ambient‐ and visible light‐promoted conditions. Extension to other electron acceptors enables the synthesis of thiocyanates and thioesters, as well as the difunctionalization of [1.1.1]propellane. The mechanistic intricacies of this photochemical paradigm are elucidated through a combination of experimental efforts and high‐level quantum mechanical calculations [dispersion‐corrected (U)DFT, DLPNO‐CCSD(T), and TD‐DFT]. This comprehensive study highlights the necessity for EDA complexation for efficient alkyl radical generation. Computation of subsequent ground state pathways reveals that SH2 addition of the alkyl radical to the intermediate radical EDA complex is extremely exergonic and results in a charge transfer event from the dihydropyridine donor to the N‐(trifluoromethylthio)phthalimide acceptor of the EDA complex. Experimental and computational results further suggest that product formation also occurs via SH2 reaction of alkyl radicals with 1,2‐bis(trifluoromethyl)disulfane, generated in‐situ through combination of thiyl radicals.magnified image
Exploring the Size‐Dependent Hydrogen Storage Property on Ti‐Doped Bn Clusters by Diatomic Deposition: Temperature Controlled H2 Release
Authors: Rodríguez‐Kessler Peter L. , Rodríguez‐Domínguez Adán R. , MacLeod‐Carey Desmond , Muñoz‐Castro Alvaro 
Published: May 2021

AbstractThe hydrogen storage properties of Ti‐doped Bn () clusters are investigated by using the “diatomic deposition method” with further evaluation by density functional theory computations. The results show that TiBn () clusters possess the ability to storage up to four H2 molecules, reaching a mass fraction of 6.12%. Further, the hydrogen release temperature is analyzed by molecular dynamics simulations with a variable temperature. It turns out that the TiB7 and TiB9 clusters release the H2 molecules at T ≲ 700 K, while TiB8 requires higher temperature due to stronger interactions with the H2 molecules, confirmed by the electronic density of states. The size‐dependent properties and odd–even nuclearity on the clusters can be useful for applications with controlled temperature. These results serve for further design of novel materials with reversible and controlled hydrogen storage properties based on TiB7/TiB9 motifs. Additionally, new lower‐energy isomers for TiB4 and TiB9 clusters were found within the accuracy of the all‐electron triple‐ζ Slater [slater type orbital (STO)‐Triple‐zeta basis set(TZP)] basis set.
A Review of Integrated Systems Based on Perovskite Solar Cells and Energy Storage Units: Fundamental, Progresses, Challenges, and Perspectives
Authors: Zhang Xuefeng , Song Wei‐Li , Tu Jiguo , Wang Jingxiu , Wang Mingyong , Jiao Shuqiang 
Published: May 2021

AbstractWith the remarkable progress of photovoltaic technology, next‐generation perovskite solar cells (PSCs) have drawn significant attention from both industry and academic community due to sustainable energy production. The single‐junction‐cell power conversion efficiency (PCE) of PSCs to date has reached up to 25.2%, which is competitive to that of commercial silicon‐based solar cells. Currently, solar cells are considered as the individual devices for energy conversion, while a series connection with an energy storage device would largely undermine the energy utilization efficiency and peak power output of the entire system. For substantially addressing such critical issue, advanced technology based on photovoltaic energy conversion–storage integration appears as a promising strategy to achieve the goal. However, there are still great challenges in integrating and engineering between energy harvesting and storage devices. In this review, the state‐of‐the‐art of representative integrated energy conversion–storage systems is initially summarized. The key parameters including configuration design and integration strategies are subsequently analyzed. According to recent progress, the efforts toward addressing the current challenges and critical issues are highlighted, with expectation of achieving practical integrated energy conversion–storage systems in the future.
Two‐Dimensional Bis(dithiolene)iron(II) Self‐Powered UV Photodetectors with Ultrahigh Air Stability
Authors: Wang Ying‐Chiao , Chiang Chun‐Hao , Chang Chi‐Ming , Maeda Hiroaki , Fukui Naoya , Wang I‐Ta , Wen Cheng‐Yen , Lu Kuan‐Cheng , Huang Shao‐Ku , Jian Wen‐Bin , Chen Chun‐Wei , Tsukagoshi Kazuhito , Nishihara Hiroshi 
Published: May 2021

AbstractOrganometallic two‐dimensional (2D) nanosheets with tailorable components have recently fascinated the optoelectronic communities due to their solution‐processable nature. However, the poor stability of organic molecules may hinder their practical application in photovoltaic devices. Instead of conventional organometallic 2D nanosheets with low weatherability, an air‐stable π‐conjugated 2D bis(dithiolene)iron(II) (FeBHT) coordination nanosheet (CONASH) is synthesized via bottom‐up liquid/liquid interfacial polymerization using benzenehexathiol (BHT) and iron(II) ammonium sulfate [Fe(NH4)2(SO4)2] as precursors. The uncoordinated thiol groups in FeBHT are easily oxidized, but the Fe(NH4)2(SO4)2 dissociation rate is slow, which facilitates the protection of sulfur groups by iron(II) ions. The density functional theory calculates that the resultant FeBHT network gains the oxygen‐repelling function for oxidation suppression. In air, the FeBHT CONASH exhibits self‐powered photoresponses with short response times (<40 ms) and a spectral responsivity of 6.57 mA W−1, a specific detectivity of 3.13 × 1011 Jones and an external quantum efficiency of 2.23% under 365 nm illumination. Interestingly, the FeBHT self‐powered photodetector reveals extremely high long‐term air stability, maintaining over 94% of its initial photocurrent after aging for 60 days without encapsulation. These results open the prospect of using organometallic 2D materials in commercialized optoelectronic fields.
Layered Perovskites in Solar Cells: Structure, Optoelectronic Properties, and Device Design
Authors: Sirbu Dumitru , Balogun Folusho Helen , Milot Rebecca L. , Docampo Pablo 
Published: May 2021

AbstractLayered hybrid perovskites (LPKs) have emerged as a viable solution to address perovskite stability concerns and enable their implementation in wide‐scale energy harvesting. Yet, although more stable, the performance of devices incorporating LPKs still lags behind that of state‐of‐the‐art, multi‐cation perovskite materials. This is typically assigned to their poor charge transport, currently caused by the choice of cations used within the organic layer. On balance, a compromise between efficiency and stability is sought, involving careful control of phase purity and distribution, interfaces and energy/charge transfer processes. Further progress is hindered by the difficulty in identifying the fundamental optoelectronic processes in these materials. Here, the high exciton binding energy of LPKs lead to the formation of multiple photoexcited species, which greatly complicate measurement interpretation. In this light, this review gives an overview of how complementary measurement techniques must be used to separate the contributions from the different species in order to identify device bottlenecks, and become a useful tool to narrow down the limitless list of organic cations. A move away from making compromises to mitigate the impact of poor charge transport is required. The root of the problem must be addressed instead through rational design of the interlayer cations.
Synthesis, Applications, and Prospects of Quantum‐Dot‐in‐Perovskite Solids
Authors: Chen Haijie , Pina Joao M. , Hou Yi , Sargent Edward H. 
Published: May 2021

AbstractQuantum‐dot‐in‐perovskite solids (QDiP), wherein colloidal quantum dots (CQDs) are inside bulk hybrid halide perovskites, have emerged as a novel class of semiconductors with mixed dimensionalities. The interfacial quality achieved enables good charge transport from the perovskite matrix to the embedded dots and leads to photon interaction functionalities that go beyond those of the single‐phase constituents. In this review, recent advances in the synthesis and compositions of QDiP are showcased, the improved optoelectronic properties are discussed, and their applications are explored. The authors focus on how the combination of CQDs and halide perovskites enhances stability, charge transport, and carrier diffusion length. Progress in device operation (prominently, light‐emitting diodes and solar cells) is summarized, and a perspective on future opportunities for QDiPs is given.
Pd‐Catalyzed Amidation of Silyl Enol Ethers With CO and Azides via an Isocyanate Intermediate
Authors: Jiang Yi‐Qian , Gu Zheng‐Yang , Chen Ye , Xia Ji‐Bao 
Published: May 2021

AbstractAn efficient Pd‐catalyzed amidation of silyl enol ethers to produce β‐ketoamides has been developed using carbon monoxide and sulfonyl azides. The tandem reaction provides a simple and straightforward approach for the synthesis of β‐ketoamides under mild conditions without any additive. The mechanistic studies indicate that the reaction undergoes via an in situ generated isocyanate intermediate.
Genetic landscape of Gullah African Americans
Authors: Zimmerman Kip D. , Schurr Theodore G. , Chen Wei‐Min , Nayak Uma , Mychaleckyj Josyf C. , Quet Queen , Moultrie Lee H. , Divers Jasmin , Keene Keith L. , Kamen Diane L. , Gilkeson Gary S. , Hunt Kelly J. , Spruill Ida J. , Fernandes Jyotika K. , Aldrich Melinda C. , Reich David , Garvey W. Timothy , Langefeld Carl D. , Sale Michèle M. , Ramos Paula S. 
Published: May 2021

AbstractObjectivesGullah African Americans are descendants of formerly enslaved Africans living in the Sea Islands along the coast of the southeastern U.S., from North Carolina to Florida. Their relatively high numbers and geographic isolation were conducive to the development and preservation of a unique culture that retains deep African features. Although historical evidence supports a West‐Central African ancestry for the Gullah, linguistic and cultural evidence of a connection to Sierra Leone has led to the suggestion of this country/region as their ancestral home. This study sought to elucidate the genetic structure and ancestry of the Gullah.Materials and MethodsWe leveraged whole‐genome genotype data from Gullah, African Americans from Jackson, Mississippi, African populations from Sierra Leone, and population reference panels from Africa and Europe to infer population structure, ancestry proportions, and global estimates of admixture.ResultsRelative to non‐Gullah African Americans from the Southeast US, the Gullah exhibited higher mean African ancestry, lower European admixture, a similarly small Native American contribution, and increased male‐biased European admixture. A slightly tighter bottleneck in the Gullah 13 generations ago suggests a largely shared demographic history with non‐Gullah African Americans. Despite a slightly higher relatedness to populations from Sierra Leone, our data demonstrate that the Gullah are genetically related to many West African populations.DiscussionThis study confirms that subtle differences in African American population structure exist at finer regional levels. Such observations can help to inform medical genetics research in African Americans, and guide the interpretation of genetic data used by African Americans seeking to explore ancestral identities.
N‐Heterocyclic Carbene/Carboxylic Acid Co‐Catalysis Enables Oxidative Esterification of Demanding Aldehydes/Enals, at Low Catalyst Loading
Authors: Harnying Wacharee , Sudkaow Panyapon , Biswas Animesh , Berkessel Albrecht 
Published: May 2021

AbstractWe report the discovery that simple carboxylic acids, such as benzoic acid, boost the activity of N‐heterocyclic carbene (NHC) catalysts in the oxidative esterification of aldehydes. A simple and efficient protocol for the transformation of a wide range of sterically hindered α‐ and β‐substituted aliphatic aldehydes/enals, catalyzed by a novel and readily accessible N‐Mes‐/N‐2,4,6‐trichlorophenyl 1,2,4‐triazolium salt, and benzoic acid as co‐catalyst, was developed. A whole series of α/β‐substituted aliphatic aldehydes/enals hitherto not amenable to NHC‐catalyzed esterification could be reacted at typical catalyst loadings of 0.02–1.0 mol %. For benzaldehyde, even 0.005 mol % of NHC catalyst proved sufficient: the lowest value ever achieved in NHC catalysis. Preliminary studies point to carboxylic acid‐induced acceleration of acyl transfer from azolium enolate intermediates as the mechanistic basis of the observed effect.
Synthesis of dioctyl sulfosuccinate‐doped polypyrrole grains by aqueous chemical oxidative polymerization and their use as light‐responsive liquid marble stabilizer
Authors: Osumi Tomoki , Seike Musashi , Oyama Keigo , Higashimoto Shinya , Hirai Tomoyasu , Nakamura Yoshinobu , Fujii Syuji 
Published: May 2021

AbstractPolypyrrole grains are synthesized by aqueous chemical oxidative polymerization using ferric chloride as an oxidant in the presence of bis(2‐ethylhexyl) sulfosuccinate sodium salt as both a dopant and a hydrophobizing agent. The resulting grain products are characterized in terms of their size, morphology, surface and bulk chemical compositions, hydrophilicity‐hydrophobicity balance, (photo) thermal property, and electrical conductivity. Scanning electron microscopy studies indicate that the grains are aggregates of atypical primary grains with submicrometer size. Elemental microanalysis and thermogravimetric analysis confirm that the polypyrrole is preferably doped with dioctyl sulfosuccinate compared with chloride ion, and dioctyl sulfosuccinate/chloride ion dopant ratio increases with an increase of bis(2‐ethylhexyl) sulfosuccinate sodium salt concentration in the polymerization systems. The grains show near‐infrared light‐to‐heat photothermal property, which is confirmed by thermography. The data obtained through X‐ray photoelectron spectroscopy indicate the presence of dioctyl sulfosuccinate dopants on the surface of the grains, and therefore the dried polypyrrole grains show hydrophobic character. The dried grains can work as a light‐responsive liquid marble (LM) stabilizer. Motions of the LM can be driven by near‐infrared laser irradiation‐induced Marangoni flow on planar air‐water surface. The release of internal liquid can be achieved by controlled disruption of the LM via external stimulus application.