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- ItemPersistent peri-Heptacene: Synthesis and In Situ Characterization(Weinheim : Wiley-VCH, 2021) Ajayakumar, M.R.; Ma, Ji; Lucotti, Andrea; Schellhammer, Karl Sebastian; Serra, Gianluca; Dmitrieva, Evgenia; Rosenkranz, Marco; Komber, Hartmut; Liu, Junzhi; Ortmann, Frank; Tommasini, Matteo; Feng, Xinliangn-peri-Acenes (n-PAs) have gained interest as model systems of zigzag-edged graphene nanoribbons for potential applications in nanoelectronics and spintronics. However, the synthesis of n-PAs larger than peri-tetracene remains challenging because of their intrinsic open-shell character and high reactivity. Presented here is the synthesis of a hitherto unknown n-PA, that is, peri-heptacene (7-PA), in which the reactive zigzag edges are kinetically protected with eight 4-tBu-C6H4 groups. The formation of 7-PA is validated by high-resolution mass spectrometry and in situ FT-Raman spectroscopy. 7-PA displays a narrow optical energy gap of 1.01 eV and exhibits persistent stability (t1/2≈25 min) under inert conditions. Moreover, electron-spin resonance measurements and theoretical studies reveal that 7-PA exhibits an open-shell feature and a significant tetraradical character. This strategy could be considered a modular approach for the construction of next-generation (3 N+1)-PAs (where N≥3). © 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH
- ItemThiophene-Based Conjugated Acetylenic Polymers with Dual Active Sites for Efficient Co-Catalyst-Free Photoelectrochemical Water Reduction in Alkaline Medium(Weinheim : Wiley-VCH, 2021) Borrelli, Mino; Querebillo, Christine Joy; Pastoetter, Dominik L.; Wang, Tao; Milani, Alberto; Casari, Carlo; Khoa Ly, Hoang; He, Fan; Hou, Yang; Neumann, Christof; Turchanin, Andrey; Sun, Hanjun; Weidinger, Inez M.; Feng, XinliangAlthough being attractive materials for photoelectrochemical hydrogen evolution reaction (PEC HER) under neutral or acidic conditions, conjugated polymers still show poor PEC HER performance in alkaline medium due to the lack of water dissociation sites. Herein, we demonstrate that tailoring the polymer skeleton from poly(diethynylthieno[3,2-b]thiophene) (pDET) to poly(2,6-diethynylbenzo[1,2-b:4,5-b′]dithiophene (pBDT) and poly(diethynyldithieno[3,2-b:2′,3′-d]thiophene) (pDTT) in conjugated acetylenic polymers (CAPs) introduces highly efficient active sites for water dissociation. As a result, pDTT and pBDT, grown on Cu substrate, demonstrate benchmark photocurrent densities of 170 μA cm−2 and 120 μA cm−2 (at 0.3 V vs. RHE; pH 13), which are 4.2 and 3 times higher than that of pDET, respectively. Moreover, by combining DFT calculations and electrochemical operando resonance Raman spectroscopy, we propose that the electron-enriched Cβ of the outer thiophene rings of pDTT are the water dissociation active sites, while the −C≡C− bonds function as the active sites for hydrogen evolution. © 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH
- ItemHigh-Quality Graphene Using Boudouard Reaction(Weinheim : Wiley-VCH, 2022) Grebenko, Artem K.; Krasnikov, Dmitry V.; Bubis, Anton V.; Stolyarov, Vasily S.; Vyalikh, Denis V.; Makarova, Anna A.; Fedorov, Alexander; Aitkulova, Aisuluu; Alekseeva, Alena A.; Gilshtein, Evgeniia; Bedran, Zakhar; Shmakov, Alexander N.; Alyabyeva, Liudmila; Mozhchil, Rais N.; Ionov, Andrey M.; Gorshunov, Boris P.; Laasonen, Kari; Podzorov, Vitaly; Nasibulin, Albert G.Following the game-changing high-pressure CO (HiPco) process that established the first facile route toward large-scale production of single-walled carbon nanotubes, CO synthesis of cm-sized graphene crystals of ultra-high purity grown during tens of minutes is proposed. The Boudouard reaction serves for the first time to produce individual monolayer structures on the surface of a metal catalyst, thereby providing a chemical vapor deposition technique free from molecular and atomic hydrogen as well as vacuum conditions. This approach facilitates inhibition of the graphene nucleation from the CO/CO2 mixture and maintains a high growth rate of graphene seeds reaching large-scale monocrystals. Unique features of the Boudouard reaction coupled with CO-driven catalyst engineering ensure not only suppression of the second layer growth but also provide a simple and reliable technique for surface cleaning. Aside from being a novel carbon source, carbon monoxide ensures peculiar modification of catalyst and in general opens avenues for breakthrough graphene-catalyst composite production.
- ItemTailoring Intermolecular Interactions Towards High‐Performance Thermoelectric Ionogels at Low Humidity(Weinheim : Wiley-VCH, 2022) Zhao, Wei; Sun, Tingting; Zheng, Yiwei; Zhang, Qihao; Huang, Aibin; Wang, Lianjun; Jiang, WanDevelopment of ionic thermoelectric (iTE) materials is of immense interest for efficient heat-to-electricity conversion due to their giant ionic Seebeck coefficient (Si), but challenges remain in terms of relatively small Si at low humidity, poor stretchability, and ambiguous interaction mechanism in ionogels. Herein, a novel ionogel is reported consisting of polyethylene oxide (PEO), polyethylene oxide-polypropylene oxide-polyethylene oxide (P123), and 1-ethyl-3-methylimidazolium acetate (Emim:OAC). By delicately designing the interactions between ions and polymers, the migration of anions is restricted due to their strong binding with the hydroxyl groups of polymers, while the transport of cations is facilitated through segmental motions due to the increased amorphous regions, thereby leading to enlarged diffusion difference between the cations and anions. Moreover, the plasticizing effect of P123 and Emim:OAC can increase the elongation at break. As a consequence, the ionogel exhibits excellent properties including high Si (18 mV K−1 at relative humidity of 60%), good ionic conductivity (1.1 mS cm−1), superior stretchability (787%), and high stability (over 80% retention after 600 h). These findings show a promising strategy to obtain multifunctional iTE materials by engineering the intermolecular interactions and demonstrate the great potential of ionogels for harvesting low-grade heat in human-comfortable humidity environments.
- ItemElectronic Doping and Enhancement of n‐Channel Polycrystalline OFET Performance through Gate Oxide Modifications with Aminosilanes(Weinheim : Wiley-VCH, 2021) Shin, Nara; Schellhammer, Karl Sebastian; Lee, Min Ho; Zessin, Jakob; Hambsch, Mike; Salleo, Alberto; Ortmann, Frank; Mannsfeld, Stefan C.B.Self-assembled monolayers (SAMs) are widely employed in organic field-effect transistors to modify the surface energy, surface roughness, film growth kinetics, and electrical surface potential of the gate oxide to control the device's operating voltage. In this study, amino-functionalized SAM molecules are compared to pure alkylsilane SAMS in terms of their impact on the electrical properties of organic field-effect transistors, using the n-type polycrystalline small molecule semiconductor material N,N′-dioctyl-3,4,9,10-perylenedicarboximide (PTCDI-C8). In order to understand the electronic impact of the amino groups, the effect of both the number of amino-containing functional groups and the SAM molecular length are systematically studied. Though amino-functionalized SAM materials have been studied previously, this study is, for the first time, able to shed light on the nature of the doping effect that occurs when the gate oxide is treated with polar aminosilane materials. By a comprehensive theoretical study of the interface on the molecular level, it is shown that the observed shift in the threshold voltage is caused by free charges, which are attracted to the PTCDI-C8 and are stabilized there by protonated aminosilanes. This attraction and the voltage shift can be systematically tuned by varying the length of the neutral terminal chain of the aminosilane. © 2021 The Authors. Advanced Materials Interfaces published by Wiley-VCH GmbH
- ItemSelf‐Patterning of Multifunctional Heusler Membranes by Dewetting(Weinheim : Wiley-VCH, 2021) Lünser, Klara; Diestel, Anett; Nielsch, Kornelius; Fähler, SebastianNi-Mn-based Heusler alloys are an emerging class of materials which enable actuation by (magnetic) shape memory effects, magnetocaloric cooling, and thermomagnetic energy harvesting. Multifunctional materials have a particular advantage for miniaturization since their functionality is already built within the material. However, often complex microtechnological processing is required to bring these materials into shape. Here, self-organized formation of single crystalline membranes having arrays of rectangular holes with high aspect ratio is demonstrated. Dewetting avoids the need for complicated processing and allows to prepare freestanding Ni–Mn–Ga–Co membranes. These membranes are martensitic and magnetic, and their functional properties are not disturbed by self-patterning. Feature sizes of these membranes can be tailored by film thickness and heat treatment, and the tendencies can be explained with dewetting. As an outlook, the advantages of these multifunctional membranes for magnetocaloric and thermomagnetic microsystems are sketched. © 2021 The Authors. Advanced Materials Interfaces published by Wiley-VCH GmbH
- ItemTailoring Plasmonics of Au@Ag Nanoparticles by Silica Encapsulation(Weinheim : Wiley-VCH, 2021) Schultz, Johannes; Kirner, Felizitas; Potapov, Pavel; Büchner, Bernd; Lubk, Axel; Sturm, Elena V.Hybrid metallic nanoparticles (NPs) encapsulated in oxide shells are currently intensely studied for plasmonic applications in sensing, medicine, catalysis, and photovoltaics. Here, a method for the synthesis of Au@Ag@SiO2 cubes with a uniform silica shell of variable and adjustable thickness in the nanometer range is introduced and their excellent, highly reproducible, and tunable optical response is demonstrated. Varying the silica shell thickness, the excitation energies of the single NP plasmon modes can be tuned in a broad spectral range between 2.55 and 3.25 eV. Most importantly, a strong coherent coupling of the surface plasmons is revealed at the silver–silica interface with Mie resonances at the silica–vacuum interface leading to a significant field enhancement at the encapsulated NP surface in the range of 100% at shell thicknesses t ≃ 20 nm. Consequently, the synthesis method and the field enhancement open pathways to a widespread use of silver NPs in plasmonic applications including photonic crystals and may be transferred to other non-precious metals. © 2021 The Authors. Advanced Optical Materials published by Wiley-VCH GmbH
- ItemBeyond Janus Geometry: Characterization of Flow Fields around Nonspherical Photocatalytic Microswimmers(Weinheim : Wiley-VCH, 2022) Heckel, Sandra; Bilsing, Clemens; Wittmann, Martin; Gemming, Thomas; Büttner, Lars; Czarske, Jürgen; Simmchen, JulianeCatalytic microswimmers that move by a phoretic mechanism in response to a self-induced chemical gradient are often obtained by the design of spherical janus microparticles, which suffer from multi-step fabrication and low yields. Approaches that circumvent laborious multi-step fabrication include the exploitation of the possibility of nonuniform catalytic activity along the surface of irregular particle shapes, local excitation or intrinsic asymmetry. Unfortunately, the effects on the generation of motion remain poorly understood. In this work, single crystalline BiVO4 microswimmers are presented that rely on a strict inherent asymmetry of charge-carrier distribution under illumination. The origin of the asymmetrical flow pattern is elucidated because of the high spatial resolution of measured flow fields around pinned BiVO4 colloids. As a result the flow from oxidative to reductive particle sides is confirmed. Distribution of oxidation and reduction reactions suggests a dominant self-electrophoretic motion mechanism with a source quadrupole as the origin of the induced flows. It is shown that the symmetry of the flow fields is broken by self-shadowing of the particles and synthetic surface defects that impact the photocatalytic activity of the microswimmers. The results demonstrate the complexity of symmetry breaking in nonspherical microswimmers and emphasize the role of self-shadowing for photocatalytic microswimmers. The findings are leading the way toward understanding of propulsion mechanisms of phoretic colloids of various shapes.
- ItemFreestanding Nanolayers of a Wide-Gap Topological Insulator through Liquid-Phase Exfoliation(Weinheim : Wiley-VCH, 2021) Lê Anh, Mai; Potapov, Pavel; Wolf, Daniel; Lubk, Axel; Glatz, Bernhard; Fery, Andreas; Doert, Thomas; Ruck, MichaelThe layered salt Bi14Rh3I9 is a weak three-dimensional (3D) topological insulator (TI), that is, a stack of two-dimensional (2D) TIs. It has a wide non-trivial band gap of 210 meV, which is generated by strong spin-orbit coupling, and possesses protected electronic edge-states. In the structure, charged layers of (Formula presented.) (Bi4Rh)3I]2+ honeycombs and (Formula presented.) Bi2I8]2− chains alternate. The non-trivial topology of Bi14Rh3I9 is an inherent property of the 2D intermetallic fragment. Here, the exfoliation of Bi14Rh3I9 was performed using two different chemical approaches: (a) through a reaction with n-butyllithium and poly(vinylpyrrolidone), (b) through a reaction with betaine in dimethylformamide at 55 °C. The former yielded few-layer sheets of the new compound Bi12Rh3I, while the latter led to crystalline sheets of Bi14Rh3I9 with a thickness down to 5 nm and edge-lengths up to several ten microns. X-ray diffraction and electron microscopy proved that the structure of Bi14Rh3I9 remained intact. Thus, it was assumed that the particles are still TIs. Dispersions of these flakes now allow for next steps towards the envisioned applications in nanoelectronics, such as the study of quantum coherence in deposited films, the combination with superconducting particles or films for the generation of Majorana fermions, or studies on their behavior under the influence of magnetic or electric fields or in contact with various materials occurring in devices. The method presented generally allows to exfoliate layers with high specific charges and thus the use of layered starting materials beyond van der Waals crystals. © 2020 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH
- ItemDual‐Salt Electrolyte Additives Enabled Stable Lithium Metal Anode/Lithium–Manganese‐Rich Cathode Batteries(Weinheim : Wiley-VCH, 2021) Zhou, Junhua; Lian, Xueyu; Shi, Qitao; Liu, Yu; Yang, Xiaoqin; Bachmatiuk, Alicja; Liu, Lijun; Sun, Jingyu; Yang, Ruizhi; Choi, Jin-Ho; Rummeli, Mark H.Although lithium (Li) metal anode/lithium–manganese-rich (LMR) cathode batteries have an ultrahigh energy density, the highly active Li metal and structural deterioration of LMR can make the usage of these batteries difficult. Herein, a multifunctional electrolyte containing LiBF4 and LiFSI dual-salt additives is designed, which enables the superior cyclability of Li/LMR cells with capacity retentions of ≈83.4%, 80.4%, and 76.6% after 400 cycles at 0.5, 1, and 2 C, respectively. The dual-salt electrolyte can form a thin, uniform, and inorganic species-rich solid electrolyte interphase (SEI) and cathode electrolyte interphase (CEI). In addition, it alleviates the bulk Li corrosion and enhances the structural sustainability of LMR cathode. Moreover, the electrolyte design strategy provides insights to develop other high-voltage lithium metal batteries (HVLMBs) to enhance the cycle stability.