- 13 articles in high-impact journals
- 2 cover pages
- 2 hot topics
- 1 special issue
- 1 very important paper
- 18 citations
- 15 press releases & highlights
- 14+ average impact factor
- 100% collaborative publications
Thiophene‐Bridged Donor–Acceptor sp2‐Carbon‐Linked 2D Conjugated Polymers as Photocathodes for Water Reduction
S. Xu, H. Sun, M. Addicoat, B. P. Biswal, F. He, S. Park, S. Paasch, T. Zhang, W. Sheng, E. Brunner, Y. Hou, M. Richter, X. Feng
Adv. Mater., 2020, in press (open access).
Photoelectrochemical (PEC) water reduction, converting solar energy into environmentally friendly hydrogen fuel, requires delicate design and synthesis of semiconductors with appropriate bandgaps, suitable energy levels of the frontier orbitals, and high intrinsic charge mobility. In this work, the synthesis of a novel bithiophene‐bridged donor–acceptor‐based 2D sp2‐carbon‐linked conjugated polymer (2D CCP) is demonstrated. The Knoevenagel polymerization between the electron‐accepting building block 2,3,8,9,14,15‐hexa(4‐formylphenyl) diquinoxalino[2,3‐a:2′,3′‐c]phenazine (HATN‐6CHO) and the first electron‐donating linker 2,2′‐([2,2′‐bithiophene]‐5,5′‐diyl)diacetonitrile (ThDAN) provides the 2D CCP‐HATNThDAN (2D CCP‐Th). Compared with the corresponding biphenyl‐bridged 2D CCP‐HATN‐BDAN (2D CCP‐BD), the bithiophene‐based 2D CCP‐Th exhibits a wide light‐harvesting range (up to 674 nm), a optical energy gap (2.04 eV), and highest energy occupied molecular orbital–lowest unoccupied molecular orbital distributions for facilitated charge transfer, which make 2D CCP‐Th a promising candidate for PEC water reduction. As a result, 2D CCP‐Th presents a superb H2‐evolution photocurrent density up to ≈7.9 µA cm−2 at 0 V versus reversible hydrogen electrode, which is superior to the reported 2D covalent organic frameworks and most carbon nitride materials (0.09–6.0 µA cm−2). Density functional theory calculations identify the thiophene units and cyano substituents at the vinylene linkage as active sites for the evolution of H2.
One‐Pot Synthesis of Boron‐Doped Polycyclic Aromatic Hydrocarbons via 1,4‐Boron Migration
J.-J. Zhang, M. C. Tang, Y. Fu, K.-H. Low, J. Ma, L. Yang, J. J. Weigand, J. Liu, V. W.-W. Yam, X. Feng
Angew. Chem. Int. Ed., 2020, in press (open access).
Here, we demonstrate a novel one‐pot synthetic method towards a series of boron‐doped polycyclic aromatic hydrocarbons (B‐PAHs, 1a-1o), including hitherto unknown B‐doped zethrene derivatives, from ortho‐aryl substituted diarylalkynes with high atom efficiency and broad substrate scopes. A reaction mechanism is proposed based on the experimental investigation together with the theoretical calculations, which involves a unique 1,4‐boron migration process. The resultant benchtop‐stable B‐PAHs are thoroughly investigated by X‐ray crystallography, cyclic voltammetry, UV/Vis absorption, and fluorescence spectroscopies. The blue and green organic light‐emitting diode (OLED) devices based on 1f and 1k are further fabricated, demonstrating the promising application potential of B‐PAHs in organic optoelectronics.
Liquid-Phase Exfoliated GeSe Nanoflakes for Photoelectrochemical-Type Photodetectors and Photoelectrochemical Water Splitting
G. Bianca, M. I. Zappia, S. Bellani, Z. Sofer, M. Serri, L. Najafi, R. Oropesa-Nuñez, B. Martín-García, T. Hartman, L. Leoncino, D. Sedmidubský, V. Pellegrini, G. Chiarello, F. Bonaccorso
ACS Appl. Mater. Interfaces, 2020, 12, 48598–48613. Link to article.
Photoelectrochemical (PEC) systems represent powerful tools to convert electromagnetic radiation into chemical fuels and electricity. In this context, two-dimensional (2D) materials are attracting enormous interest as potential advanced photo(electro)catalysts and, recently, 2D group-IVA metal monochalcogenides have been theoretically predicted to be water splitting photocatalysts. In this work, we use density functional theory calculations to theoretically investigate the photocatalytic activity of single-/few-layer GeSe nanoflakes for both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) in pH conditions ranging from 0 to 14. Our simulations show that GeSe nanoflakes with different thickness can be mixed in the form of nanoporous films to act as nanoscale tandem systems, in which the flakes, depending on their thickness, can operate as HER- and/or OER photocatalysts. On the basis of theoretical predictions, we report the first experimental characterization of the photo(electro)catalytic activity of single-/few-layer GeSe flakes in different aqueous media, ranging from acidic to alkaline solutions: 0.5 M H2SO4 (pH 0.3), 1 M KCl (pH 6.5), and 1 M KOH (pH 14). The films of the GeSe nanoflakes are fabricated by spray coating GeSe nanoflakes dispersion in 2-propanol obtained through liquid-phase exfoliation of synthesized orthorhombic (Pnma) GeSe bulk crystals. The PEC properties of the GeSe nanoflakes are used to design PEC-type photodetectors, reaching a responsivity of up to 0.32 AW–1 (external quantum efficiency of 86.3%) under 455 nm excitation wavelength in acidic electrolyte. The obtained performances are superior to those of several self-powered and low-voltage solution-processed photodetectors, approaching that of self-powered commercial UV–Vis photodetectors. The obtained results inspire the use of 2D GeSe in proof-of-concept water photoelectrolysis cells.
Synthesis of Vinylene‐Linked Two‐Dimensional Conjugated Polymers via the Horner–Wadsworth–Emmons Reaction
D. L. Pastoetter, S. Xu, M. Borrelli, M. Addicoat, B. P. Biswal, S. Paasch, A. Dianat, H. Thomas, R. Berger, S. Reineke, E. Brunner, G. Cuniberti, M. Richter, X. Feng
In this work, we demonstrate the first synthesis of vinylene‐linked 2D CPs, namely, 2D poly(phenylenequinoxalinevinylene)s 2D‐PPQV1 and 2D‐PPQV2, via the Horner–Wadsworth–Emmons (HWE) reaction of C2‐symmetric 1,4‐bis(diethylphosphonomethyl)benzene or 4,4′‐bis(diethylphosphonomethyl)biphenyl with C3‐symmetric 2,3,8,9,14,15‐hexa(4‐formylphenyl)diquinoxalino[2,3‐a:2′,3′‐c]phenazine as monomers. Density functional theory (DFT) simulations unveil the crucial role of the initial reversible C−C single bond formation for the synthesis of crystalline 2D CPs. Powder X‐ray diffraction (PXRD) studies and nitrogen adsorption‐desorption measurements demonstrate the formation of proclaimed crystalline, dual‐pore structures with surface areas of up to 440 m2 g−1. More importantly, the optoelectronic properties of the obtained 2D‐PPQV1 (Eg=2.2 eV) and 2D‐PPQV2 (Eg=2.2 eV) are compared with those of cyano‐vinylene‐linked 2D‐CN‐PPQV1 (Eg=2.4 eV) produced by the Knoevenagel reaction and imine‐linked 2D COF analog (2D‐C=N‐PPQV1, Eg=2.3 eV), unambiguously proving the superior conjugation of the vinylene‐linked 2D CPs using the HWE reaction.
Graphene transistors for real-time monitoring molecular self-assembly dynamics
M. Gobbi, A. Galanti, M.-A. Stoeckel, B. Zyska, S. Bonacchi, S. Hecht, P. Samorì
Mastering the dynamics of molecular assembly on surfaces enables the engineering of predictable structural motifs to bestow programmable properties upon target substrates. Yet, monitoring self-assembly in real time on technologically relevant interfaces between a substrate and a solution is challenging, due to experimental complexity of disentangling interfacial from bulk phenomena. Here, we show that graphene devices can be used as highly sensitive detectors to read out the dynamics of molecular self-assembly at the solid/liquid interface in-situ. Irradiation of a photochromic molecule is used to trigger the formation of a metastable self-assembled adlayer on graphene and the dynamics of this process are monitored by tracking the current in the device over time. In perspective, the electrical readout in graphene devices is a diagnostic and highly sensitive means to resolve molecular ensemble dynamics occurring down to the nanosecond time scale, thereby providing a practical and powerful tool to investigate molecular self-organization in 2D.
Scalable spray-coated graphene-based electrodes for high-power electrochemical double-layer capacitors operating over a wide range of temperature
M. A. Garakani, S. Bellani, V. Pellegrini, R. Oropesa-Nuñez, A. E. Del Rio Castillo, S. Abouali, L. Najafi, B. Martín-García, A. Ansaldo, P. Bondavalli, C. Demirci, V. Romano, E. Mantero, L. Marasco, M. Prato, G. Bracciale, F. Bonaccorso
Energy Storage Mater., 2021, 34, 1–11. Link to article (open access).
Advancements in electrochemical double-layer capacitor (EDLC) technology require the concomitant use of novel efficient electrode materials and viable electrode manufacturing methods. Cost-effectiveness, scalability and sustainability are key-drivers for fulfilling product development chain accepted by worldwide legislations. Herein, we report a scalable and sprayable “green” electrode material-based ink based on activated carbon and single-/few-layer graphene (SLG/FLG) flakes. We show that, contrary to commercial reduced graphene oxide, defect-free and flat SLG/FLG flakes reduce the friction of ions over the electrode films, while spray coating deposition of our ink maximises the electrolyte accessibility to the electrode surface area. Sprayed SLG/FLG flakes-based EDLCs display superior rate capability performance (e.g., specific energies of 31.5, 23.7 and 12.5 Wh kg−1 at specific powers of 150, 7500 and 30000 W kg−1, respectively) compared to both SLG/FLG flakes-free devices and commercial-like EDLCs produced by slurry-coating method. The use of SLG/FLG flakes enables our sprayed EDLCs to operate in a wide range of temperature (−40/+100°C) compatible with ionic liquid/organic solvent-based electrolytes, overcoming the specific power limits of AC-based EDLCs. A prototype EDLCs stack consisting of multiple large-area EDLCs, each one displaying a capacitance of 25 F, demonstrates the industrial potential of our technology.
Luminescent sp2-Carbon-Linked 2D Conjugated Polymers with High Photostability
Y. Li, B. P. Biswal, M. A. Addicoat, S. Paasch, P. Imbrasas, S. Park, H. Shi, E. Brunner, M. Richter, S. Lenk, S. Reineke, X. Feng
Chem. Mater., 2020, 32, 7985–7991. Link to article.
Luminescent organic materials with high photostability are essential in optoelectronics, sensor, and photocatalysis applications. However, small organic molecules are generally sensitive to UV irradiation, giving rise to chemical decompositions. In this work, we demonstrate two novel CN-substituted two-dimensional sp2-carbon-linked conjugated polymers (2D CCPs) containing a chromophore triphenylene unit. The Knoevenagel polymerization between 2,3,6,7,10,11-hexakis(4-formylphenyl)triphenylene (HFPTP) and 1,4-phenylenediacetonitrile (PDAN) or 2,2′-(biphenyl-4,4′-diyl)diacetonitrile (BDAN), provides the crystalline 2D CCP-HFPTP-PDAN (2D CCP-1) and 2D CCP-HFPTP-BDAN (2D CCP-2) with dual pore structures, respectively. 2D CCP-1 and 2D CCP-2 exhibit the photoluminescence quantum yield (PLQY) up to 24.9 and 32.3%, which are the highest values among the reported 2D conjugated polymers and π-conjugated 2D covalent organic frameworks. Furthermore, compared with the well-known emissive small molecule tetrakis(carbazol-9-yl)-4,6-dicyanobenzene (4CzIPN), both 2D CCPs show superior photostability under UV irradiation for 2 h, profiting from the twisted and rigid structures of the CN-substituted vinylene linkages. The present work will trigger the further explorations of novel organic emitters embedded in 2D CCPs with high PLQY and photostability, which can be useful for optoelectronic devices.
Role of Exchange Interactions in the Magnetic Response and Intermolecular Recognition of Chiral Molecules
A. Dianat, R. Gutierrez, H. Alpern, V. Mujica, A. Ziv, S. Yochelis, O. Millo, Y. Paltiel, G. Cuniberti
Nano Lett., 2020, 20, 7077–7086. Link to article.
The physical origin of the so-called chirality-induced spin selectivity (CISS) effect has puzzled experimental and theoretical researchers over the past few years. Early experiments were interpreted in terms of unconventional spin–orbit interactions mediated by the helical geometry. However, more recent experimental studies have clearly revealed that electronic exchange interactions also play a key role in the magnetic response of chiral molecules in singlet states. In this investigation, we use spin-polarized closed-shell density functional theory calculations to address the influence of exchange contributions to the interaction between helical molecules as well as of helical molecules with magnetized substrates. We show that exchange effects result in differences in the interaction properties with magnetized surfaces, shedding light into the possible origin of two recent important experimental results: enantiomer separation and magnetic exchange force microscopy with AFM tips functionalized with helical peptides.
Synthesis of Robust MOFs@COFs Porous Hybrid Materials via an Aza‐Diels–Alder Reaction: Towards High‐Performance Supercapacitor Materials
H. Peng, J. Raya, F. Richard, W. Baaziz, O. Ersen, A. Ciesielski, P. Samorì
Angew. Chem. Int. Ed., 2020, 59, 19602–19609. Link to article and accepted manuscript (open access). Featured in Special Issue: Functional Porous Materials Chemistry and Hot Topic: Batteries and Supercapacitors. Selected as a Very Important Paper.
Metal–organic frameworks (MOFs) and covalent organic frameworks (COFs) have attracted enormous attention in recent years. Recently, MOF@COF are emerging as hybrid architectures combining the unique features of the individual components to enable the generation of materials displaying novel physicochemical properties. Herein we report an unprecedented use of aza‐Diels–Alder cycloaddition reaction as post‐synthetic modification of MOF@COF‐LZU1, to generate aza‐MOFs@COFs hybrid porous materials with extended π‐delocalization. A a proof‐of‐concept, the obtained aza‐MOFs@COFs is used as electrode in supercapacitors displaying specific capacitance of 20.35 μF cm−2 and high volumetric energy density of 1.16 F cm−3. Our approach of post‐synthetic modification of MOFs@COFs hybrids implement rational design for the synthesis of functional porous materials and expands the plethora of promising application of MOFs@COFs hybrid porous materials in energy storage applications.
On-surface synthesis of super-heptazethrene
S. Mishra, J. Melidonie, K. Eimre, S. Obermann, O. Gröning, C. A. Pignedoli, P. Ruffieux, X. Feng, R. Fasel
Zethrenes are model diradicaloids with potential applications in spintronics and optoelectronics. Despite a rich chemistry in solution, on-surface synthesis of zethrenes has never been demonstrated. We report the on-surface synthesis of super-heptazethrene on Au(111). Scanning tunneling spectroscopy investigations reveal that super-heptazethrene exhibits an exceedingly low HOMO–LUMO gap of 230 meV and, in contrast to its open-shell singlet ground state in the solution phase and in the solid-state, likely adopts a closed-shell ground state on Au(111).
Photomodulation of Charge Transport in All‐Semiconducting 2D–1D van der Waals Heterostructures with Suppressed Persistent Photoconductivity Effect
Z. Liu, H. Qiu, C. Wang, Z. Chen, B. Zyska, A. Narita, A. Ciesielski, S. Hecht, L. Chi, K. Müllen, P. Samorì
Van der Waals heterostructures (VDWHs), obtained via the controlled assembly of 2D atomically thin crystals, exhibit unique physicochemical properties, rendering them prototypical building blocks to explore new physics and for applications in optoelectronics. As the emerging alternatives to graphene, monolayer transition metal dichalcogenides and bottom‐up synthesized graphene nanoribbons (GNRs) are promising candidates for overcoming the shortcomings of graphene, such as the absence of a bandgap in its electronic structure, which is essential in optoelectronics. Herein, VDWHs comprising GNRs onto monolayer MoS2 are fabricated. Field‐effect transistors (FETs) based on such VDWHs show an efficient suppression of the persistent photoconductivity typical of MoS2, resulting from the interfacial charge transfer process. The MoS2‐GNR FETs exhibit drastically reduced hysteresis and more stable behavior in the transfer characteristics, which is a prerequisite for the further photomodulation of charge transport behavior within the MoS2‐GNR VDWHs. The physisorption of photochromic molecules onto the MoS2‐GNR VDWHs enables reversible light‐driven control over charge transport. In particular, the drain current of the MoS2‐GNR FET can be photomodulated by 52%, without displaying significant fatigue over at least 10 cycles. Moreover, four distinguishable output current levels can be achieved, demonstrating the great potential of MoS2‐GNR VDWHs for multilevel memory devices.
Ultrathin two-dimensional conjugated metal–organic framework single-crystalline nanosheets enabled by surfactant-assisted synthesis
Z. Wang, G. Wang, H. Qi, M. Wang, M. Wang, S. Park, H. Wang, M. Yu, U. Kaiser, A. Fery, S. Zhou, R. Dong, X. Feng
Chem. Sci., 2020, 11, 7665–7671. Link to article (open access).
Two-dimensional conjugated metal–organic frameworks (2D c-MOFs) have recently emerged for potential applications in (opto-)electronics, chemiresistive sensing, and energy storage and conversion, due to their excellent electrical conductivity, abundant active sites, and intrinsic porous structures. However, developing ultrathin 2D c-MOF nanosheets (NSs) for facile solution processing and integration into devices remains a great challenge, mostly due to unscalable synthesis, low yield, limited lateral size and low crystallinity. Here, we report a surfactant-assisted solution synthesis toward ultrathin 2D c-MOF NSs, including HHB-Cu (HHB = hexahydroxybenzene), HHB-Ni and HHTP-Cu (HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene). For the first time, we achieve single-crystalline HHB-Cu(Ni) NSs featured with a thickness of 4–5 nm (∼8–10 layers) and a lateral size of 0.25–0.65 μm2, as well as single-crystalline HHTP-Cu NSs with a thickness of ∼5.1 ± 2.6 nm (∼10 layers) and a lateral size of 0.002–0.02 μm2. Benefiting from the ultrathin feature, the synthetic NSs allow fast ion diffusion and high utilization of active sites. As a proof of concept, when serving as a cathode material for Li-ion storage, HHB-Cu NSs deliver a remarkable rate capability (charge within 3 min) and long-term cycling stability (90% capacity retention after 1000 cycles), superior to the corresponding bulk materials and other reported MOF cathodes.
Demonstration of a Broadband Photodetector Based on a Two‐Dimensional Metal–Organic Framework
H. Arora, R. Dong, T. Venanzi, J. Zscharschuch, H. Schneider, M. Helm, X. Feng, E. Cánovas, A. Erbe
Adv. Mater., 2020, 32, 1907063. Link to article (open access). COVER PAGE. cfaed, HZDR, EurekAlert!, NWA, Phys.org, ScienceDaily, Laser Focus World, Optics & Photonics News and PhotonicsViews press releases.
Metal–organic frameworks (MOFs) are emerging as an appealing class of highly tailorable electrically conducting materials with potential applications in optoelectronics. Yet, the realization of their proof‐of‐concept devices remains a daunting challenge, attributed to their poor electrical properties. Following recent work on a semiconducting Fe3(THT)2(NH4)3 (THT: 2,3,6,7,10,11‐triphenylenehexathiol) 2D MOF with record‐high mobility and band‐like charge transport, here, an Fe3(THT)2(NH4)3 MOF‐based photodetector operating in photoconductive mode capable of detecting a broad wavelength range from UV to NIR (400–1575 nm) is demonstrated. The narrow IR bandgap of the active layer (≈0.45 eV) constrains the performance of the photodetector at room temperature by band‐to‐band thermal excitation of charge carriers. At 77 K, the device performance is significantly improved; two orders of magnitude higher voltage responsivity, lower noise equivalent power, and higher specific detectivity of 7 × 108 cm Hz1/2 W−1 are achieved under 785 nm excitation. These figures of merit are retained over the analyzed spectral region (400–1575 nm) and are commensurate to those obtained with the first demonstrations of graphene‐ and black‐phosphorus‐based photodetectors. This work demonstrates the feasibility of integrating conjugated MOFs as an active element into broadband photodetectors, thus bridging the gap between materials' synthesis and technological applications.