Structure elucidation of polyheptazine imide by electron diffraction — a templated 2D carbon nitride networkw

Structure elucidation of a condensed carbon IV) nitride with a stoichiometry close to C3N4 by electron diffraction reveals a two-dimensional planar heptazine-based network containing isolated melamine molecules in the trigonal voids

Unprecedented Zeolite-Like Framework Topology Constructed from Cages with 3-Rings in a Barium Oxonitridophosphate

A novel oxonitridophosphate, Ba19P36O6+xN66-xCl8+x(x≈4.54), has been synthesized by heating a multicomponent reactant mixture consisting of phosphoryl triamide OP(NH2)3, thiophosphoryl triamide SP(NH2)3, BaS, and NH4Cl enclosed in an evacuated and sealed silica glass ampule up to 750°C. Despite the presence of side phases, the crystal structure was elucidated ab initio from high-resolution synchrotron powder diffraction data (λ=39.998 pm) applying the charge flipping algorithm supported by independent symmetry information derived from electron diffraction (ED) and scanning transmission electron microscopy (STEM). The compound crystallizes in the cubic space group Fm3c (no. 226) with a = 2685.41(3) pm and Z = 8. As confirmed by Rietveld refinement, the structure comprises all-side vertex sharing P(O,N)4 tetrahedra forming slightly distorted 3846812 cages representing a novel composite building unit (CBU). Interlinked through their 4-rings and additional 3-rings, the cages build up a 3D network with a framework density FD = 14.87 T/1000 Å3 and a 3D 8-ring channel system. Ba2+ and Clˉ as extra-framework ions are located within the cages and channels of the framework. The structuralmodel is corroborated by 31P double-quantum(DQ) /single-quantum (SQ) and triple-quantum (TQ) /single-quantum (SQ) 2D correlation MAS NMR spectroscopy. According to 31P{1H} C-REDOR NMR measurements, the H content is less than one H atom per unit cell

Photobase effect for just-in-time delivery in photocatalytic hydrogen generation

Carbon dots (CDs) are a promising nanomaterial for photocatalytic applications. However, the mechanism of the photocatalytic processes remains the subject of a debate due to the complex internal structure of the CDs, comprising crystalline and molecular units embedded in an amorphous matrix, rendering the analysis of the charge and energy transfer pathways between the constituent parts very challenging. Here we propose that the photobasic effect, that is the abstraction of a proton from water upon excitation by light, facilitates the photoexcited electron transfer to the proton. We show that the controlled inclusion in CDs of a model photobase, acridine, resembling the molecular moieties found in photocatalytically active CDs, strongly increases hydrogen generation. Ultrafast spectroscopy measurements reveal proton transfer within 30ps of the excitation. This way, we use a model system to show that the photobasic effect may be contributing to the photocatalytic H-2 generation of carbon nanomaterials and suggest that it may be tuned to achieve further improvements. The study demonstrates the critical role of the understanding the dynamics of the CDs in the design of next generation photocatalysts

Tailoring Plasmonic Bimetallic Nanocatalysts Toward Sunlight-Driven H-2 Production

Hybrid nanoparticles combining plasmonic and catalytic components have recently gained interest for their potential use in sunlight-to-chemical energy conversion. However, a deep understanding of the structure-performance that maximizes the use of the incoming energy remains elusive. Here, a suite of Au and Pd based nanostructures in core-shell and core-satellites configurations are designed and their photocatalytic activity for Hydrogen (H-2) generation under sunlight illumination is tested. Formic acid is employed as H-2 source. Core-satellite systems show a higher enhancement of the reaction upon illumination, compared to core-shell ones. Electromagnetic simulations reveal that a key difference between both configurations is the excitation of highly localized and asymmetric electric fields in the gap between both materials. In this scheme, the core Au particle acts as an antenna, efficiently capturing visible light via the excitation of localized plasmon resonances, while the surrounding Pd satellites transduce the locally-enhanced electric field into catalytic activity. These findings advance the understanding of plasmon-driven photocatalysis, and provide an important benchmark to guide the design of the next generation of plasmonic bimetallic nanostructures

Fine‐Tuning Blue‐Emitting Halide Perovskite Nanocrystals

Lead halide perovskite nanocrystals (NCs) with narrow, bright emission in the visible range are promising candidates for light-emitting applications. Near-unity quantum yields have been realized for green and red-emitting perovskites, but efficient, stable blue-emitting perovskite materials are scarce. Current methods to synthesize quantum-confined CsPbBr3 NCs with blue emission are limited to specific wavelength ranges and still suffer from inhomogeneously broadened emission profiles. Herein, anisotropic blue-green emitting CsPbBr3 NCs are synthesized in ambient atmosphere using a spontaneous crystallization method. Optical spectroscopy reveals a gradual, asymptotic photoluminescence (PL) redshift of pristine colloidal NCs after synthesis. During this process, the emission quality improves notably as the PL spectra become narrower and more symmetric, accompanied by a PL intensity increase. Electron microscopy indicates that the gradual redshift stems from an isotropic growth of the CsPbBr3 NCs in at least two dimensions, likely due to residual precursor ions in the dispersion. Most importantly, the growth process can be halted at any point by injecting an enhancement solution containing PbBr2 and organic capping ligands. Thus, excellent control over NC size is achieved, allowing for nanometer-precise tunability of the respective emission wavelength in the range between 475 and 500 nm, enhancing the functionality of these already impressive NCs

Interfacial Manganese-Doping in CsPbBr3 Nanoplatelets by Employing a Molecular Shuttle

Mn-doping in cesium lead halide perovskite nanoplatelets (NPls) is of particular importance where strong quantum confinement plays a significant role towards the exciton-dopant coupling. In this work, we report an immiscible bi-phasic strategy for post-synthetic Mn-doping of CsPbX3 (X=Br, Cl) NPls. A systematic study shows that electron-donating oleylamine acts as a shuttle ligand to transport MnX2 through the water-hexane interface and deliver it to the NPls. The halide anion also plays an essential role in maintaining an appropriate radius of Mn2+ and thus fulfilling the octahedral factor required for the formation of perovskite crystals. By varying the thickness of parent NPls, we can tune the dopant incorporation and, consequently, the exciton-to-dopant energy transfer process in doped NPls. Time-resolved optical measurements offer a detailed insight into the exciton-to-dopant energy transfer process. This new approach for post-synthetic cation doping paves a way towards exploring the cation exchange process in several other halide perovskites at the polar-nonpolar interface

Manganese‐Doping‐Induced Quantum Confinement within Host Perovskite Nanocrystals through Ruddlesden–Popper Defects

The concept of doping Mn2+ ions into II–VI semiconductor nanocrystals (NCs) was recently extended to perovskite NCs. To date, most studies on Mn2+ doped NCs focus on enhancing the emission related to the Mn2+ dopant via an energy transfer mechanism. Herein, we found that the doping of Mn2+ ions into CsPbCl3 NCs not only results in a Mn2+‐related orange emission, but also strongly influences the excitonic properties of the host NCs. We observe for the first time that Mn2+ doping leads to the formation of Ruddlesden–Popper (R.P.) defects and thus induces quantum confinement within the host NCs. We find that a slight doping with Mn2+ ions improves the size distribution of the NCs, which results in a prominent excitonic peak. However, with increasing the Mn2+ concentration, the number of R.P. planes increases leading to smaller single‐crystal domains. The thus enhanced confinement and crystal inhomogeneity cause a gradual blue shift and broadening of the excitonic transition, respectively

Building blocks and COFs formed in concert —Three‐component synthesis of pyrene‐fused Azaacene covalent organic framework in the bulk and as films

A three‐component synthesis methodology is described for the formation of covalent organic frameworks (COFs) containing extended aromatics. Notably, this approach enables synthesis of the building blocks and COF along parallel reaction landscapes, on a similar timeframe. The use of fragmental building block components, namely pyrene dione diboronic acid as aggregation‐inducing COF precursor and the diamines o‐phenylenediamine (Ph), 2,3‐diaminonaphthalene (Naph), or (1R,2R)‐(+)‐1,2‐diphenylethylenediamine (2Ph) as extending functionalization units in conjunction with 2,3,6,7,10,11‐hexahydroxytriphenylene, resulted in the formation of the corresponding pyrene‐fused azaacene, i.e., Aza‐COF series with full conversion of the dione moiety, long‐range order, and high surface area. In addition, the novel three‐component synthesis was successfully applied to produce highly crystalline, oriented thin films of the Aza‐COFs with nanostructured surfaces on various substrates. The Aza‐COFs exhibit light absorption maxima in the blue spectral region, and each Aza‐COF presents a distinct photoluminescence profile. Transient absorption measurements of Aza‐Ph‐ and Aza‐Naph‐COFs suggest ultrafast relaxation dynamics of excited‐states within these COFs.Deutsche Forschungsgemeinschaft | Ref. ME 4515/1-2Fundação para a Ciência e a Tecnologia | Ref. SFRH/BD/141865/2018Fundação para a Ciência e a Tecnologia | Ref. PTDC/QUI-OUT/2095/2021Fundação para a Ciência e a Tecnologia | Ref. UIDB/50011/2020Fundação para a Ciência e a Tecnologia | Ref. UIDP/50011/2020Fundação para a Ciência e a Tecnologia | Ref. LA/P/0006/2020National Science Foundation (EE.UU.) | Ref. DMR-1848067Engineering and Physical Sciences Research Council (Reino Unido) | Ref. EP/V055127/1Agencia Estatal de Investigación | Ref. RYC2020-030414-IUniversidade de Vigo/CISU

Pyrite nanocrystals: shape-controlled synthesis and tunable optical properties via reversible self-assembly

Nanocrystals from non-toxic, earth abundant materials have recently received great interest for their potential large-scale application in photovoltaics and photocatalysis. Here, we report for the first time on the shape-controlled and scalable synthesis of phase-pure pyrite (FeS2) nanocrystals employing the simple, inexpensive, thermal reaction of iron–oleylamine complexes with sulfur in oleylamine. Either dendritic nanocrystals (nanodendrites) or nanocubes are obtained by adjusting the iron-oleylamine concentration and thereby controlling the nucleus concentration and kinetics of the nanocrystal growth. Pyrite nanodendrites are reversibly assembled by washing with toluene and redispersed by adding the ligand oleylamine. The assembly–redispersion-process is accompanied by an increased absorption in the red/near-infrared spectral region for the aggregated state. This increased low-energy absorption is due to interactions between the closed-packed nanocrystals. High-concentration nanodendrite dispersions are used to prepare pyrite thin films with strong broadband extinction in the visible and near-infrared. These films are attractive candidates for light harvesting in all inorganic solar cells based on earth abundant, non-toxic materials as well as for photocatalytic applications