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Water pollution by hexavalent chromium, Cr(VI), poses serious concerns due to its detrimental public health effects. In this work, we report the synthesis, characterization, and sorption properties for Cr(VI) by MoS42- intercalated layered double hydroxide, CoAl-MoS4-LDH (CoAl-MoS4). Our results show that CoAl-MoS4 can effectively remove Cr(VI) ions from acidic, neutral, and basic media. At neutral medium, it exhibits a very strong affinity, Kd ∼ 1.91 × 105 mL/g, toward Cr(VI) ions. Under such conditions, this material can remove over 99% of Cr(VI) from a ∼104 ppb of Cr(VI) contaminated solutions, leaving behind residual concentration below the World Health Organization (WHO) defined limit for drinking water. Moreover, our study shows that CoAl-MoS4 is a highly-competent Cr(VI) adsorbent exhibiting a removal capacity (qm) as high as ∼231 mg/g. The CoAl-MoS4 follows pseudo-second order rate kinetics for the sorption of chromate, and the concentration dependent sorption data can be fitted well with the Langmuir sorption isotherm. Furthermore, CoAl-MoS4 is highly selective to Cr(VI) ions in the presence of various competitive ions in contaminated water systems. All these results suggest that CoAl-MoS4 is a very efficient sorbent for decontamination of hexavalent chromate from wastewater systems.

Strong coupling between light and matter can produce hybrid eigenstates known as exciton-polaritons. Although polariton dynamics are important photophysical properties, the relaxation pathways of polaritons in different coupling regimes have seen limited attention. This paper reports the dynamics of hybridized states from 2D Ruddlesden-Popper perovskites coupled to plasmonic nanoparticle lattices. The open cavity architecture of Al lattices enables the coupling strength to be modulated by varying either the lead halide perovskite film thickness or the superstrate refractive index. Both experiments and finite-difference time-domain simulations of the optical dispersion diagrams showed avoided crossings that are a signature of strong coupling. Our analytical model also elucidated the correlation between the exciton/plasmon mixing ratio and polariton coupling strength. Using fs-transient absorption spectroscopy, we found that both the upper and lower polaritons have shorter lifetimes than the excitons and that polaritons can show faster excited-state dynamics when they have access to additional energy transfer channels.

International audience; Two-dimensional (2D) hybrid lead iodide perovskites have gained prominence due to their remarkable structural tunability, optoelectronic features, and moisture stability, which have rendered them as attractive alternatives to 3D MAPbI3 for optoelectronic devices. 2D multilayer lead bromide perovskites remain an unfathomed phase space with the lack of systematic studies to establish the structure, photophysical properties and stability behavior of this family of 2D halide perovskites. Herein, we present new members of bilayer lead bromide perovskites (CmH2m+1NH3)2(CH3NH3)Pb2Br7 (m = 6–8) that belong to the Ruddlesden–Popper structure type, incorporating long chain alkyl-monoammonium cations (CmH2m+1NH3) of hexylammonium (m = 6), heptylammonium (m = 7), and octylammonium (m = 8). A universal solution synthetic methodology for bulk multilayer lead bromide perovskites is presented with all structures solved and refined using single crystal X-ray diffraction. The studied bilayer lead bromide perovskites demonstrate a decrease in the lattice rigidity and lattice match of the inorganic perovskite layer–organic layer, as the alkyl-monoammonium chain length increases. In comparison to their iodide analogues, the bilayer lead bromide compounds exhibit elongation of their stacking axis despite the smaller dimensions of the [PbBr6]4− lattice, while their internal lattice strain was calculated to be reduced, inferring a greater lattice match between the inorganic [PbBr6]4− perovskite layer and organic layer. The (CmH2m+1NH3)2(CH3NH3)Pb2Br7 (m = 4, 6–8) compounds exhibit narrow-band emission near 2.5 eV. Time-resolved photoluminescence (PL) displays longer carrier lifetimes on the nanosecond time scale comparing to their iodide analogues, where electronic structure calculations indicate that the increase of the alkyl chain length and, thus, lattice softness enhances nonradiative recombinations. A complete set of air, light, and heat stability tests on unencapsulated thin films of (CmH2m+1NH3)2(CH3NH3)Pb2Br7 (m = 4, 6–8) and MAPbBr3 show they are stable in ambient air for at least 5 months, exhibiting greater extrinsic stability than the 2D lead iodide congeners. Extraordinarily, 3D MAPbBr3 films prove to be more stable than films of 2D lead bromide perovskites, in contrast to MAPbI3 which is less stable than the 2D lead iodide perovskites.

We report the open framework semiconductor, Sn4B12Se12, synthesized using a Sn/Se flux method. The framework in this compound features the rare icosahedral [B12Se12]14– anion assembled into a 3D tu...

The recently developed family of 3D halide perovskites with general formula (A)1-x(en)x(M)1-0.7x(I)3-0.4x (A = MA, FA; M = Pb2+, Sn2+ en = ethylenediammonium), often referred to as "hollow"perovskites, exhibits exceptional air stability and crystallizes in the high symmetry α phase at room temperature. These properties are counterintuitive, considering that these structures include the large divalent en cation charge-compensated by vacancies of Pb cations and I anions. Moreover, the understanding of their transport behavior is incomplete. To provide new insights into the ionic and electronic transport properties of these "hollow"perovskites, we performed DC polarization experiments and ab initio calculations on the {en}MAPbI3 material. We observe large variations of ionic and electronic conductivities with en concentration, which can be explained by charge and site arguments in conjunction with trapping effects. The latter is reflected by the increase of the activation energies for iodide ion transport with higher en content that we observe from both experimental and computational results. The connection between these transport phenomena and the stability of "hollow"perovskite materials and devices is discussed.

Halide perovskite semiconductors are poised to revitalize the field of ionizing radiation detection as they have done to solar photovoltaics. We show that all-inorganic perovskite CsPbBr3 devices resolve 137Cs 662-keV γ-rays with 1.4% energy resolution, as well as other X- and γ-rays with energies ranging from tens of keV to over 1 MeV in ambipolar sensing and unipolar hole-only sensing modes with crystal volumes of 6.65 mm3 and 297 mm3, respectively. We report the scale-up of CsPbBr3 ingots to up to 1.5 inches in diameter with an excellent hole mobility–lifetime product of 8 × 10−3 cm2 V−1 and a long hole lifetime of up to 296 μs. CsPbBr3 detectors demonstrate a wide temperature region from ~2 °C to ~70 °C for stable operation. Detectors protected with suitable encapsulants show a uniform response for over 18 months. Consequently, we identify perovskite CsPbBr3 semiconductor as an exceptional candidate for new-generation high-energy γ-ray detection. Energy resolution of high-energy photon detectors is desired for applications ranging from biomedical imaging to homeland security. In this work, perovskite-based γ-ray detection with 1.4% energy resolution is demonstrated.

The halide perovskite Ruddlesden-Popper (RP) phases are a homologous layered subclass of solution-processable semiconductors that have aroused great attention, especially for developing long-term solar photovoltaics. They are defined as (A′)2(A)n-1PbnX3n+1 (A′ = spacer cation, A = cage cation, and X = halide anion). The orientation control of low-temperature self-assembled thin films is a fundamental issue associated with the ability to control the charge carrier transport perpendicular to the substrate. Here we report new chemical derivatives designed from a molecular perspective using a novel spacer cation 3-phenyl-2-propenammonium (PPA) with conjugated backbone as a low-temperature strategy to assemble more efficient solar cells. First, we solved and refined the crystal structures of single crystals with the general formula (PPA)2(FA0.5MA0.5)n-1PbnI3n+1 (n = 2 and 3, space group C2) using X-ray diffraction and then used the mixed halide (PPA)2(Cs0.05(FA0.88MA0.12)0.95)n-1Pbn(I0.88Br0.12)3n+1 analogues to achieve more efficient devices. While forming the RP phases, multiple hydrogen bonds between PPA and inorganic octahedra reinforce the layered structure. For films we observe that as the targeted layer thickness index increases from n = 2 to n = 4, a less horizontal preferred orientation of the inorganic layers is progressively realized along with an increased presence of high-n or 3D phases, with an improved flow of free charge carriers and vertical to substrate conductivity. Accordingly, we achieve an efficiency of 14.76% for planar p-i-n solar cells using PPA-RP perovskites, which retain 93.8 ± 0.25% efficiency with encapsulation after 600 h at 85 °C and 85% humidity (ISOS-D-3).

Guanidinium (GA) has been widely used as an additive in solar cells for enhanced performance. However, the size of the guanidinium cation is too large to be incorporated in the cage of the perovskite structure. Instead, GA forms a variety of structures with lead iodide, where its role in the perovskite crystal as well as solar cell devices is unclear. In this study, we demonstrate that GA can be incorporated into the structure of MAPbI3 as (GA)x(MA)1-xPbI3. From single-crystal X-ray crystallographic refinement, we observe lattice expansion and Pb-I bond elongation with GA incorporation similar to exerting "negative pressure", which weakens orbital overlap and widens the band gap from 1.49 to 1.53 eV. We find that the highest percentage of GA that can be incorporated into the 3D MAPbI3 structure is 5.26%, as confirmed by nuclear magnetic resonance. The alloyed (GA)x(MA)1-xPbI3 exhibits increased PL lifetimes from 154.4 to 266.3 ns after GA incorporation while the Voc of (GA)x(MA)1-xPbI3 devices enlarges from 1.05 to 1.11 V. High efficiencies in solar cell devices up to 20.38% with a Jsc of 23.55 mA cm-2, Voc of 1.11 V, and FF of 0.78 have been achieved, with stable photovoltaic performance for 900 h in air.

The advent of the two-dimensional (2D) family of halide perovskites and their demonstration in 2D/three-dimensional (3D) hierarchical film structures broke new ground toward high device performance and good stability. The 2D Dion-Jacobson (DJ) phase halide perovskites are especially attractive in solar cells because of their superior charge transport properties. Here, we report on 2D DJ phase perovskites using a 3-(aminomethyl)piperidinium (3AMP) organic spacer for the fabrication of mixed Pb/Sn-based perovskites, exhibiting a narrow bandgap of 1.27 eV and a long carrier lifetime of 657.7 ns. Consequently, solar cells employing mixed 2D DJ 3AMP-based and 3D MA

International audience; The optical and light emission properties of tin and lead halide perovskites are remarkable because of the robust room-temperature (RT) performance, broad wavelength tunability, high efficiency, and good quenching resistance to defects. These highly desirable attributes promise to transform current light-emitting devices, phosphors, and lasers. One disadvantage in most of these materials is the sensitivity to moisture. Here, we report a new air-stable one-dimensional (1D) hybrid lead-free halide material (DAO)SnI (DAO, 1,8-octyldiammonium) that is resistant to water for more than 15 h. The material exhibits a sharp optical absorption edge at 2.70 eV and a strong broad orange light emission centered at 634 nm, with a full width at half-maximum (fwhm) of 142 nm (0.44 eV). The emission has a long photoluminescence (PL) lifetime of 582 ns, while the intensity is constant over a very broad temperature range (145-415 K) with a photoluminescence quantum yield (PLQY) of at least 20.3% at RT. Above 415 K the material undergoes a structural phase transition from monoclinic (2/) to orthorhombic ( accompanied by a red shift in the band gap and a quench in the photoluminescence emission. Density functional theory calculations support the trend in the optical properties and the 1D electronic nature of the structure, where the calculated carrier effective masses along the inorganic chain are significantly lower than those perpendicular to the chain. Thin films of the compound readily fabricated from solutions exhibit the same optical properties, but with improved PLQY of 36%, for a 60 nm thick film, among the highest reported for lead-free low-dimensional 2D and 1D perovskites and metal halides.

International audience; Hybrid layered halide perovskites have achieved impressive performance in optoelectronics. New structural types in the two-dimensional (2D) halide system such as the Dion-Jacobson phases have attracted wide research attention due to the short interlayer distance and unique layer orientation that facilitate better charge-transport and higher stability in optoelectronic devices. Here, we report the first solid solution series incorporating both A and A’ cations in the 2D Jacobson-Dion family, with the general formula (A’)(A)Pb2Br7 ((A’ = 3-(aminomethyl)piperidinium (3AMP) and 4-(aminomethyl)piperidinium) (4AMP); A= methylammonium (MA) and formamidinium (FA)). Mixing the spacing A’ cations and perovskitizer A cations generates the new (3AMP)a(4AMP)1-a(FA)b(MA)1-bPb2Br7 perovskites. The crystallographically refined crystal structures using single-crystal X-ray diffraction data re-veal that the distortion of the inorganic framework is heavily influenced by the degree of A’ and A alloying. A rising fraction of 4AMP in the structure, decreases the Pb-Br-Pb angles, making the framework more distorted. On the contrary, higher FA fractions increase the Pb-Br-Pb angles. This structural evolution fine tunes the optical properties where the larger the Pb-Br-Pb angle, the narrower the band gap. The photoluminescence emission energy mirrors this trend. Raman spectroscopy reveals a highly dynamical lattice similar to MAPbBr3 and consistent with the local distortion environment of the [Pb2Br7] framework. Density Functional Theory (DFT) calculations of the electronic structures reveal the same trend as the experimental results where (3AMP)(FA)Pb2Br7 has the smallest band gap while (4AMP)(MA)Pb2Br7 has the largest band gap. The structural effects from solely the organic cati-ons in the 2D system highlight the importance of understanding the high sensitivity of the optoelectronic properties on the struc-tural tuning in this broad class of materials.

Transformative and reconstructive reactions impart significant structural changes at particle boundaries of hybrid perovskites, which influence environmental stability and optoelectronic properties of these materials. Here, we investigate the moisture-induced transformative reactions in formamidinium based perovskites FAPbX3 (X=I, Br) and show that the ambient stability of these materials can be adjusted from a few hours to several months. For FAPbI3, roles of water vapor, particle size, and light illumination on the kinetic pathways of the cubic () transformation to the hexagonal () phase are analyzed by X-ray diffraction, optical microscopy, photoluminescence and solid-state NMR spectroscopy techniques. The grain and sub-grain boundaries exhibit different →-FAPbI3 phase transformation kinetics. Our study suggests that the dynamic transformation involves the local water-induced dissolution of the cubic phase

International audience; The nature of the organic cation in two-dimensional (2D) hybrid lead iodide perovskites tailors the structural and technological features of the resultant material. Herein, we present three new homologous series of (100) lead iodide perovskites with the organic cations allylammonium (AA) containing an unsaturated C═C group and iodopropylammonium (IdPA) containing iodine on the organic chain: (AA)2MAn–1PbnI3n+1 (n = 3–4), [(AA)x(IdPA)1–x]2MAn–1PbnI3n+1 (n = 1–4), and (IdPA)2MAn–1PbnI3n+1 (n = 1–4), as well as their perovskite-related substructures. We report the in situ transformation of AA organic layers into IdPA and the incorporation of these cations simultaneously into the 2D perovskite structure. Single-crystal X-ray diffraction shows that (AA)2MA2Pb3I10 crystallizes in the space group P21/c with a unique inorganic layer offset (0

Understanding and tailoring the physical behaviour of halide perovskites under practical environments is critical for designing efficient and durable optoelectronic devices. Here, we report that continuous light illumination leads to >1% contraction in the out-of-plane direction in two-dimensional hybrid perovskites, which is reversible and strongly dependent on the specific superlattice packing. X-ray photoelectron spectroscopy measurements show that constant light illumination results in the accumulation of positive charges in the terminal iodine atoms, thereby enhancing the bonding character of inter-slab I–I interactions across the organic barrier and activating out-of-plane contraction. Correlated charge transport, structural and photovoltaic measurements confirm that the onset of the light-induced contraction is synchronized to a threefold increase in carrier mobility and conductivity, which is consistent with an increase in the electronic band dispersion predicted by first-principles calculations. Flux-dependent space-charge-limited current measurement reveals that light-induced interlayer contraction activates interlayer charge transport. The enhanced charge transport boosts the photovoltaic efficiency of two-dimensional perovskite solar cells up to 18.3% by increasing the device’s fill factor and open-circuit voltage. Light-induced contraction in the out-of-plane direction in two-dimensional (2D) hybrid perovskites enables the realization of high-efficiency 2D perovskite solar cells.

International audience; The Goldschmidt tolerance factor in halide perovskites limits the number of cations that can enter their cages without destabilizing their overall structure. Here we have explored the limits of this geometric factor and found that the ethylammonium (EA) cations which lie outside the tolerance factor range can still enter the cages of the 2D halide perovskites by stretching them. The new perovskites allow us to study how these large cations occupying the perovskite cages affect the structural, optical, and electronic properties. We report a series of cation engineered 2D Ruddlesden-Popper lead iodide perovskites (BA)2(EAxMA1-x)2Pb3I10 (x = 0-1, BA is n-butylammonium, MA is methylammonium) by incorporating large EA cation in the cage. Analysis of the single-crystal structures reveals that the incorporation of EA in the cage significantly stretches Pb-I bonds, expands the cage, and induces a large octahedral distortion in the inorganic framework. Spectroscopic and theoretical studies show that such structural deformation leads to a blue-shifted bandgap, sub-bandgap trap states with wider energetic distribution, and stronger photoluminescence quenching. These results enrich the family of 2D perovskites and provide new insights for understanding the structure-property relationship in perovskite materials.

Semiconductors possessing both magnetic and optoelectronic properties are rare and promise applications in opto-spintronics. Here we report the mixed-anion semiconductor BaFMn0.5Te with a band gap ...

There is strong interest in improving the environmental stability of hybrid perovskite solar cells while maintaining high efficiency. Here, we solve this problem by using epilayers of a wide-band-g...

Thorium as a potential nuclear fuel for the next-generation thorium-based molten salt reactors holds significant environmental and economic promise over the current uranium-based nuclear reactors. However, because thorium (Th4+) usually coexists with other rare earth elements, alkali or alkaline earth metals in minerals, or highly acidic radioactive waste, seeking acid-resistant sorbents with excellent selectivity, high capacity, and fast removal rate for Th4+ is still a challenging task. In this work, we investigated a robust layered metal sulfide (KInSn2S6, KMS-5) for Th4+ removal from strong acidic solutions. We report that KMS-5 could capture Th4+ from a 0.1 M HNO3 solution with extremely high efficiency (∼99.9%), fast sorption kinetics (equilibrium time < 10 min), and large distribution coefficient (up to 1.5 × 106 mL/g). Furthermore, KMS-5 exhibited excellent sorption selectivity towards Th4+ in the presence of large amounts of competitive metal ions like Eu3+, Na+, and Ca2+. This extraordinary capture property for Th4+ is attributed to the facile ion exchange of Th4+ with K+ in the interlayers and subsequent formation of a stable coordination complex via Th-S bonds. These results indicate that KMS-5 is a promising functional sorbent for the effective capture of Th4+ from highly acidic solutions.

In-plane strains are commonly found in two-dimensional (2D) metal halide organic-inorganic perovskites (HOIPs). The in-plane mechanical properties of 2D HOIPs are vital for mitigating the strain-induced stability issues of 2D HOIPs, yet their structure and mechanical property relationship largely remains unknown. Here, we employed atomic force microscope indentation to systematically investigate the in-plane Young's moduli E∥ of 2D lead halide Ruddlesden-Popper HOIPs with a general formula of (R-NH3)2PbX4, where the spacer molecules R-NH3+ are linear alkylammonium cations (CmH2m+1-NH3+, m = 4, 6, 8, or 12) and X = I, Br, or Cl. Fixing the spacer molecule to butylammonium, we discovered that the E∥ of 2D HOIPs generally follows the trend of Pb-X bond strength, different from the tendency found in the out-of-plane moduli E⊥, showing more prominent effects of the metal halide inorganic framework on E∥ than E⊥. E∥ exhibits nonmonotonic dependence on the chain length of the linear alkyl spacer molecules, which would first decrease and plateau but then increase again. This is likely due to the competition of the bond strength and structural distortion in the inorganic layer, the relative fraction of the soft organic spacers, and the interfacial mechanical coupling associated with the interdigitation of the alkyl chains. The mechanical anisotropy of 2D HOIPs, marked by E∥/E⊥, shows wide tunability based on structural composition, particularly for iodide-based 2D HOIPs. Our results provide valuable insights into the structure-property relationships regarding the mechanical anisotropy and in-plane mechanical behaviors of 2D HOIPs, which can guide the materials design and device optimization to achieve required mechanical performance in 2D HOIP-based applications.

Two-dimensional (2D) hybrid organic-inorganic halide perovskites are a preeminent class of low-cost semiconductors whose inherent structural tunability and attractive photophysical properties have led to the successful fabrication of solar cells with high power conversion efficiencies. Despite the observed superior stability of 2D lead iodide perovskites over their 3D parent structures, an understanding of their thermochemical profile is missing. Herein, the calorimetric studies reveal that the Ruddlesden-Popper (RP) series, incorporating the monovalent-monoammonium spacer cations of pentylammonium (PA) and hexylammonium (HA): (PA)

This roadmap on Nanotechnology for Catalysis and Solar Energy Conversion focuses on the application of nanotechnology in addressing the current challenges of energy conversion: ‘high efficiency, stability, safety, and the potential for low-cost/scalable manufacturing’ to quote from the contributed article by Nathan Lewis. This roadmap focuses on solar-to-fuel conversion, solar water splitting, solar photovoltaics and bio-catalysis. It includes dye-sensitized solar cells (DSSCs), perovskite solar cells, and organic photovoltaics. Smart engineering of colloidal quantum materials and nanostructured electrodes will improve solar-to-fuel conversion efficiency, as described in the articles by Waiskopf and Banin and Meyer. Semiconductor nanoparticles will also improve solar energy conversion efficiency, as discussed by Boschloo et al in their article on DSSCs. Perovskite solar cells have advanced rapidly in recent years, including new ideas on 2D and 3D hybrid halide perovskites, as described by Spanopoulos et al ‘Next generation’ solar cells using multiple exciton generation (MEG) from hot carriers, described in the article by Nozik and Beard, could lead to remarkable improvement in photovoltaic efficiency by using quantization effects in semiconductor nanostructures (quantum dots, wires or wells). These challenges will not be met without simultaneous improvement in nanoscale characterization methods. Terahertz spectroscopy, discussed in the article by Milot et al is one example of a method that is overcoming the difficulties associated with nanoscale materials characterization by avoiding electrical contacts to nanoparticles, allowing characterization during device operation, and enabling characterization of a single nanoparticle. Besides experimental advances, computational science is also meeting the challenges of nanomaterials synthesis. The article by Kohlstedt and Schatz discusses the computational frameworks being used to predict structure–property relationships in materials and devices, including machine learning methods, with an emphasis on organic photovoltaics. The contribution by Megarity and Armstrong presents the ‘electrochemical leaf’ for improvements in electrochemistry and beyond. In addition, biohybrid approaches can take advantage of efficient and specific enzyme catalysts. These articles present the nanoscience and technology at the forefront of renewable energy development that will have significant benefits to society.

We present an effective approach to favorably modify the electronic structure of PbSe using Ag doping coupled with SrSe or BaSe alloying. The Ag 4d states make a contribution to in the top of the heavy hole valence band and raise its energy. The Sr and Ba atoms diminish the contribution of Pb 6s2 states and decrease the energy of the light hole valence band. This electronic structure modification increases the density-of-states effective mass, and strongly enhances the thermoelectric performance. Moreover, the Ag-rich nanoscale precipitates, discordant Ag atoms, and Pb/Sr, Pb/Ba point defects in the PbSe matrix work together to reduce the lattice thermal conductivity, resulting a record high average ZTavg of around 0.86 over 400–923 K. Agency for Science, Technology and Research (A*STAR) Accepted version

Guanidinium (GA) has been widely used as an additive in solar cells for enhanced performance. However, the size of the guanidinium cation is too large to be incorporated in the cage of the perovskite structure. Instead, GA forms a variety of structures with lead iodide, where its role in the perovskite crystal as well as solar cell devices is unclear. In this study, we demonstrate that GA can be incorporated into the structure of MAPbI

In photovoltaics and flexible electronics applications, two-dimensional (2D) hybrid organic–inorganic perovskites (HOIPs) are often subjected to mechanical strain arising from materials processing, device functioning, and thermal expansion. Here we report for the first time a study of the band gap response to uniaxial tensile strain in thin 2D HOIP flakes with a general formula of (CH3(CH2)3NH3)2(CH3–NH3)n−1PbnI3n+1. At large n (n > 3), the band gap will increase as the strain increases, and the strain response of band gap can be as high as 13.3 meV/% for n = 5, which is due to the rotation of the inorganic [PbI6]4– octahedra and the consequential Pb–I bond stretching and increase of Pb–I–Pb. Our findings provide a route to engineer the electronic properties of 2D HOIPs. The observed band gap–strain relationship can be harnessed to map the local mechanical strain in 2D HOIP-based devices and allow 2D HOIPs for sensing applications.

Hybrid layered halide perovskites have achieved impressive performance in optoelectronics. New structural types in the two-dimensional (2D) halide system such as the Dion-Jacobson phases have attracted wide research attention due to the short interlayer distance and unique layer orientation that facilitate better charge-transport and higher stability in optoelectronic devices. Here, we report the first solid solution series incorporating both A and A' cations in the 2D Dion-Jacobson family, with the general formula (A')(A)Pb

Mechanical stability of hybrid organic-inorganic perovskites (HOIPs) is essential to achieve long-term durable HOIP-based devices. While HOIPs in two-dimensional (2D) form offer numerous options in the structure and composition to tune their mechanical properties, little is known about the structure-mechanical-property relationship in this family of materials. Here, we investigated a series of 2D lead halide HOIPs by nanoindentation to explore the impact of critical factors controlling the properties of both the organic and inorganic layers on the materials' out-of-plane mechanical performance. We find that the lead-halide bond in the inorganic framework can significantly influence the mechanical properties of 2D Ruddlesden-Popper (RP) HOIPs with

Two-dimensional (2D) hybrid organic-inorganic perovskites (HOIPs) are recent members of the 2D materials family with wide tunability, highly dynamic structural features, and excellent physical properties. Ultrathin 2D HOIPs and their heterostructures with other 2D materials have been exploited for study of physical phenomena and device applications. The in-plane mechanical properties of 2D ultrathin HOIPs are critical for understanding the coupling between mechanical and other physical fields and for integrated devices applications. Here we report the in-plane mechanical properties of ultrathin freestanding 2D lead iodide perovskite membranes and their dependence on the membrane thickness. The in-plane Young's moduli of 2D HOIPs are smaller than that of conventional covalently bonded 2D materials. As the thickness increases from monolayer to three-layer, both the Young's modulus and breaking strength decrease, while three-layer and four-layer 2D HOIPs have almost identical in-plane mechanical properties. These thickness-dependent mechanical properties can be attributed to interlayer slippage during deformation. Our results show that ultrathin 2D HOIPs exhibit outstanding breaking strength/Young's modulus ratio compared to many other widely used engineering materials and polymeric flexible substrates, which renders them suitable for application into flexible electronic devices.

The targeted synthesis of metal–organic frameworks (MOFs) with open metal sites, following reticular chemistry rules, provides a straightforward methodology toward the development of advanced porous materials especially for gas storage/separation applications. Using a palladated tetracarboxylate metalloligand as a 4-connected node, we succeeded in synthesizing the first heterobimetallic In(III)/Pd(II)-based MOF with square-octahedron (soc) topology. The new MOF, formulated as [In3O(L)1.5(H2O)2Cl]·n(solv) (1), features the oxo-centered trinuclear clusters, [In3(μ3-O)(−COO)6], acting as trigonal-prismatic 6-connected nodes that linked together with the metalloligand trans-[PdCl2(PDC)2] (L4–) (PDC: pyridine-3,5-dicarboxylate) to form a 3D network. After successful activation of 1 using supercritical CO2, high-resolution microporous analysis revealed the presence of small micropores (5.8 A) with BET area of 795 m2 g–1 and total pore volume of 0.35 cm3 g–1. The activated solid shows high gravimetric (92.3 cm3 ...

Hybrid halide perovskite solar cells with mixed cations demonstrate superior optical and electrical properties, especially for lead-based perovskite devices. Here, we report lead-free tin-based perovskite solar cells with diammonium cations, which can significantly improve the device performance. Formamidinium tin iodide (FASnI3) perovskite can incorporate propylenediammonium (PN) and trimethylenediammonium (TN) and retain its three-dimensional structure while at the same time providing better film morphology and optoelectronic properties. As a result, solar cell devices using FASnI3 absorbers mixed with 10% PN and 10% TN achieve higher power conversion efficiencies of 5.85% and 5.53%, respectively, compared to 2.53% of the pristine FASnI3 solar cell. This difference in device performance can be mainly attributed to the reduced leakage current, lower trap-state density, and reduced recombination, as evidenced by our dark current–voltage, space-charge-limited current, and impedance measurements. The result...

Excellent-quality graphene sheets produced via the direct liquid phase exfoliation of highly crystalline graphite (avoiding any oxidative treatment), were employed for the first time as 2D scaffolds for the in-situ synthesis of zeolitic-imidazolate-framework (ZIF-8) material. Our synthetic approach involved the efficient, urea-assisted exfoliation of natural graphite (without using any acids), and the subsequent selective, mild functionalization of the resulting high-quality graphene sheets with benzoic acid functional groups. The graphene derivatives were next decorated via the in-situ development of ultrasmall (approx. 30 nm) ZIF-8 nanocrystals. We discuss the critical role of the functionalized graphene to the selective nucleation and crystal growth of ZIF-8 nanocrystals exclusively at their surface. In-depth gas sorption studies of different gases revealed that the novel ZIF-8@Graph nano-composites exhibited improved porosity (in terms of surface area and pore volume) compared to analogous Graphene Oxide/ZIF-8 hybrids. In addition, the gate effect of the ZIF-8 nanocrystals anchored onto the high-quality graphene, was found very different compared to bulk ZIF-8, a behavior that is attributed mainly to the significantly smaller crystal size and the perfect 2D confinement of ZIF-8 along graphene. Finally, preliminary CO2 adsorption properties of the synthesized novel nano-composites are reported, at near ambient temperature.

The sorption properties of [Zr6O4(OH)4(NH3+-BDC)6]Cl6·xH2O (MOR-1) and H16[Zr6O16(H2PATP)4]Cl8·xH2O (MOR-2) towards ReO4− and TcO4− were studied in detail. Both MOR-1 and MOR-2 are very effective sorbents for ReO4− and TcO4− anions, with MOR-2 showing the highest sorption capacity (up to 4.1 ± 0.4 mmol g−1) among the known metal organic materials. Importantly, the exceptional sorption capacity of MOR-2 is retained even under conditions simulating acidic nuclear waste. In addition, MOR-1 and MOR-2 exhibit selective luminescence ReO4− sensing properties, demonstrated for the first time for MOF materials.

Developing dopant-free hole transporting layers (HTLs) is critical in achieving high-performance and robust state-of-the-art perovskite photovoltaics, especially for the air-sensitive tin-based perovskite systems. The commonly used HTLs require hygroscopic dopants and additives for optimal performance, which adds extra cost to manufacturing and limits long-term device stability. Here we demonstrate the use of a novel tetrakis-triphenylamine (TPE) small molecule prepared by a facile synthetic route as a superior dopant-free HTL for lead-free tin-based perovskite solar cells. The best-performing tin iodide perovskite cells employing the novel mixed-cation ethylenediammonium/formamidinium with the dopant-free TPE HTL achieve a power conversion efficiency as high as 7.23%, ascribed to the HTL's suitable band alignment and excellent hole extraction/collection properties. This efficiency is one of the highest reported so far for tin halide perovskite systems, highlighting potential application of TPE HTL material in low-cost high-performance tin-based perovskite solar cells.

In recent years, the design and discovery of new metal-organic framework (MOF) platforms with distinct structural features and tunable chemical composition has remarkably enhanced by applying reticular chemistry rules and the molecular building block (MBB) approach. We targeted the synthesis of new rare earth (RE)-MOF platforms based on a rectangular-shaped 4-c linker, acting as a rigid organic MBB. Accordingly, we designed and synthesized the organic ligand 1,2,4,5-tetrakis(4-carboxyphenyl)-3,6-dimethyl-benzene (H4L), in which the two methyl groups attached to the central phenyl ring lock the four peripheral carboxyphenyl groups to an orthogonal/vertical position. We report here a new family of RE-MOFs featuring the novel inorganic building unit, RE4(μ3-O)2 (RE: Y3+, Tb3+, Dy3+, Ho3+, Er3+, and Yb3+), with planar D2h symmetry. The rigid 4-c linker, H4L, directs the in situ assembly of the unique 8-c RE4(μ3-O)2(COO)8 cluster, resulting in the formation of the first (4, 8)-c RE-MOFs with csq topology, RE-c...

Tin-based perovskites have very comparable electronic properties to lead-based perovskites and are regarded as possible lower toxicity alternates for solar cell applications. However, the efficiency of tin-based perovskite solar cells is still low and they exhibit poor air stability. Here, we report lead-free tin-based solar cells with greatly enhanced performance and stability using so-called “hollow” ethylenediammonium and methylammonium tin iodide ({en}MASnI3) perovskite as absorbers. Our results show that en can improve the film morphology and most importantly can serve as a new cation to be incorporated into the 3D MASnI3 lattice. When the cation of en becomes part of the 3D structure, a high density of SnI2 vacancies is created resulting in larger band gap, larger unit cell volume, lower trap-state density, and much longer carrier lifetime compared to classical MASnI3. The best-performing {en}MASnI3 solar cell has achieved a high efficiency of 6.63% with an open circuit voltage of 428.67 mV, a short...

This work combines, for the first time, 3D-printing technology and a highly efficient metal organic framework (Ca-MOF) as an electrode modifier to produce a novel fully integrated lab-in-a-syringe device for the sensitive determination of Hg(II) by anodic stripping voltammetry. The specific Ca-MOF ([Ca(H4L)(DMA)(2)]center dot 2DMA where H6L is the N,N’-bis(2,4-dicarboxyphenyl)-oxalamide and DMA is the N,N-dimethylacetamide) shows an exceptional Hg(II) sorption capability over a wide pH range and its mechanism is elucidated via spectroscopic and Xray diffraction studies. The voltammetric lab-in-a-syringe device is fabricated through a single-step process using a dual extruder 3D printer and is composed of a vessel integrating two thermoplastic conductive electrodes (serving as the counter and pseudo-reference electrodes) and of a small detachable 3D-printed syringe loaded with a graphite paste/Ca-MOF mixture (which serves as the working electrode). After optimization of the fabrication and operational variables, a limit of detection of 0.6 mu g L-1 Hg(II) was achieved, which is comparable or lower than that of existing sensors (plastic 3D-printed, gold and MOF-based electrodes). The adoption of 3D printing technology in combination with the highly efficient Ca-MOF enables the fabrication of a simple, low-cost and sensitive electrochemical sensor for Hg(II), which is suitable for on-site applications.

Semiconductors possessing both magnetic and optoelectronic properties are rare and promise applications in opto-spintronics. Here we report the mixed-anion semiconductor BaFMn