3D to 0D cesium lead bromide: A 79/81Br NMR, NQR and theoretical investigation.

Inorganic metal halides offer unprecedented tunability through elemental variation of simple three-element compositions, but can exhibit complicated phase behaviour, degradation, and microscopic phenomena (disorder/dynamics) that play an integral role for the bulk-level chemical and physical properties of these materials. Understanding the halogen chemical environment in such materials is crucial to addressing many of the concerns regarding implementing these materials in commercial applications. In this study, a combined solid-state nuclear magnetic resonance, nuclear quadrupole resonance and quantum chemical computation approach is used to interrogate the Br chemical environment in a series of related inorganic lead bromide materials: CsPbBr3, CsPb2Br5, and Cs4PbBr6. The quadrupole coupling constants (CQ) were determined to range from 61 to 114 MHz for 81Br, with CsPbBr3 exhibiting the largest measured CQ and Cs4PbBr6 the smallest. GIPAW DFT was shown to be an excellent pre-screening tool for estimating the EFG of Br materials and can increase experimental efficiency by providing good starting estimates for acquisition. Finally, the combination of theory and experiment to inform the best methods for expanding further to the other quadrupolar halogens is discussed.

Ultrahigh Size Exclusion Selectivity for Carbon Dioxide from Nitrogen/Methane in an Ultramicroporous Metal-Organic Framework.

Separations based on molecular size (molecular sieving) are a solution for environmental remediation. We have synthesized and characterized two new metal-organic frameworks (MOFs) (Zn2M; M = Zn, Cd) with ultramicropores (<0.7 nm) suitable for molecular sieving. We explore the synthesis of these MOFs and the role that the DMSO/H2O/DMF solvent mixture has on the crystallization process. We further explore the crystallographic data for the DMSO and methanol solvated structures at 273 and 100 K; this not only results in high-quality structural data but also allows us to better understand the structural features at temperatures around the gas adsorption experiments. Structurally, the main difference between the two MOFs is that the central metal in the trimetallic node can be changed from Zn to Cd and that results in a sub-Å change in the size of the pore aperture, but a stark change in the gas adsorption properties. The separation selectivity of the MOF when M = Zn is infinite given the pore aperture of the MOF can accommodate CO2 while N2 and/or CH4 is excluded from entering the pore. Furthermore, due to the size exclusion behavior, the MOF has an adsorption selectivity of 4800:1 CO2/N2 and 5 × 1028:1 CO2/CH4. When M = Cd, the pore aperture of the MOF increases slightly, allowing N2 and CH4 to enter the pore, resulting in a 27.5:1 and a 10.5:1 adsorption selectivity, respectively; this is akin to UiO-66, a MOF that is not able to function as a molecular sieve for these gases. The data delineate how subtle sub-Å changes to the pore aperture of a framework can drastically affect both the adsorption selectivity and separation selectivity.

Exploring Structural Nuances in Germanium Halide Perovskites Using Solid-State 73Ge and 133Cs NMR Spectroscopy.

Metal halide perovskites remain top candidates for higher-performance photovoltaic devices, but concerns about leading lead-based materials remain. Ge perovskites remain understudied for use in solar cells compared to their Sn-based counterparts. In this work, we undertake a combined 73Ge and 133Cs solid-state Nuclear Magnetic Resonance (NMR) spectroscopy and density functional theory (DFT) study of the bulk CsGeX3 (X = Cl, Br, or I) series. We show how seemingly small structural variations within germanium halide perovskites have major effects on their 73Ge and 133Cs NMR signatures and reveal a near-cubic phase at room temperature for CsGeCl3 with severe local Ge polyhedral distortion. Quantum chemical computations are effective at predicting the structural impact on NMR parameters for 73Ge and 133Cs. This study demonstrates the value of a combined solid-state NMR and DFT approach for investigating promising materials for energy applications, providing information that is out of reach with conventional characterization methods, and adds the challenging 73Ge nucleus to the NMR toolkit.

Photocatalytic Mechanism Control and Study of Carrier Dynamics in CdS@C3N5 Core-Shell Nanowires.

We present a potential solution to the problem of extraction of photogenerated holes from CdS nanocrystals and nanowires. The nanosheet form of C3N5 is a low-band-gap (Eg = 2.03 eV), azo-linked graphenic carbon nitride framework formed by the polymerization of melem hydrazine (MHP). C3N5 nanosheets were either wrapped around CdS nanorods (NRs) following the synthesis of pristine chalcogenide or intercalated among them by an in situ synthesis protocol to form two kinds of heterostructures, CdS-MHP and CdS-MHPINS, respectively. CdS-MHP improved the photocatalytic degradation rate of 4-nitrophenol by nearly an order of magnitude in comparison to bare CdS NRs. CdS-MHP also enhanced the sunlight-driven photocatalytic activity of bare CdS NWs for the decolorization of rhodamine B (RhB) by a remarkable 300% through the improved extraction and utilization of photogenerated holes due to surface passivation. More interestingly, CdS-MHP provided reaction pathway control over RhB degradation. In the absence of scavengers, CdS-MHP degraded RhB through the N-deethylation pathway. When either hole scavenger or electron scavenger was added to the RhB solution, the photocatalytic activity of CdS-MHP remained mostly unchanged, while the degradation mechanism shifted to the chromophore cleavage (cycloreversion) pathway. We investigated the optoelectronic properties of CdS-C3N5 heterojunctions using density functional theory (DFT) simulations, finite difference time domain (FDTD) simulations, time-resolved terahertz spectroscopy (TRTS), and photoconductivity measurements. TRTS indicated high carrier mobilities >450 cm2 V-1 s-1 and carrier relaxation times >60 ps for CdS-MHP, while CdS-MHPINS exhibited much lower mobilities <150 cm2 V-1 s-1 and short carrier relaxation times <20 ps. Hysteresis in the photoconductive J-V characteristics of CdS NWs disappeared in CdS-MHP, confirming surface passivation. Dispersion-corrected DFT simulations indicated a delocalized HOMO and a LUMO localized on C3N5 in CdS-MHP. C3N5, with its extended π-conjugation and low band gap, can function as a shuttle to extract carriers and excitons in nanostructured heterojunctions, and enhance performance in optoelectronic devices. Our results demonstrate how carrier dynamics in core-shell heterostructures can be manipulated to achieve control over the reaction mechanism in photocatalysis.

"Turning the dials": controlling synthesis, structure, composition, and surface chemistry to tailor silicon nanoparticle properties.

Silicon nanoparticles (SiNPs) can be challenging to prepare with defined size, crystallinity, composition, and surface chemistry. As is the case for any nanomaterial, controlling these parameters is essential if SiNPs are to realize their full potential in areas such as alternative energy generation and storage, sensors, and medical imaging. Numerous teams have explored and established innovative synthesis methods, as well as surface functionalization protocols to control these factors. Furthermore, substantial effort has been expended to understand how the abovementioned parameters influence material properties. In the present review we provide a commentary highlighting the benefits and limitations of available methods for preparing silicon nanoparticles as well as demonstrations of tailoring optical and electronic properties through definition of structure (i.e., crystalline vs. amorphous), composition and surface chemistry. Finally, we highlight potential opportunities for future SiNP studies.