Sb-Doped Biphasic P2/O3-Type Mn-Rich Layered Oxide Cathode Material for High-Performance Sodium-Ion Batteries.

Mn-rich P2-type layered oxide cathode materials suffer from severe capacity loss caused by detrimental phase transition and transition metal dissolution, making their implementation difficult in large-scale sodium-ion battery applications. Herein, we introduced a high-valent Sb5+ substitution, leading to a biphasic P2/O3 cathode that suppresses the P2-O2 phase transformation in the high-voltage condition attributed to the stronger Sb-O covalency that introduces extra electrons to the O atom, reducing oxygen loss from the lattices and improving structural stability, as confirmed by first-principle calculations. Besides, the enhanced Na+ diffusion kinetics and thermodynamics in the modified sample are associated with the enlarged lattice parameters. As a result, the proposed cathode delivers a discharge capacity of 142.6 mAh g-1 at 0.1C between 1.5 and 4.3 V and excellent performance at a high mass loading of 8 mg cm3 with a specific capacity of 131 mAh g-1 at 0.2C. Furthermore, it also possesses remarkable rate capability (90.3 mAh g-1 at 5C), specifying its practicality in high-energy-density sodium-ion batteries. Hence, this work provides insights into incorporating high-valent dopants for high-performance Mn-rich cathodes.

Dicarboxylic Acid-Assisted Surface Oxide Removal and Passivation of Indium Antimonide Colloidal Quantum Dots for Short-Wave Infrared Photodetectors.

Heavy-metal-free III-V colloidal quantum dots (CQDs) are promising materials for solution-processed short-wave infrared (SWIR) photodetectors. Recent progress in the synthesis of indium antimonide (InSb) CQDs with sizes smaller than the Bohr exciton radius enables quantum-size effect tuning of the band gap. However, it has been challenging to achieve uniform InSb CQDs with band gaps below 0.9 eV, as well as to control the surface chemistry of these large-diameter CQDs. This has, to date, limited the development of InSb CQD photodetectors that are sensitive to ≥ ${\ge }$ 1400 nm light. Here we adopt solvent engineering to facilitate a diffusion-limited growth regime, leading to uniform CQDs with a band gap of 0.89 eV. We then develop a CQD surface reconstruction strategy that employs a dicarboxylic acid to selectively remove the native In/Sb oxides, and enables a carboxylate-halide co-passivation with the subsequent halide ligand exchange. We find that this strategy reduces trap density by half compared to controls, and enables electronic coupling among CQDs. Photodetectors made using the tailored CQDs achieve an external quantum efficiency of 25 % at 1400 nm, the highest among III-V CQD photodetectors in this spectral region.

Next-Generation Tags for Fluorine Nuclear Magnetic Resonance: Designing Amplification of Chemical Shift Sensitivity.

Fluorine NMR is a highly sensitive technique for delineating the conformational states of biomolecules and has shown great utility in drug screening and in understanding protein function. Current fluorinated protein tags leverage the intrinsic chemical shift sensitivity of the 19F nucleus to detect subtle changes in protein conformation and topology. This chemical shift sensitivity can be amplified by embedding the fluorine or trifluoromethyl reporter within a pyridone. Due to their polarizability and rapid tautomerization, pyridones exhibit a greater range of electron delocalization and correspondingly greater 19F NMR chemical shift dispersion. To assess the chemical shift sensitivity of these tautomeric probes to the local environment, 19F NMR spectra of all possible monofluorinated and trifluoromethyl-tagged versions of 2-pyridone were recorded in methanol/water mixtures ranging from 100% methanol to 100% water. 4-Fluoro-2-pyridone and 6-(trifluoromethyl)-2-pyridone (6-TFP) displayed the greatest sensitivity of the monofluorinated and trifluoromethylated pyridones, exceeding that of known conventional CF3 reporters. To evaluate the utility of tautomeric pyridone tags for 19F NMR of biomolecules, the alpha subunit of the stimulatory G protein (Gsα) and human serum albumin (HSA) were each labeled with a thiol-reactive derivative of 6-TFP and the spectra were recorded as a function of various adjuvants and drugs. The tautomeric tag outperformed the conventional tag, 2-bromo-N-(4-(trifluoromethyl)phenyl)acetamide through the improved resolution of several functional states.

Halide-Driven Synthetic Control of InSb Colloidal Quantum Dots Enables Short-Wave Infrared Photodetectors.

In the III-V family of colloidal quantum dot (CQD) semiconductors, InSb promises access to a wider range of infrared wavelengths compared to many light-sensing material candidates. However, achieving the necessary size, size-dispersity, and optical properties has been challenging. Here the synthetic challenges associated with InSb CQDs are investigated and it is found that uncontrolled reduction of the antimony precursor hampers the controlled growth of CQDs. To overcome this, a synthetic strategy that combines nonpyrophoric precursors with zinc halide additives is developed. The experimental and computational studies show that zinc halide additives decelerate the reduction of the antimony precursor, facilitating the growth of more uniformly sized CQDs. It is also found that the halide choice provides additional control over the strength of this effect. The resultant CQDs exhibit well-defined excitonic transitions in spectral range of 1.26-0.98 eV, along with strong photoluminescence. By implementing a postsynthesis ligand exchange, colloidally stable inks enabling the fabrication of high-quality CQD films are achieved. The first demonstration of InSb CQD photodetectors is presented reaching 75% external quantum efficiency (QE) at 1200 nm, to the knowledge the highest short-wave infrared (SWIR) QE reported among heavy-metal-free infrared CQD-based devices.

Homomeric chains of intermolecular bonds scaffold octahedral germanium perovskites.

Perovskites with low ionic radii metal centres (for example, Ge perovskites) experience both geometrical constraints and a gain in electronic energy through distortion; for these reasons, synthetic attempts do not lead to octahedral [GeI6] perovskites, but rather, these crystallize into polar non-perovskite structures1-6. Here, inspired by the principles of supramolecular synthons7,8, we report the assembly of an organic scaffold within perovskite structures with the goal of influencing the geometric arrangement and electronic configuration of the crystal, resulting in the suppression of the lone pair expression of Ge and templating the symmetric octahedra. We find that, to produce extended homomeric non-covalent bonding, the organic motif needs to possess self-complementary properties implemented using distinct donor and acceptor sites. Compared with the non-perovskite structure, the resulting [GeI6]4- octahedra exhibit a direct bandgap with significant redshift (more than 0.5 eV, measured experimentally), 10 times lower octahedral distortion (inferred from measured single-crystal X-ray diffraction data) and 10 times higher electron and hole mobility (estimated by density functional theory). We show that the principle of this design is not limited to two-dimensional Ge perovskites; we implement it in the case of copper perovskite (also a low-radius metal centre), and we extend it to quasi-two-dimensional systems. We report photodiodes with Ge perovskites that outperform their non-octahedral and lead analogues. The construction of secondary sublattices that interlock with an inorganic framework within a crystal offers a new synthetic tool for templating hybrid lattices with controlled distortion and orbital arrangement, overcoming limitations in conventional perovskites.

Investigating Metal-Tributyl Phosphate Complexes during Supercritical Fluid Extraction of the NdFeB Magnet Using Density Functional Theory and X-ray Absorption Spectroscopy.

Supercritical fluid extraction (SCFE) is gaining significant interest as a green technology for the recycling of end-of-life waste electrical and electronic equipment (WEEE). Neodymium iron boron (NdFeB) magnets, which contain large quantities of critical rare-earth elements such as neodymium, praseodymium, and dysprosium, are widely used in wind turbines and electric/hybrid vehicles. Hence, they are considered a promising secondary resource for these elements when they reach their end-of-life. Previously, the SCFE process was developed for recycling WEEE, including NdFeB; however, the process mechanism remains unexplored. Here, density functional theory, followed by extended X-ray absorption fine structure and X-ray absorption near-edge structure analyses, are utilized to determine the structural coordination and interatomic interactions of complexes formed during the SCFE of the NdFeB magnet. The results indicate that Fe(II), Fe(III), and Nd(III) form Fe(NO3)2(TBP)2, Fe(NO3)3(TBP)2, and Nd(NO3)3(TBP)3 complexes, respectively. This theory-guided investigation elucidates the complexation chemistry and mechanism during the SCFE process by rigorously determining the structural models.

Strain data augmentation enables machine learning of inorganic crystal geometry optimization.

Machine-learning (ML) models offer the potential to rapidly evaluate the vast inorganic crystalline materials space to efficiently find materials with properties that meet the challenges of our time. Current ML models require optimized equilibrium structures to attain accurate predictions of formation energies. However, equilibrium structures are generally not known for new materials and must be obtained through computationally expensive optimization, bottlenecking ML-based material screening. A computationally efficient structure optimizer is therefore highly desirable. In this work, we present an ML model capable of predicting the crystal energy response to global strain by using available elasticity data to augment the dataset. The addition of global strains improves our model's understanding of local strains too, significantly improving the accuracy of energy predictions on distorted structures. This allows us to construct an ML-based geometry optimizer, which we used for improving the predictions of formation energy for structures with perturbed atomic positions.

Electroreduction of Carbon Dioxide to Acetate using Heterogenized Hydrophilic Manganese Porphyrins.

The electrochemical reduction of carbon dioxide (CO2 ) to value-added chemicals is a promising strategy to mitigate climate change. Metalloporphyrins have been used as a promising class of stable and tunable catalysts for the electrochemical reduction reaction of CO2 (CO2 RR) but have been primarily restricted to single-carbon reduction products. Here, we utilize functionalized earth-abundant manganese tetraphenylporphyrin-based (Mn-TPP) molecular electrocatalysts that have been immobilized via electrografting onto a glassy carbon electrode (GCE) to convert CO2 with overall 94 % Faradaic efficiencies, with 62 % being converted to acetate. Tuning of Mn-TPP with electron-withdrawing sulfonate groups (Mn-TPPS) introduced mechanistic changes arising from the electrostatic interaction between the sulfonate groups and water molecules, resulting in better surface coverage, which facilitated higher conversion rates than the non-functionalized Mn-TPP. For Mn-TPP only carbon monoxide and formate were detected as CO2 reduction products. Density-functional theory (DFT) calculations confirm that the additional sulfonate groups could alter the C-C coupling pathway from *CO→*COH→*COH-CO to *CO→*CO-CO→*COH-CO, reducing the free energy barrier of C-C coupling in the case of Mn-TPPS. This opens a new approach to designing metalloporphyrin catalysts for two carbon products in CO2 RR.

Asymmetric Interfacet Adatom Migration as a Mode of Anisotropic Nanocrystal Growth.

Crystals are known to grow nonclassically or via four classical modes (the layer-by-layer, dislocation-driven, dendritic, and normal modes, which generally involve minimal interfacet surface diffusion). The field of nanoscience considers this framework to interpret how nanocrystals grow; yet, the growth of many anisotropic nanocrystals remains enigmatic, suggesting that the framework may be incomplete. Here, we study the solution-phase growth of pentatwinned Au nanorods without Br, Ag, or surfactants. Lower supersaturation conditions favored anisotropic growth, which appeared at variance with the known modes. Temporal electron microscopy revealed kinetically limited adatom funneling, as adatoms diffused asymmetrically along the vicinal facets (situated inbetween the {100} side-facets and {111} end-facets) of our nanorods. These vicinal facets were perpetuated throughout the synthesis and, especially at lower supersaturation, facilitated {100}-to-vicinal-to-{111} adatom diffusion. We derived a growth model from classical theory in view of our findings, which showed that our experimental growth kinetics were consistent with nanorods growing via two modes simultaneously: radial growth occurred via the layer-by-layer mode on {100} side-facets, whereas the asymmetric interfacet diffusion of adatoms to {111} end-facets mediated longitudinal growth. Thus, shape anisotropy was not driven by modulating the relative rates of monomer deposition on different facets, as conventionally thought, but rather by modulating the relative rates of monomer integration via interfacet diffusion. This work shows how controlling supersaturation, a thermodynamic parameter, can uncover distinct kinetic phenomena on nanocrystals, such as asymmetric interfacet surface diffusion and a fundamental growth mode for which monomer deposition and integration occur on different facets.

High-Throughput Evaluation of Emission and Structure in Reduced-Dimensional Perovskites.

High-throughput experimentation (HTE) seeks to accelerate the exploration of materials space by uniting robotics, combinatorial methods, and parallel processing. HTE is particularly relevant to metal halide perovskites (MHPs), a diverse class of optoelectronic materials with a large chemical space. Here we develop an HTE workflow to synthesize and characterize light-emitting MHP single crystals, allowing us to generate the first reported data set of experimentally derived photoluminescence spectra for low-dimensional MHPs. We leverage the accelerated workflow to optimize the synthesis and emission of a new MHP, methoxy-phenethylammonium lead iodide ((4-MeO-PEAI)2-PbI2). We then synthesize 16 000 MHP single crystals and measure their photoluminescence to study the effects of synthesis parameters and compositional engineering on the emission intensity of 54 distinct MHPs: we achieve an acceleration factor of more than 100 times over previously reported HTE MHP synthesis and characterization methods. Using insights derived from this analysis, we screen an existing database for new, potentially emissive MHPs. On the basis of the Tanimoto similarity of the bright available emitters, we present our top candidates for future exploration. As a proof of concept, we use one of these (3,4-difluorophenylmethanamine) to synthesize an MHP which we find has a photoluminescence quantum yield of 10%.

Buffer Components Incorporate into the Framework of Polyserotonin Nanoparticles and Films during Synthesis.

Polyserotonin nanoparticles (PSeNP) and films are bioinspired nanomaterials that have potential in biomedical applications and surface coatings. As studies on polyserotonin (PSe) nanoparticles and films are still in their infancy, synthetic pathways and material development for this new class of nanomaterial await investigation. Here, we sought to determine how different buffers used during the polymerization of serotonin to form nanoparticles and films impact the physicochemical properties of PSe materials. We show that buffer components are incorporated into the polymer matrix, which is also supported by density functional theory calculations. While we observed no significant differences between the elasticity of nanoparticles synthesized in the different buffers, the nanoscale surface properties of PSe films revealed dissimilarities in surface functional groups influenced by solvent molecules. Overall, the results obtained in this work can be used towards the rational design of PSe nanomaterials with tailored properties and for specific applications.

Fast Near-Infrared Photodetection Using III-V Colloidal Quantum Dots.

Colloidal quantum dots (CQDs) are promising materials for infrared (IR) light detection due to their tunable bandgap and their solution processing; however, to date, the time response of CQD IR photodiodes is inferior to that provided by Si and InGaAs. It is reasoned that the high permittivity of II-VI CQDs leads to slow charge extraction due to screening and capacitance, whereas III-Vs-if their surface chemistry can be mastered-offer a low permittivity and thus increase potential for high-speed operation. In initial studies, it is found that the covalent character in indium arsenide (InAs) leads to imbalanced charge transport, the result of unpassivated surfaces, and uncontrolled heavy doping. Surface management using amphoteric ligand coordination is reported, and it is found that the approach addresses simultaneously the In and As surface dangling bonds. The new InAs CQD solids combine high mobility (0.04 cm2 V-1 s-1 ) with a 4× reduction in permittivity compared to PbS CQDs. The resulting photodiodes achieve a response time faster than 2 ns-the fastest photodiode among previously reported CQD photodiodes-combined with an external quantum efficiency (EQE) of 30% at 940 nm.

Multiscale hierarchical structures from a nanocluster mesophase.

Spontaneous hierarchical self-organization of nanometre-scale subunits into higher-level complex structures is ubiquitous in nature. The creation of synthetic nanomaterials that mimic the self-organization of complex superstructures commonly seen in biomolecules has proved challenging due to the lack of biomolecule-like building blocks that feature versatile, programmable interactions to render structural complexity. In this study, highly aligned structures are obtained from an organic-inorganic mesophase composed of monodisperse Cd37S18 magic-size cluster building blocks. Impressively, structural alignment spans over six orders of magnitude in length scale: nanoscale magic-size clusters arrange into a hexagonal geometry organized inside micrometre-sized filaments; self-assembly of these filaments leads to fibres that then organize into uniform arrays of centimetre-scale bands with well-defined surface periodicity. Enhanced patterning can be achieved by controlling processing conditions, resulting in bullseye and 'zigzag' stacking patterns with periodicity in two directions. Overall, we demonstrate that colloidal nanomaterials can exhibit a high level of self-organization behaviour at macroscopic-length scales.

In Situ Inorganic Ligand Replenishment Enables Bandgap Stability in Mixed-Halide Perovskite Quantum Dot Solids.

Instability in mixed-halide perovskites (MHPs) is a key issue limiting perovskite solar cells and light-emitting diodes (LEDs). One form of instability arises during the processing of MHP quantum dots using an antisolvent to precipitate and purify the dots forming surface traps that lead to decreased luminescence, compromised colloidal stability, and emission broadening. Here, the introduction of inorganic ligands in the antisolvents used in dot purification is reported in order to overcome this problem. MHPs that are colloidally stable for over 1 year at 25 °C and 40% humidity are demonstrated and films that are stable under 100 W cm-2 photoirradiation, 4× longer than the best previously reported MHPs, are reported. In LEDs, the materials enable an EQE of 24.4% (average 22.5 ± 1.3%) and narrow emission (full-width at half maximum of 30 nm). Sixfold-enhanced operating stability relative to the most stable prior red perovskite LEDs having external quantum efficiency >20% is reported.

Wide-Bandgap Perovskite Quantum Dots in Perovskite Matrix for Sky-Blue Light-Emitting Diodes.

The epitaxial growth of a perovskite matrix on quantum dots (QDs) has enabled the emergence of efficient red light-emitting diodes (LEDs) because it unites efficient charge transport with strong surface passivation. However, the synthesis of wide-band gap (Eg) QD-in-matrix heterostructures has so far remained elusive in the case of sky-blue LEDs. Here, we developed CsPbBr3 QD-in-perovskite matrix solids that enable high luminescent efficiency and spectral stability with an optical Eg of over 2.6 eV. We screened alloy candidates that modulate the perovskite Eg and allow heteroepitaxy, seeking to implement lattice-matched type-I band alignment. Specifically, we introduced a CsPb1-xSrxBr3 matrix, in which alloying with Sr2+ increased the Eg of the perovskite and minimized lattice mismatch. We then developed an approach to passivation that would overcome the hygroscopic nature of Sr2+. We found that bis(4-fluorophenyl)phenylphosphine oxide strongly coordinates with Sr2+ and provides steric hindrance to block H2O, a finding obtained by combining molecular dynamics simulations with experimental results. The resulting QD-in-matrix solids exhibit enhanced air- and photo-stability with efficient charge transport from the matrix to the QDs. LEDs made from this material exhibit an external quantum efficiency of 13.8% and a brightness exceeding 6000 cd m-2.

Enhanced emission directivity from asymmetrically strained colloidal quantum dots.

Current state-of-the-art quantum dot light-emitting diodes have reached close to unity internal quantum efficiency. Further improvement in external quantum efficiency requires more efficient photon out-coupling. Improving the directivity of the photon emission is considered to be the most feasible approach. Here, we report improved emission directivity from colloidal quantum dot films. By growing an asymmetric compressive shell, we are able to lift their band-edge state degeneracy, which leads to an overwhelming population of exciton with in-plane dipole moment, as desired for high-efficiency photon out-coupling. The in-plane dipole proportion determined by back-focal plane imaging method is 88%, remarkably higher than 70% obtained from conventional hydrostatically strained colloidal quantum dots. Enhanced emission directivity obtained here opens a path to increasing the external quantum efficiencies notably.

Bright and Stable Light-Emitting Diodes Based on Perovskite Quantum Dots in Perovskite Matrix.

Light-emitting diodes (LEDs) based on metal halide perovskite quantum dots (QDs) have achieved impressive external quantum efficiencies; however, the lack of surface protection of QDs, combined with efficiency droop, decreases device operating lifetime at brightnesses of interest. The epitaxial incorporation of QDs within a semiconducting shell provides surface passivation and exciton confinement. Achieving this goal in the case of perovskite QDs remains an unsolved challenge in view of the materials' chemical instability. Here, we report perovskite QDs that remain stable in a thin layer of precursor solution of perovskite, and we use strained QDs as nucleation centers to drive the homogeneous crystallization of a perovskite matrix. Type-I band alignment ensures that the QDs are charge acceptors and radiative emitters. The new materials show suppressed Auger bi-excition recombination and bright luminescence at high excitation (600 W cm-2), whereas control materials exhibit severe bleaching. Primary red LEDs based on the new materials show an external quantum efficiency of 18%, and these retain high performance to brightnesses exceeding 4700 cd m-2. The new materials enable LEDs having an operating half-life of 2400 h at an initial luminance of 100 cd m-2, representing a 100-fold enhancement relative to the best primary red perovskite LEDs.

Facet-Oriented Coupling Enables Fast and Sensitive Colloidal Quantum Dot Photodetectors.

Charge carrier transport in colloidal quantum dot (CQD) solids is strongly influenced by coupling among CQDs. The shape of as-synthesized CQDs results in random orientational relationships among facets in CQD solids, and this limits the CQD coupling strength and the resultant performance of optoelectronic devices. Here, colloidal-phase reconstruction of CQD surfaces, which improves facet alignment in CQD solids, is reported. This strategy enables control over CQD faceting and allows demonstration of enhanced coupling in CQD solids. The approach utilizes post-synthetic resurfacing and unites surface passivation and colloidal stability with a propensity for dots to couple via (100):(100) facets, enabling increased hole mobility. Experimentally, the CQD solids exhibit a 10× increase in measured hole mobility compared to control CQD solids, and enable photodiodes (PDs) exhibiting 70% external quantum efficiency (vs 45% for control devices) and specific detectivity, D* > 1012  Jones, each at 1550 nm. The photodetectors feature a 7 ns response time for a 0.01 mm2 area-the fastest reported for solution-processed short-wavelength infrared PDs.

Electro-Optic Modulation Using Metal-Free Perovskites.

Electro-optic (EO) modulation is of interest to impart information onto an optical carrier. Inorganic crystals-most notably LiNbO3 and BaTiO3-exhibit EO modulation and good stability, but are difficult to integrate with silicon photonic technology. Solution-processed organic EO materials are readily integrated but suffer from thermal degradation at the temperatures required in operating conditions for accelerated reliability studies. Hybrid organic-inorganic metal halide perovskites have the potential to overcome these limitations; however, these have so far relied on heavy metals such as lead and cadmium. Here, we report linear EO modulation using metal-free perovskites, which maintain the crystalline features of the inorganic EO materials and incorporate the flexible functionality of organic EO chromophores. We find that, by introducing a deficiency of cations, we reduce the symmetry in the perovskite crystal and produce thereby an increased EO response. The best-engineered perovskites reported herein showcase an EO coefficient of 14 pm V-1 at a modulation frequency of 80 kHz, an order of magnitude higher than in the nondefective materials. We observe split peaks in the X-ray diffraction and neutron diffraction patterns of the defective sample, indicating that the crystalline structure has been distorted and the symmetry reduced. Density functional theory (DFT) studies link this decreased symmetry to NH4+ deficiencies. This demonstration of EO from metal-free perovskites highlights their potential in next-generation optical information transmission.