Selective and Stable CO2 Electroreduction to CH4 via Electronic Metal-Support Interaction upon Decomposition/Redeposition of MOF.

The CO2 electroreduction to fuels is a feasible approach to provide renewable energy sources. Therefore, it is necessary to conduct experimental and theoretical investigations on various catalyst design strategies, such as electronic metal-support interaction, to improve the catalytic selectivity. Here a solvent-free synthesis method is reported to prepare a copper (Cu)-based metal-organic framework (MOF) as the precursor. Upon electrochemical CO2 reduction in aqueous electrolyte, it undergoes in situ decomposition/redeposition processes to form abundant interfaces between Cu nanoparticles and amorphous carbon supports. This Cu/C catalyst favors the selective and stable production of CH4 with a Faradaic efficiency of ≈55% at -1.4 V versus reversible hydrogen electrode (RHE) for 12.5 h. The density functional theory calculation reveals the crucial role of interfacial sites between Cu and amorphous carbon support in stabilizing the key intermediates for CO2 reduction to CH4 . The adsorption of COOH* and CHO* at the Cu/C interface is up to 0.86 eV stronger than that on Cu(111), thus promoting the formation of CH4 . Therefore, it is envisioned that the strategy of regulating electronic metal-support interaction can improve the selectivity and stability of catalyst toward a specific product upon electrochemical CO2 reduction.

Site specificity of halogen bonding involving aromatic acceptors.

Halogen bonding (XB) has become one of the most studied non-covalent interactions in the past two decades, owing to its wide range of applications in materials and biological applications. Most of the current theoretical and experimental studies focus on XB involving lone-pair acceptors due to its predictability in terms of crystal geometries. However, recent reports have advocated the importance of XB materials involving aromatic-type acceptors because of their relevance in functional materials, catalysis and biological systems. Herein, we report the XB site-specificity in several polycyclic aromatic hydrocarbons (PAHs) and N-heteroaromatic compounds that are ubiquitous in chemical systems. Based on a series of quantum chemical studies of Cl2 and Br2 XB complexes with 14 representative systems, these XB sites can be easily predicted using occupied molecular orbitals and atomic charges. We envisage that the predicted site maps will be useful for materials and drug design involving this class of non-covalent interactions.

Computational and Experimental Investigation of the Structure of Peptide Monolayers on Gold Nanoparticles.

The self-assembly and self-organization of small molecules on the surface of nanoparticles constitute a potential route toward the preparation of advanced proteinlike nanosystems. However, their structural characterization, critical to the design of bionanomaterials with well-defined biophysical and biochemical properties, remains highly challenging. Here, a computational model for peptide-capped gold nanoparticles (GNPs) is developed using experimentally characterized Cys-Ala-Leu-Asn-Asn (CALNN)- and Cys-Phe-Gly-Ala-Ile-Leu-Ser-Ser (CFGAILSS)-capped GNPs as a benchmark. The structure of CALNN and CFGAILSS monolayers is investigated using both structural biology techniques and molecular dynamics simulations. The calculations reproduce the experimentally observed dependence of the monolayer secondary structure on the peptide capping density and on the nanoparticle size, thus giving us confidence in the model. Furthermore, the computational results reveal a number of new features of peptide-capped monolayers, including the importance of sulfur movement for the formation of secondary structure motifs, the presence of water close to the gold surface even in tightly packed peptide monolayers, and the existence of extended 2D parallel ß-sheet domains in CFGAILSS monolayers. The model developed here provides a predictive tool that may assist in the design of further bionanomaterials.

Using non-empirically tuned range-separated functionals with simulated emission bands to model fluorescence lifetimes.

Fluorescence lifetimes were evaluated using TD-DFT under different approximations for the emitting molecule and various exchange-correlation functionals, such as B3LYP, BMK, CAM-B3LYP, LC-BLYP, M06, M06-2X, M11, PBE0, ωB97, ωB97X, LC-BLYP*, and ωB97X* where the range-separation parameters in the last two functionals were tuned in a non-empirical fashion. Changes in the optimised molecular geometries between the ground and electronically excited states were found to affect the quality of the calculated lifetimes significantly, while the inclusion of vibronic features led to further improvements over the assumption of a vertical electronic transition. The LC-BLYP* functional was found to return the most accurate fluorescence lifetimes with unsigned errors that are mostly within 1.5 ns of experimental values.

A Review of Databases Used in Orthopaedic Surgery Research and an Analysis of Database Use in Arthroscopy: The Journal of Arthroscopic and Related Surgery.

PURPOSE: The purpose of this study was to evaluate how database use has changed over time in Arthroscopy: The Journal of Arthroscopic and Related Surgery and to inform readers about available databases used in orthopaedic literature. METHODS: An extensive literature search was conducted to identify databases used in Arthroscopy and other orthopaedic literature. All articles published in Arthroscopy between January 1, 2006, and December 31, 2015, were reviewed. A database was defined as a national, widely available set of individual patient encounters, applicable to multiple patient populations, used in orthopaedic research in a peer-reviewed journal, not restricted by encounter setting or visit duration, and with information available in English. RESULTS: Databases used in Arthroscopy included PearlDiver, the American College of Surgeons National Surgical Quality Improvement Program, the Danish Common Orthopaedic Database, the Swedish National Knee Ligament Register, the Hospital Episodes Statistics database, and the National Inpatient Sample. Database use increased significantly from 4 articles in 2013 to 11 articles in 2015 (P = .012), with no database use between January 1, 2006, and December 31, 2012. CONCLUSIONS: Database use increased significantly between January 1, 2006, and December 31, 2015, in Arthroscopy. LEVEL OF EVIDENCE: Level IV, systematic review of Level II through IV studies.

Thioamide-Directed Cobalt(III)-Catalyzed Selective Amidation of C(sp3 )-H Bonds.

A mild, oxidant-free, and selective Cp*CoIII -catalyzed amidation of thioamides with robust dioxazolone amidating agents via C(sp3 )-H bond activation to generate the desired amidated products is reported. The method is efficient and allows for the C-H amidation of a wide range of functionalized thioamides with aryl-, heteroaryl-, and alkyl-substituted dioxazolones under the Cp*CoIII -catalyzed conditions. The observed regioselectivity towards primary C(sp3 )-H activation is supported by computational studies and the cyclometalation is proposed to proceed by means of an external carboxylate-assisted concerted metalation/deprotonation mechanism. The reported method is a rare example of the use of a directing group other than the commonly used pyridine and quinolone classes for Cp*CoIII -catalyzed C(sp3 )-H functionalization and the first to exploit thioamides.

First principles (DFT) characterization of Rh(I) /dppp-catalyzed C-H activation by tandem 1,2-addition/1,4-Rh shift reactions of norbornene to phenylboronic acid.

The C-H activation in the tandem, "merry-go-round", [(dppp)Rh]-catalyzed (dppp=1,3-bis(diphenylphosphino)propane), four-fold addition of norborene to PhB(OH)2 has been postulated to occur by a C(alkyl)H oxidative addition to square-pyramidal Rh(III) -H species, which in turn undergoes a C(aryl)-H reductive elimination. Our DFT calculations confirm the Rh(I) /Rh(III) mechanism. At the IEFPCM(toluene, 373.15 K)/PBE0/DGDZVP level of theory, the oxidative addition barrier was calculated to be 12.9 kcal mol(-1) , and that of reductive elimination was 5.0 kcal mol(-1) . The observed selectivity of the reaction correlates well with the relative energy barriers of the cycle steps. The higher barrier (20.9 kcal mol(-1) ) for norbornyl-Rh protonation ensures that the reaction is steered towards the 1,4-shift (total barrier of 16.3 kcal mol(-1) ), acting as an equilibration shuttle. The carborhodation (13.2 kcal mol(-1) ) proceeds through a lower barrier than the protonation (16.7 kcal mol(-1) ) of the rearranged aryl-Rh species in the absence of o- or m-substituents, ensuring multiple carborhodations take place. However, for 2,5-dimethylphenyl, which was used as a model substrate, the barrier for carborhodation is increased to 19.4 kcal mol(-1) , explaining the observed termination of the reaction at 1,2,3,4-tetra(exo-norborn-2-yl)benzene. Finally, calculations with (Z)-2-butene gave a carborhodation barrier of 20.2 kcal mol(-1) , suggesting that carborhodation of non-strained, open-chain substrates would be disfavored relative to protonation.

Natural tri- to hexapeptides self-assemble in water to amyloid beta-type fiber aggregates by unexpected alpha-helical intermediate structures.

Many fatal neurodegenerative diseases such as Alzheimer's, Parkinson, the prion-related diseases, and non-neurodegenerative disorders such as type II diabetes are characterized by abnormal amyloid fiber aggregates, suggesting a common mechanism of pathogenesis. We have discovered that a class of systematically designed natural tri- to hexapeptides with a characteristic sequential motif can simulate the process of fiber assembly and further condensation to amyloid fibrils, probably via unexpected dimeric α-helical intermediate structures. The characteristic sequence motif of the novel peptide class consists of an aliphatic amino acid tail of decreasing hydrophobicity capped by a polar head. To our knowledge, the investigated aliphatic tripeptides are the shortest ever reported naturally occurring amino acid sequence that can adopt α-helical structure and promote amyloid formation. We propose the stepwise assembly process to be associated with characteristic conformational changes from random coil to α-helical intermediates terminating in cross-ß peptide structures. Circular dichroism and X-ray fiber diffraction analyses confirmed the concentration-dependent conformational changes of the peptides in water. Molecular dynamics simulating peptide behavior in water revealed monomer antiparallel pairing to dimer structures by complementary structural alignment that further aggregated and stably condensed into coiled fibers. The ultrasmall size and the dynamic facile assembly process make this novel peptide class an excellent model system for studying the mechanism of amyloidogenesis, its evolution and pathogenicity. The ability to modify the properties of the assembled structures under defined conditions will shed light on strategies to manipulate the pathogenic amyloid aggregates in order to prevent or control aggregate formation.

Step flow versus mosaic film growth in hexagonal boron nitride.

Many emerging applications of hexagonal boron nitride (h-BN) in graphene-based nanoelectronics require high-quality monolayers as the ultrathin dielectric. Here, the nucleation and growth of h-BN monolayer on Ru(0001) surface are investigated using scanning tunneling microscopy with a view toward understanding the process of defect formation on a strongly interacted interface. In contrast to homoelemental bonding in graphene, the heteroelemental nature of h-BN gives rise to growth fronts with elemental polarity. This can have consequences in the different stages of film growth, from the nucleation of h-BN magic clusters and their sintering to form compact triangular islands to the growth of patchwork mosaic monolayer with a high density of misfit boundaries. The parallel alignment of triangular islands on the same terrace produces translational fault lines when growth fronts merge, while antiparallel alignment of islands on adjacent terraces produces non-bonded fault lines between domains terminated by like atoms. With these insights into the generation of void defects and fault lines at grain boundaries, we demonstrate a strategy to obtain high-quality h-BN monolayer film based on step flow growth.

Surface charge as activity descriptors for electrochemical CO2 reduction to multi-carbon products on organic-functionalised Cu.

Intensive research in electrochemical CO2 reduction reaction has resulted in the discovery of numerous high-performance catalysts selective to multi-carbon products, with most of these catalysts still being purely transition metal based. Herein, we present high and stable multi-carbon products selectivity of up to 76.6% across a wide potential range of 1 V on histidine-functionalised Cu. In-situ Raman and density functional theory calculations revealed alternative reaction pathways that involve direct interactions between adsorbed histidine and CO2 reduction intermediates at more cathodic potentials. Strikingly, we found that the yield of multi-carbon products is closely correlated to the surface charge on the catalyst surface, quantified by a pulsed voltammetry-based technique which proved reliable even at very cathodic potentials. We ascribe the surface charge to the population density of adsorbed species on the catalyst surface, which may be exploited as a powerful tool to explain CO2 reduction activity and as a proxy for future catalyst discovery, including organic-inorganic hybrids.

Thiophene-containing Pechmann dyes and related compounds: synthesis, and experimental and DFT characterisation.

Attaching 2-thienyl residues to the Pechmann dye core chromophore (5,5-exo-dilactone situated around a C-C double bond) results in a novel magenta-coloured compound (UV/Vis spectroscopy λ(max) =570 nm in CHCl(3)), which can be rearranged to a yellow 6,6-endo-dilactone (λ(max) =462 nm in CHCl(3)). Single and double amidation results in pronounced redshift in the 5,5-exo series (violet, λ(max) =570 nm and blue, λ(max) =606 nm in CHCl(3), respectively) but pronounced blueshift in the 6,6-endo series (yellow, λ(max) =424 nm and pale yellow bordering on colourless, λ(max) =395 nm in CHCl(3), respectively). Incorporation of a 3-alkyl substituent on the thiophene ring allows for sharp increase of solubility in organic solvents concomitant with fine-tuning of the colour: a redshift in 5,5-exo-dilactones but a blueshift in 5,5-exo-dilactams. DFT computations demonstrate that both lactone classes are planar regardless of the presence of a 3-alkyl group. The lactam derivatives are non-planar: the thiophene-core chromophore dihedral angles increase on going from 5,5-exo to 6,6-endo and from thiophene to 3-alkyl thiophene. Depending on the core heteroatom (O vs. N-alkyl), ring junction (5,5-exo vs. 6,6-endo) and 3-thiophene substituent (H vs. alkyl), two, three, four or six conformers are possible. All of these conformers were characterised by DFT and were found to be very close in energy at both IEFPCM/B3LYP/DGDZVP and SMD/M06/DGDZVP levels of theory. Within each conformer set, the HOMO and LUMO energies were within 0.05 eV and the predicted λ(max) values (TD-DFT) within 10 nm, and this implies low sensitivity of the optical and electronic properties to conformation. Cyclic voltammetry measurements of selected compounds demonstrated good matching to the HOMO and LUMO energies from IEFPCM/B3LYP/DGDZVP computations. M06-2X was the best DFT functional for TD-DFT, giving predicted λ(max) values within about 20 nm.

Electronic excitation of [(µ4-η2-alkyne)Rh4(CO)8(µ-CO)2]: an in situ UV/Vis spectroscopy, spectral reconstruction and DFT study.

Reactions of three alkynes, namely, 1-heptyne, 3-hexyne and 1-phenyl-1-butyne, with [Rh(4)(CO)(9)(µ-CO)(3)] are performed in anhydrous hexane under argon atmosphere with multiple perturbations of alkynes and [Rh(4)(CO)(9)(µ-CO)(3)]. The reactions are monitored by in situ UV/Vis spectroscopy, and the collected electronic spectra are further analyzed with the band-target entropy minimization (BTEM) family of algorithms to reconstruct the pure component spectra. Three BTEM estimates of [(µ(4)-η(2)-alkyne)Rh(4)(CO)(8)(µ-CO)(2)], in addition to that of [Rh(4)(CO)(9)(µ-CO)(3)], are successfully reconstructed from the experimental spectra. Time-dependent density functional theory (TD-DFT) predicted spectra at the PBE0/DGDZVP level are consistent with the corresponding BTEM estimates. The present study demonstrates that: 1) the BTEM family of algorithms is successful in analyzing multi-component UV/Vis spectra and results in good spectral estimates of the trace organometallics present; and 2) the subsequent DFT/TD-DFT methods provide an interpretation of the nature of the electronic excitation and can be used to predict the electronic spectra of similar transition organometallic complexes.

Time-dependent density functional theory (TDDFT) modelling of Pechmann dyes: from accurate absorption maximum prediction to virtual dye screening.

The red Pechmann dye (λ(max) = 550 nm) is the exo-dimer of 4-phenyl-3-butenolide connected at the α-carbon by a double bond in a trans-fashion. The ring system is easily rearranged to the trans-endo-fused bicyclic 6-membered lactone dimer (yellow). Both lactones can be singly or doubly amidated with primary amines leading to further colour changes. The nature of the core heterocycle (exo- vs. endo-; 5- or 6-membered ring), core heteroatom (O vs. N) and additional substituents on the phenyl ring allows for exquisite control over colour achievable within a single dye family. Herein we present a detailed investigation of the modelling of the electronic spectra of the Pechmann dye family by time-dependent density functional theory (TDDFT). Whereas pure Hartree-Fock (TDHF) ab-initio calculation underestimates the UV/Vis absorption maximum, pure TDDFT leads to a large overestimation. The accuracy of the prediction is highly dependent on the mix of HF and DFT, with BMK (42% HF) and M06-2X (54% HF) giving the closest match with the experimental value. Among all basis sets evaluated, the computationally-efficient, DFT-optimized DGDZVP showed the best chemical accuracy/size profile. Finally, the dispersion interaction-corrected (SMD) implicit solvation model was found to be advantageous compared to the original IEFPCM. The absorption maxima of substituted Pechmann dyes and their rearranged lactone counterparts can be predicted with excellent accuracy (±6 nm) at the optimal SMD(toluene)/TD-BMK/DGDZVP//SMD(toluene)B3LYP/DGDZVP level of theory. Using this procedure, a small virtual library of novel, heterocycle-substituted Pechmann dyes were screened. Such substitution was shown to be a viable strategy for colour tuning, giving λ(max) from 522 (4-pyridyl) to 627 (2-indolyl) nm.

First-principles study of silicon nanowire approaching the bulk limit.

First-principles density functional theory calculations on hydrogenated silicon nanowires (SiNWs) with diameters up to 7.3 nm are carried out for comparing to experimentally relevant SiNWs and evaluating its radial doping profiles. We show that the direct band gap nature of both the small diameter (110) and (100) SiNWs fades when the diameter reaches beyond about 4 nm, where the difference of direct and indirect band gaps are close, within the experimental measurement uncertainty of ±0.1 eV, suggesting the diameter size where the gap nature transition starts. In addition, we reveal that core-surface boron (B) codoped SiNW forms more preferably at large diameter than that of the surface-surface codoped one, attributing to the lower energy configuration raised by the core B dopant at large diameter SiNW. More importantly, the diameter for such a preferential transition increases as the doping concentration decreases. Our results rationalize photoluminescent measurements and radial doping distributions of SiNWs.

Insight into the Origin of Trapping in Polymer/Fullerene Blends with a Systematic Alteration of the Fullerene to Higher Adducts.

The bimolecular recombination characteristics of conjugated polymer poly[(4,4'-bis(2-ethylhexyl)dithieno[3,2-b:2',3'-d]silole)-2,6-diyl-alt-(2,5-bis 3-tetradecylthiophen-2-yl thiazolo 5,4-d thiazole)-2,5diyl] (PDTSiTTz) blended with the fullerene series PC60BM, ICMA, ICBA, and ICTA have been investigated using microsecond and femtosecond transient absorption spectroscopy, in conjunction with electroluminescence measurements and ambient photoemission spectroscopy. The non-Langevin polymer PDTSiTTz allows an inspection of intrinsic bimolecular recombination rates uninhibited by diffusion, while the low oscillator strengths of fullerenes allow polymer features to dominate, and we compare our results to those of the well-known polymer Si-PCPDTBT. Using µs-TAS, we have shown that the trap-limited decay dynamics of the PDTSiTTz polaron becomes progressively slower across the fullerene series, while those of Si-PCPDTBT are invariant. Electroluminescence measurements showed an unusual double peak in pristine PDTSiTTz, attributed to a low energy intragap charge transfer state, likely interchain in nature. Furthermore, while the pristine PDTSiTTz showed a broad, low-intensity density of states, the ICBA and ICTA blends presented a virtually identical DOS to Si-PCPDTBT and its blends. This has been attributed to a shift from a delocalized, interchain highest occupied molecular orbital (HOMO) in the pristine material to a dithienosilole-centered HOMO in the blends, likely a result of the bulky fullerenes increasing interchain separation. This HOMO localization had a side effect of progressively shifting the polymer HOMO to shallower energies, which was correlated with the observed decrease in bimolecular recombination rate and increased "trap" depth. However, since the density of tail states remained the same, this suggests that the traditional viewpoint of "trapping" being dominated by tail states may not encompass the full picture and that the breadth of the DOS may also have a strong influence on bimolecular recombination.

Lithium monoxide anion: a ground-state triplet with the strongest base to date.

Lithium monoxide anion (LiO(-)) has been generated in the gas phase and is found to be a stronger base than methyl anion (CH(3)(-)). This makes LiO(-) the strongest base currently known, and it will be a challenge to produce a singly charged or multiply charged anion that is more basic. The experimental acidity of lithium hydroxide is DeltaH degrees (acid) = 425.7 +/- 6.1 kcal.mol(-1) (1 kcal = 4.184 kJ) and, when combined with results of high-level computations, leads to our best estimate for the acidity of 426 +/- 2 kcal.mol(-1).

An epidemiological analysis of revision aetiologies in total hip arthroplasty at a single high-volume centre.

AIMS: Advances in surgical technique and implant design may influence the incidence and mechanism of failure resulting in revision total hip arthroplasty (rTHA). The purpose of the current study was to characterize aetiologies requiring rTHA, and to determine whether temporal changes existed in these aetiologies over a ten-year period. METHODS: All rTHAs performed at a single institution from 2009 to 2019 were identified. Demographic information and mode of implant failure was obtained for all patients. Data for rTHA were stratified into two time periods to assess for temporal changes: 2009 to 2013, and 2014 to 2019. Operative reports, radiological imaging, and current procedural terminology (CPT) codes were cross-checked to ensure the accurate classification of revision aetiology for each patient. RESULTS: In all, 2,924 patients with a mean age of 64.6 years (17 to 96) were identified. There were 1,563 (53.5%) female patients, and the majority of patients were Caucasian (n = 2,362, 80.8%). The three most frequent rTHA aetiologies were infection (27.2%), aseptic loosening (25.2%), and wear (15.2%). The frequency of rTHA for adverse local tissue reaction (ALTR) was significantly greater from 2014 to 2019 (4.7% vs 10.0%; p < 0.001), while the frequency of aseptic loosening was significantly greater from 2009 to 2013 (28.6% vs 21.9%; p < 0.001). CONCLUSION: Periprosthetic joint infection was the most common cause for rTHA in the current cohort of patients. Complications associated with ALTR necessitating rTHA was more frequent between 2014 to 2019, while aseptic loosening necessitating rTHA was significantly more frequent between 2009 to 2013. Optimizing protocols for prevention and management of infection and ALTR after THA may help to avoid additional financial burden to institutions and healthcare systems.Cite this article: Bone Joint Open 2020;2(1):16-21.

Temporal Trends of Revision Etiologies in Total Knee Arthroplasty at a Single High-Volume Institution: An Epidemiological Analysis.

BACKGROUND: Temporal changes in revision total knee arthroplasty (rTKA) may have implications in determining the etiology for implant failure. The purpose of this study was to 1) perform an epidemiologic analysis of etiologies that required rTKA and 2) determine whether temporal changes existed for revision over the study period. METHODS: All rTKA procedures performed at a single institution from 2009 to 2019 were analyzed. Revision procedures were stratified into 2 time periods, 2009-2013 and 2014-2019, to assess for changes over time. Patients' electronic medical record, operative report, and radiographs were reviewed to ensure diagnosis information was accurately documented in relation to the predominate etiology necessitating the revision procedure. RESULTS: Three thousand and nine patients undergoing rTKA between 2009 and 2019 were identified with a mean age of 64.6 years. A total of 1,666 (55.4%) patients were female, and the majority of patients were Caucasian (2,306, 76.6%). The 3 most frequent rTKA etiologies were aseptic loosening (35.1%), periprosthetic infection (33.2%), and instability (16.0%). A higher proportion of patients underwent rTKA for arthrofibrosis (5.1% vs 3.4%, P = .023) and periprosthetic joint infection (38.9% vs 28.6%, P < .001) between 2009 and 2013, while a significantly higher proportion of patients underwent rTKA for instability (12.6% vs 18.8%, P < .001) between 2014 and 2019. CONCLUSION: Aseptic loosening was the most common cause for rTKA over the last decade. rTKA for arthrofibrosis and periprosthetic joint infection was more frequent between 2009 and 2013, while a significantly higher proportion of patients underwent rTKA for instability in 2014-2019. Future studies will need to focus on identifying and reducing risk factors for the trending causes of rTKA.

Electronic transport descriptors for the rapid screening of thermoelectric materials.

The discovery of novel materials for thermoelectric energy conversion has potential to be accelerated by data-driven screening combined with high-throughput calculations. One way to increase the efficacy of successfully choosing a candidate material is through its evaluation using transport descriptors. Using a data-driven screening, we selected 12 potential candidates in the trigonal ABX2 family, followed by charge transport property simulations from first principles. The results suggest that carrier scattering processes in these materials are dominated by ionised impurities and polar optical phonons, contrary to the oft-assumed acoustic-phonon-dominated scattering. Using these data, we further derive ground-state transport descriptors for the carrier mobility and the thermoelectric powerfactor. In addition to low carrier mass, high dielectric constant was found to be an important factor towards high carrier mobility. A quadratic correlation between dielectric constant and transport performance was established and further validated with literature. Looking ahead, dielectric constant can potentially be exploited as an independent criterion towards improved thermoelectric performance. Combined with calculations of thermal conductivity including Peierls and inter-branch coherent contributions, we conclude that the trigonal ABX2 family has potential as high performance thermoelectrics in the intermediate temperature range for low grade waste heat harvesting.

Unravelling V6O13 Diffusion Pathways via CO2 Modification for High-Performance Zinc Ion Battery Cathode.

Vanadium-based oxide is widely investigated as a zinc ion battery (ZIB) cathode due to its ability to react reversibly with Zn2+. Despite its successful demonstration, modification with simple molecules has shown some promise in enhancing the performance of ZIBs. Thus, this presents an immense opportunity to explore simple molecules that can dramatically improve the electrochemical performance of electrodes. Thus, the effect of CO2 modification is studied in this work by decomposing oxalic acid within a hydrated V6O13 framework. Based on the collective results, the presence of CO2 drastically lowers the relative energy of Zn2+ diffusion through the pathways by forming weak electrostatic interactions between OCO2 and Zn2+. This leads to an enlarged diffusion contribution, which consequently results in enhanced stability and better rate performance. The as-synthesized CO2-V6O13 electrode delivers one of the highest specific capacities reported for vanadium-based oxides of ca. 471 mAh g-1. Furthermore, an excellent cyclic stability of 80% capacity retention after 4000 cycles at 2 A g-1 is recorded for CO2-V6O13, which suggests the importance of simple molecules in the material framework toward the enhancement of ZIB cathode performance.