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Dataset posted on 2025-03-04, 15:29 authored by Henry La Pierre, Andrew Boggiano, Chad Studvick, Sabyasachi Roy Chowdhury, Julie Niklas, Haruko Tateyama, Hongwei Wu, Johannes Leisen, Florian Kleemiss, Bess Vlaisavljevich, Ivan Popov
Heterogeneous catalysts generally have a variety of active-site structures due to the innate heterogeneity of the surface,resulting in complicated correlations between activity and active-site structure. Single site heterogeneous cobalt catalysts with a uniform catalytic surface were utilized as a platform to probe surface sensitive reactions; in this case CO 2 hydrogenation. It was found that atomically isolated cobalt single sites, which exist solely in the tetrahedral Co 2+ coordination, exclusively form CO under typical CO 2 methanation conditions,while cobalt clusters yielded the highest rate of CO 2 reactionand began to form methane. Utilizing the principles of Ostwald Ripening to probe the ensemble effects for CO 2 hydrogenation, the transition from atomic isolation to small clusters of atoms to nanoparticles was explored. Furthermore, the chemical structure of the cobalt was elucidated primarily via X-Ray Absorption Spectroscopy (XANES/EXAFS) and X-Ray Photoelectron Spectroscopy (XPS).
Conventional ligands for CsPbBr 3 perovskite nanocrystals (NCs), composed of polar, coordinating head groups (e.g., ammonium or zwitterionic) and aliphatic tails, are instrumental in stabilizing the NCs against sintering and aggregation. Nonetheless, the aliphatic (insulating) nature of these ligands represents drawbacks with respect to objectives in optoelectronics, and yet removing these ligands typically leads to a loss of colloidal stability. Here, in this paper, we describe the preparation of CsPbBr 3 NCs in the presence of discrete conjugated oligomers that were prepared by an iterative synthetic approach and capped at their chain ends with sulfobetaine zwitterions for perovskite coordination. Notably, these zwitterionic oligofluorenes are compatible with the hot injection and ligand exchange conditions used to prepare CsPbBr 3 NCs, yielding stable NC dispersions with high photoluminescence quantum yields (PLQY, >90%) and spectral features representative of both the perovskite core and conjugated ligand shell. Controlling the chain length of these capping ligands effectively regulated inter-NC spacing and packing geometry when cast into solid films, with evidence derived from both transmission electron microscopy (TEM) and grazing incidence X-ray scattering measurements.
Two periodic series of homoleptic rare earth nitrato com plexes, [R 4 N] x [M(NO 3 ) y ](M = La-Nd, Sm-Lu, Y); R = Et, $n$ Pr; x = 2-3; y = 5-6) have been synthesized, and charac terized by single crystal X-ray diffraction, IR and Raman spectroscopy, comparing the solid state speciation of the nitrate ions as a function of lanthanide ion and quarternary ammonium cation. The series of the form [Et 4 N] 3 [Ln(NO 3 ) 6 ] crystallizes in the rhombohedral space group $R$$\bar{3}$, as a twelve-coordinate hexanitrato complex [Et 4 N] 3 [Ln(NO 3 ) 6 ] with cocrystallized HNO 3 for La, Pr, and Nd. For Ce, a distinct orthorhombic phase retaining the same formula, [Et 4 N] 3 [Ce(NO 3 ) 6 ] is isolated in the absence of HNO 3 to prevent oxidation of the Ce(III) to Ce(IV) in nitric acid. A ten-coordinate pentanitrato complex, [Et 4 N] 2 [Ln(NO 3 ) 5 ], in monoclinic symmetry forms for the remainder of the series, and for Y(III). The entire series crystallized in the presence of [ $n$ Pr 4 N] + counterions forms a pentanitrato complex [ $n$ Pr 4 N] 2 [M(NO 3 ) 5 ] in the orthorhombic space group, $Pccn$. In conclusion, analysis of trends in the structural and spectroscopic characteristics of these series reveal insight into the structure directing influences of both the lanthanide contraction and the quarternary ammonium cations.
Heterogeneous photocatalysis is less common but can provide unique avenues for inducing novel chemical transformations and can also be utilized for energy transductions, i.e., the energy in the photons can be captured in chemical bonds. Here, we developed a novel heterogeneous photocatalytic system that employs a lead-halide perovskite nanocrystal (NC) to capture photons and direct photogenerated holes to a surface bound transition metal Cu-site, resulting in a N–N heterocyclization reaction. The reaction starts from surface coordinated diamine substrates and requires two subsequent photo-oxidation events per reaction cycle. We establish a photocatalytic pathway that incorporates sequential inner sphere electron transfer events, photons absorbed by the NC generate holes that are sequentially funneled to the Cu-surface site to perform the reaction. The photocatalyst is readily prepared via a controlled cation-exchange reaction and provides new opportunities in photodriven heterogeneous catalysis.
Direct implementation of metal-organic frameworks as the catalyst for CO 2 electroreduction has been challenging due to issues such as poor conductivity, stability, and limited > 2e - products. In this study, Au nanoneedles are impregnated into a cupric porphyrin-based metal-organic framework by exploiting ligand carboxylates as the Au 3+ -reducing agent, simultaneously cleaving the ligand-node linkage. Surprisingly, despite the lack of a coherent structure, the Au-inserted framework affords a superb ethylene selectivity up to 52.5% in Faradaic efficiency, ranking among the best for metal-organic frameworks reported in the literature. Through operando X-ray, infrared spectroscopies and density functional theory calculations, the enhanced ethylene selectivity is attributed to Au-activated nitrogen motifs in coordination with the Cu centers for C-C coupling at the metalloporphyrin sites. Furthermore, the Au-inserted catalyst demonstrates both improved structural and catalytic stability, ascribed to the altered charge conduction path that bypasses the incoherent framework. This study underlines the modulation of reticular metalloporphyrin structure by metal impregnation for steering the CO 2 reduction reaction pathway.
Building molecular conducting magnets has been of considerable interest due to their metallic transport and magnetic properties. Conjugated aniline anions and transition-metal cations are recognized to synthesize such π–d interaction frameworks. Here, an interfacial assembly of quasi-two-dimensional aniline heterojunction frameworks is developed, which consists of a proton-aniline conducting layer (conductivity of 9.2 × 10 2 S cm -1 ) and a transition metal–aniline magnetic layer. The two-dimensional aniline coordination framework with pronounced π–d interactions is indispensable for obtaining ordered spin states and metallic transport conductivity. We apply optical and Raman spectroscopy to study the interactions between the metal cations and nitrogen atoms in the aniline chains. The bilayer heterostructure maintains a high conductivity of 3.5 × 10 2 S cm -1 and increased magnetization, while the coupling of metallic conducting and magnetic layers leads to an enhanced magnetoconductance of 0.4% under a magnetic field of 70 kOe.
The synthesis and characterization of a series of Sn(II) and Sn(IV) complexes supported by the highly electron-withdrawing dianionic perfluoropinacolate (pinF) ligand are reported herein. Three analogs of [Sn IV (pin F ) 3 ] 2- with NEt 3 H + (1), K + (2), and {K(18C6)} + (3) counter cations and two analogs of [SnII(pinF)2]2- with K+ (4) and {K(15C5) 2 } + (5) counter cations were prepared and characterized by standard analytical methods, single-crystal X-ray diffraction, and 119 Sn Mössbauer and NMR spectroscopies. The six-coordinate SnIV(pinF) complexes display 119 Sn NMR resonances and 119 Sn Mössbauer spectra similar to SnO 2 (cassiterite). In contrast, the four-coordinate SnII(pinF) complexes, featuring a stereochemically-active lone pair, possess low 119 Sn NMR chemical shifts and relatively high quadrupolar splitting. Furthermore, the Sn(II) complexes are unreactive towards both Lewis bases (pyridine, NEt 3 ) and acids (BX 3 , Et 3 NH + ). Calculations confirm that the Sn(II) lone pair is localized within the 5s orbital and reveal that the Sn 5p x LUMO is energetically inaccessible, which effectively abates reactivity.
Excellent ethylene selectivity in acetylene semi-hydrogenation is often obtained at the expense of activity. To break the activity-selectivity trade-off, precise control and in-depth understanding of the three-dimensional atomic structure of surfacial active sites are crucial. Here, we designed a novel Au@PdCu core–shell nanocatalyst featuring diluted and stretched Pd sites on the ultrathin shell (1.6 nm), which showed excellent reactivity and selectivity, with 100% acetylene conversion and 92.4% ethylene selectivity at 122 °C, and the corresponding activity was 3.3 times higher than that of the PdCu alloy. The atomic three-dimensional decoding for the activity-selectivity balance was revealed by combining pair distribution function (PDF) and reverse Monte Carlo simulation (RMC). The results demonstrate that a large number of active sites with a low coordination number of Pd–Pd pairs and an average 3.25% tensile strain are distributed on the surface of the nanocatalyst, which perform a pivotal function in the simultaneous improvement of hydrogenation activity and ethylene selectivity. Our work not only develops a novel strategy for unlocking the linear scaling relation in heterogeneous catalysis but also provides a paradigm for atomic 3D understanding of lattice strain in core–shell nanocatalysts.
Multifidelity modeling is a technique for fusing the information from two or more datasets into one model. It is particularly advantageous when one dataset contains few accurate results and the other contains many less accurate results. Within the context of modeling potential energy surfaces, the low-fidelity dataset can be made up of a large number of inexpensive energy computations that provide adequate coverage of the N-dimensional space spanned by the molecular internal coordinates. The high-fidelity dataset can provide fewer but more accurate electronic energies for the molecule in question. Here, we compare the performance of several neural network-based approaches to multifidelity modeling. We show that the four methods (dual, Δ-learning, weight transfer, and Meng–Karniadakis neural networks) outperform a traditional implementation of a neural network, given the same amount of training data. We also show that the Δ-learning approach is the most practical and tends to provide the most accurate model.
Reanalysis datasets are widely used to understand numerous atmospheric processes. Different reanalyses may give very different results for the same diagnostics. The Stratosphere-troposphere Processes And their Role in Climate (SPARC) Reanalysis Intercomparison Project (S-RIP, https://s-rip.github.io/) is a coordinated activity to compare key diagnostics among available reanalyses, identify differences among reanalyses and their underlying causes, provide guidance on appropriate usage of reanalyses in scientific studies, and contribute to future improvements in the reanalysis products via collaborations with reanalysis centers and data users. S-RIP Phase 1 (completed in early 2022) focused primarily on the upper troposphere through the middle atmosphere and processes linking these regions to the troposphere and surface. We look forward to broadening our efforts in Phase 2 (S-RIP2), with new foci including studies of tropospheric circulation, extreme weather events, and their links to the stratosphere, and focusing on evaluation of chemical reanalyses, both those with a stratosphere / upper troposphere focus and those that focus on air quality applications. This presentation will provide a summary of Phase 1 results and discussion of future directions for S-RIP2, emphasizing applications to composition and chemistry studies as well as fostering capacity building for Early Career Scientists.
Reanalysis datasets are widely used to understand numerous atmospheric processes. Different reanalyses may give very different results for the same diagnostics. The Stratosphere-troposphere Processes And their Role in Climate (SPARC) Reanalysis Intercomparison Project (S-RIP, https://s-rip.github.io/) is a coordinated activity to compare key diagnostics among available reanalyses, identify differences among reanalyses and their underlying causes, provide guidance on appropriate usage of reanalyses in scientific studies, and contribute to future improvements in the reanalysis products via collaborations with reanalysis centers and data users. S-RIP Phase 1 (completed in early 2022) focused primarily on the upper troposphere through the middle atmosphere and processes linking these regions to the troposphere and surface. We look forward to broadening our efforts in Phase 2 (S-RIP2), with new foci including studies of tropospheric circulation, extreme weather events, and their links to the stratosphere, and focusing on evaluation of chemical reanalyses, both those with a stratosphere / upper troposphere focus and those that focus on air quality applications. This presentation will provide a summary of Phase 1 results and discussion of future directions for S-RIP2, emphasizing applications to composition and chemistry studies as well as fostering capacity building for Early Career Scientists.
Reanalysis datasets are widely used to understand numerous atmospheric processes. Different reanalyses may give very different results for the same diagnostics. The Stratosphere-troposphere Processes And their Role in Climate (SPARC) Reanalysis Intercomparison Project (S-RIP, https://s-rip.github.io/) is a coordinated activity to compare key diagnostics among available reanalyses, identify differences among reanalyses and their underlying causes, provide guidance on appropriate usage of reanalyses in scientific studies, and contribute to future improvements in the reanalysis products via collaborations with reanalysis centers and data users. S-RIP Phase 1 (completed in early 2022) focused primarily on the upper troposphere through the middle atmosphere and processes linking these regions to the troposphere and surface. We look forward to broadening our efforts in Phase 2 (S-RIP2), with new foci including studies of tropospheric circulation, extreme weather events, and their links to the stratosphere, and focusing on evaluation of chemical reanalyses, both those with a stratosphere / upper troposphere focus and those that focus on air quality applications. This presentation will provide a summary of Phase 1 results and discussion of future directions for S-RIP2, emphasizing applications to composition and chemistry studies as well as fostering capacity building for Early Career Scientists.
Parkinson’s disease (PD) is a prevalent age-related neurodegenerative syndrome, partially thought to be caused by a decrease in alpha-synuclein proteostasis. Anle138b = 5-(1,3-benzodioxol-5-yl)-3-(3-bromophenyl)-1H-pyrazole (HL), is undergoing clinical trials as a promising mitigator of alpha-synuclein aggregation. Because complexation to metals is known to modulate the activity of several drugs, we have prepared and characterized: H2L(ClO4), [CuI(µ-L)]3, and [AgI(µ-L)]3. To better understand the bioviability of these compounds, we monitored their effects in a cell culture model of alpha-synuclein protein aggregation using human alpha-synuclein pre-formed fibrils (PFFs). Using two different anti-alpha-synuclein antibodies, our data suggests that [AgI(µ-L)]3 decreases a C-terminal truncated protein that is approximately 12.4 kDa, as well as increases the size and alters the shape of PFF-induced aggregates. This indicates that [AgI(µ-L)]3 impacts aggregation in a manner different from HL and may serve as a novel tool for studying C-terminal truncation related aggregation chemistry.
Phoenix results, combined with coordinated observations from the Mars Reconnaissance Orbiter of the Phoenix lander site, indicate that the water vapor is nonuniform (i.e., not well mixed) up to a calculated cloud condensation level. It is important to understand the mixing profile of water vapor because (a) the assumption of a well-mixed atmosphere up to a cloud condensation level is common in retrievals of column water abundances which are in turn used to understand the seasonal and interannual behavior of water, (b) there is a long history of observations and modeling that conclude both that water vapor is and is not well-mixed, and some studies indicate that the water vapor vertical mixing profile may, in fact, change with season and location, (c) the water vapor in the lowest part of the atmosphere is the reservoir that can exchange with the regolith and higher amounts may have an impact on the surface chemistry, and (d) greater water vapor abundances close to the surface may enhance surface exchange thereby reducing regional transport, which in turn has implications to the net transport of water vapor over seasonal and annual timescales.
Metal–organic frameworks (MOFs) are crystalline, 2- and 3-dimensional coordination polymers formed by bonding interactions between metals and multitopic organic ligands. These are typically formed using hard Lewis basic organic ligands with high oxidation state metal ions. The use of low-valent metals as structural elements in MOFs is far less common, despite the widespread use of such metals for catalysis, luminescence, and other applications. Furthermore, this Minireview focuses on recent advances in the field of low-valent MOFs and offers a perspective on the future development of these materials.
The thermocatalytic reduction of CO2 by H2 often proceeds via two competing reaction mechanisms—the reverse water gas shift reaction (rWGSR, CO2 + H2 ⇌ CO + H2O) and methanation (CO2 + 4H2 ⇌ CH4 + 2H2O). Atomically dispersed Rh1 catalysts on TiO2 show high selectivity toward the rWGSR compared with larger Rh nanoclusters, but the origin of this size-dependent selectivity has not been fully explained. Here we report density functional theory (DFT) calculations and microkinetic simulations that clarify the Rh1 active sites and rWGSR pathway on anatase TiO2(101), as well as the high rWGSR selectivity of Rh1 compared with supported Rhx (x = 2–8 atoms) nanoclusters. DFT-computed formation energies, vibrational frequency analysis, and microkinetic modeling suggest three plausible active sites: Rh1 on titania (Rh1/TiO2(101)), Rh1 with a nearby hydroxyl group (Rh1OH/TiO2(101)), and Rh1 near an oxygen vacancy at a three-fold coordinated site (Rh1 near O3cvac). Predicted turnover frequencies and apparent activation barriers for Rh1 indicate a faster reaction involving CO2 dissociation assisted by a support oxygen vacancy via Rh1 near O3cvac, as well as slower reactions involving Rh1OH/TiO2(101) or Rh1/TiO2(101) through a COOH intermediate. Furthermore, these Rh1 sites are selective toward CO rather than CH4 because of the weak adsorption of CO, large barrier for C-O bond dissociation, and the lack of nearby metal sites for H2 dissociation, in contrast to Rhx nanoclusters, including Rh2 dimers.
"Water-in-salt" electrolytes open up exciting new avenues for expanding the electrochemical window of aqueous electrolytes. We investigated the solvation structure and dynamics of highly concentrated lithium bis(trifluoromethane)sulfonimide aqueous electrolyte using experimentally corroborated molecular dynamics simulations. The simulations revealed that the heterogeneous structure of the electrolyte comprises percolating networks of ion and water domains/aggregates. Interestingly, the ionic regions are composed of more TFSI - ions than Li + ions. The Li + -ion transport mechanism was further explored. Li + ions can hop along the coordinated TFSI- ions in the ionic aggregates. The calculated correlated transference number of the 20 m electrolyte is similar to 0.32, which is reasonably high for the high concentration due to a weak negative correlation between the motion of cations and anions within the heterogeneous microscopic domains. These molecular dynamics results connect the heterogeneous structure of the electrolyte to the correlated dynamics of the Li + ion and provide a new understanding of the Li + -ion transport mechanism in this novel electrolyte.