Theoretically Designed Cu10 Sn3 -Cu-SnOx as Three-Component Electrocatalyst for Efficient and Tunable CO2 Reduction to Syngas.

Electrocatalytic transformation of CO2 to various syngas compositions is an exceedingly attractive approach to carbon-neutral recycling. Meanwhile, the achievement of selectivity, stability, and tunability of product ratios using single-component electrocatalysts is challenging. Herein, the theoretically-assisted design of the triple-component nanocomposite electrocatalyst Cu10 Sn3 -Cu-SnOx that addresses this challenge is presented. It is shown that Cu10 Sn3 is a valuable electrocatalyst for suitable CO2 reduction to CO, SnO2 for CO2 reduction to formate at large overpotentials, and that the Cu-SnO2 interface facilitates H2 evolution. Accordingly, the interaction between the three functional components affords tunable CO/H2 ratios, from 1:2 to 2:1, of the produced syngas by controlling the applied potentials and relative contents of functional components. The syngas generation is selective (Faradaic efficiency, FE = 100%) at relatively lower cathodic potentials, whereas formate is the only liquid product detected at relatively higher cathodic potentials. The theoretically guided design approach therefore provides a new opportunity to boost the selectivity and stability of CO2 reduction to tunable syngas.

Underlying Mechanisms and Tunability of the Anomalous Hall Effect in NiCo2 O4 Films with Robust Perpendicular Magnetic Anisotropy.

Their high tunability of electronic and magnetic properties makes transition-metal oxides (TMOs) highly intriguing for fundamental studies and promising for a wide range of applications. TMOs with strong ferrimagnetism provide new platforms for tailoring the anomalous Hall effect (AHE) beyond conventional concepts based on ferromagnets, and particularly TMOs with perpendicular magnetic anisotropy (PMA) are of prime importance for today's spintronics. This study reports on transport phenomena and magnetic characteristics of the ferrimagnetic TMO NiCo2 O4 (NCO) exhibiting PMA. The entire electrical and magnetic properties of NCO films are strongly correlated with their conductivities governed by the cation valence states. The AHE exhibits an unusual sign reversal resulting from a competition between intrinsic and extrinsic mechanisms depending on the conductivity, which can be tuned by the synthesis conditions independent of the film thickness. Importantly, skew-scattering is identified as an AHE contribution for the first time in the low-conductivity regime. Application wise, the robust PMA without thickness limitation constitutes a major advantage compared to conventional PMA materials utilized in today's spintronics. The great potential for applications is exemplified by two proposed novel device designs consisting only of NCO films that open a new route for future spintronics, such as ferrimagnetic high-density memories.

Manipulating the Alkyl Chains of Naphthodithiophene Imide-Based Polymers to Concurrently Boost the Efficiency and Stability of Organic Solar Cells.

Morphology instability holds the major responsibility for efficiency degradation of organic solar cells (OSCs). However, how to develop polymer donors simultaneously with high efficiency and excellent morphology stability remains challenging. Herein, we reported naphtho[2,1-b:3,4-b']dithiophene-5,6-imide (NDTI)-based new polymers PNDT1 and PNDT2. The alkyl chain engineering leads to high crystallinity, high hole mobility (>10-3 cm2 V-1 S-1), and nanofibrous film morphology, which enable PNDT2 to exhibit an efficiency of 18.13% and a remarkable FF value of 0.80. Moreover, the NDTIs have short π-π stacking and abundant short interactions, and their polymers exhibit superior morphological stability. Therefore, the PNDT2-based OSCs exhibit much better device stability than that of PNDT1, PAB-α, and benchmark polymers PM6 and D18. This work suggests the great importance of the large conjugated backbone of the monomer and alkyl chain engineering to develop high-performance and morphology-stable polymers for OSCs.

Insights into Electrochemical CO2 Reduction on SnS2 : Main Product Switch from Hydrogen to Formate by Pulsed Potential Electrolysis.

Tin disulfide (SnS2 ) is a promising candidate for electrosynthesis of CO2 -to-formate while the low activity and selectivity remain a great challenge. Herein, we report the potentiostatic and pulsed potential CO2 RR performance of SnS2 nanosheets (NSs) with tunable S-vacancy and exposure of Sn-atoms or S-atoms prepared controllably by calcination of SnS2 at different temperatures under the H2 /Ar atmosphere. The catalytic activity of S-vacancy SnS2 (Vs -SnS2 ) is improved 1.8 times, but it exhibits an exclusive hydrogen evolution with about 100 % FE under all potentials investigated in the static conditions. The theoretical calculations reveal that the adsorption of *H on the Vs -SnS2 surface is energetically more favorable than the carbonaceous intermediates, resulting in active site coverage that hinders the carbon intermediates from being adsorbed. Fortunately, the main product can be switched from hydrogen to formate by applying pulsed potential electrolysis benefiting from in situ formed partially oxidized SnS2-x with the oxide phase selective to formate and the S-vacancy to hydrogen. This work highlights not only the Vs -SnS2 NSs lead to exclusively H2 formation, but also provides insights into the systematic design of highly selective CO2 reduction catalysts reconstructed by pulsed potential electrolysis.

Building a cobaloxime-based metal-organic framework for photocatalytic aerobic oxidation of arylboronic acids to phenols.

Herein, the design and synthesis of an unprecedented cobaloxime-based zirconium metal-organic framework (Zr-TCPCo) with an she net is reported. This heterogeneous material as a photocatalyst exhibits excellent catalytic activity for aerobic oxidation of arylboronic acids to phenols. Recycling experiments demonstrate the stability and reusability of Zr-TCPCo as a robust catalyst.

A Multifluorination Strategy Toward Wide Bandgap Polymers for Highly Efficient Organic Solar Cells.

Creating new electron-deficient unit is highly demanded to develop high-performance polymer donors for non-fullerene organic solar cells (OSCs). Herein, we reported a multifluorinated unit 4,5,6,7-tetrafluoronaphtho[2,1-b : 3,4-b']dithio-phene (FNT) and its polymers PFNT-F and PFNT-Cl. The advantages of multifluorination: (1) it enables the polymers to exhibit low-lying HOMO (≈-5.5 eV) and wide band gap (≈2.0 eV); (2) the short interactions (F⋅⋅⋅H, F⋅⋅⋅F) endow the polymers with properties of high film crystallinity and efficient hole transport; (3) well miscibility with NFAs that leads to a more well-defined nanofibrous morphology and face-on orientation in the blend films. Therefore, the PFNT-F/Cl : N3 based OSCs exhibit impressive FF values of 0.80, and remarkable PCEs of 17.53 % and 18.10 %, which make them ranked the best donor materials in OSCs. This work offers new insights into the rational design of high-performance polymers by multifluorination strategy.

Facile Solution-Refluxing Synthesis and Photocatalytic Dye Degradation of a Dynamic Covalent Organic Framework.

Covalent organic frameworks (COFs), as a novel crystalline porous adsorbent, have been attracting significant attention for their synthesis and application exploration due to the advantages of designability, stability, and functionalization. Herein, through increasing the concentration of the acid catalyst, a facile solution-refluxing synthesis method was developed for the preparation of a three-dimensional dynamic COF material, COF-300, with high yields (>90%) and high space−time yields (>28 kg m−3 day−1). This synthesis method not only permits gram-scale synthesis, but also yields products that well maintain porosity and unique guest-dependent dynamic behavior. Moreover, the catalytic activity of COF-300 as a metal-free photocatalyst was explored for the first time. Under 365 nm ultra-violet light irradiation, COF-300 can effectively catalyze the dye degradation (>99%) in wastewater with good recyclability. By adding magnetic Fe3O4 nanoparticles into the solution-refluxing synthesis of COF-300, Fe3O4/COF-300 nanocomposites can be obtained and used as magnetically recyclable photocatalysts, demonstrating the superiority of this facile synthesis procedure. Our study provides new insights for the preparation of COF materials and a constructive exploration for their water treatment application.

Ligand Tailoring Strategy of a Metal-Organic Framework for Optimizing Methane Storage Working Capacities.

Methane, as the main component of natural gas, shale gas, and marsh gas, is regarded as an ideal clean energy to replace traditional fossil fuels and reduce carbon emissions. Porous materials with superior methane storage capacities are the key to the wide application of adsorbed natural gas technology in vehicle transportation. In this work, we applied a ligand tailoring strategy to a metal-organic framework (NOTT-101) to fine-tune its pore geometry, which was well characterized by gas and dye sorption measurements. High-pressure methane sorption isotherms revealed that the methane storage performance of the modified NOTT-101 can be effectively improved by decreasing the unusable uptake at 5 bar and increasing the total uptake under high pressures, achieving a substantially high volumetric methane storage working capacity of 190 cm3 (STP) cm-3 at 298 K and 5-80 bar.

Ultrafast Study of Exciton Transfer in Sb(III)-Doped Two-Dimensional [NH3(CH2)4NH3]CdBr4 Perovskite.

Antimony-based metal halide hybrids have attracted enormous attention due to the stereoactive 5s2 electron pair that drives intense triplet broadband emission. However, energy/charge transfer has been rarely achieved for Sb3+-doped materials. Herein, Sb3+ ions are homogeneously doped into 2D [NH3(CH2)4NH3]CdBr4 perovskite (Cd-PVK) using a wet-chemical method. Compared to the weak singlet exciton emission of Cd-PVK at 380 nm, 0.01% Sb3+-doped Cd-PVK exhibits intense triplet emission located at 640 nm with a near-unity quantum yield. Further increasing the doping concentration of Sb3+ completely quenches singlet exciton emission of Cd-PVK, concurrently with enhanced Sb3+ triplet emission. Delayed luminescence and femtosecond-transient absorption studies suggest that Sb3+ emission originates from exciton transfer (ET) from Cd-PVK host to Sb3+ dopant, while such ET cannot occur with Pb2+-doped Cd-PVK because of the mismatch of energy levels. In addition, density function theory calculations indicate that the introduced Sb3+ likely replace the Cd2+ ions along with the deprotonation of butanediammonium for charge balance, instead of generating Cd2+ vacancies. This work provides a deeper understanding of the ET of Sb3+-doped Cd-PVK and suggests an effective strategy to achieve efficient triplet Sb3+ emission beyond 0D Cl-based hybrids.

Harnessing Shape Complementarity for Upgraded Cyclohexane Purification through Adaptive Bottlenecked Pores in an Imidazole-Containing MOF.

Shape complementarity is a biological craft for precisely binding substrates at protein-protein interfaces. An analogy to such a function can be drawn conceptually for crystalline porous solids; yet the manifested entities are rare in reticular chemistry. The bottleneck-shaped pores carved out of a metal-organic framework, Zn(MIBA)2 (aka. MAF-stu-13), can perfectly accommodate benzene molecules. Remarkably, its framework adapts to the optimal guest binding-the enhanced host-guest interactions in the neck in turn minimize the guest-guest repulsion in the pore to the extent it turns into attraction-as demonstrated by the combined X-ray structural and DFT computational studies. This adaptive material can be used for liquid-phase production of ultrahigh-purity (≥99 %) cyclohexane, achieving a balance between uptake capacity and separation selectivity and surpassing the performances of other porous and nonporous crystals reported recently (e.g. product purity 99.4 % vs. 97.5 % to date).

Risk Score Based on Two microRNAs as a Prognostic Marker of Hepatocellular Carcinoma and the Corresponding Competitive Endogenous RNA Network.

PURPOSE: Liver transplantation (LT) currently yields the best outcomes for hepatocellular carcinoma (HCC). However, tumor recurrence still occurs in some patients. Identifying markers that predict HCC recurrence after LT is an unmet medical need. METHODS: In this study, differential expression analysis was used to identify differentially expressed microRNAs (DEmiRs) between HCC and liver tissues in the The Cancer Genome Atlas database and in data from patients with recurrent or non-recurrent HCC in the GSE64989 dataset. The expression profiles of the overlap DEmiRs were used to construct an miRNA-based risk score to predict prognosis using Cox regression analysis. The target genes of the miRNAs of interest were predicted, and they were analyzed for functional enrichment. Furthermore, we used the miRNAs of interest to construct a competitive endogenous RNA (ceRNA) network of long non-coding RNAs (lncRNAs), miRs and mRNAs. RESULTS: Four up-regulated and three down-regulated miRNAs in HCC and recurrent HCC after LT were considered as candidate miRs. MiR-3200-3p and miR-3690 were selected to construct the miR-based risk score, which was found to be associated with poor overall survival and progression-free survival. Furthermore, it proved to be an independent prognostic factor after adjusting for other clinicopathological factors. The corresponding ceRNA networks of these two miRs that we constructed may help to understand their regulatory mechanisms in HCC. CONCLUSION: We propose a risk score based on miR-3200-3p and miR-3690 that may be useful as a prognostic marker to predict HCC recurrence after LT. We generated a ceRNA network involving these miRNAs, which may help reveal their regulatory roles in HCC.

Defect-Related Broadband Emission in Two-Dimensional Lead Bromide Perovskite Microsheets.

Low-dimensional hybrid lead halide perovskites (LHPs) with broadband emission (BE) have been developed as promising candidates for single-source white-light-emitting diodes. However, the underlying origin of such BE is poorly understood. Herein, dual-emissive [NH3(CH2)8NH3]PbBr4 perovskite microsheets (PMSs) with good dispersibility are successfully prepared. Besides the general narrowband emission (NE) originating from free excitons, BE (∼522 nm) is generated under a Br-poor condition, which is not observed in the single-crystal sample. Unlike self-trapped exciton emission, the BE observed in PMSs is experimentally determined to be related to bromide vacancies (VBr), thereby exhibiting quasisaturation under high excitation intensity. Femtosecond transient absorption spectroscopy first shows that the trapping time of the photogenerated electrons by acceptor-like VBr- is ∼15 ps, slower than that by surface defects (<1 ps). This study provides new insight into the underlying mechanism of BE and an effective approach to manipulating the optical properties of 2D perovskites.

Breaking Forbidden Transitions for Emission of Self-Trapped Excitons in Two Dimensional (F2CHCH2NH3)2CdBr4 Perovskite through Pb Alloying.

In this work, a new two-dimensional Cd-based (F2CHCH2NH3)2CdBr4 perovskite (Cd-P) with indirect bandgap and a direct Pb-based (F2CHCH2NH3)2PbBr4 (Pb-P) are successfully synthesized with isostructural features. Compared to the blueish white light emission of Pb-P, almost no white light can be observed for Cd-P due to the forbidden transition of self-trapped exciton (STE) emission. Interestingly, the white light emission of CdxPb1-x-P (x represents the feed ratio of Cd) is significantly improved with the photoluminescence (PL) quantum yield (QY) raising from <1% to 32.5% by alloying these two isostructural perovskites, which is attributed to the breaking of selection rules for forbidden transitions of STEs with Jahn-Teller like octahedral distortion, as suggested by the results from density functional theory (DFT) calculations and time-resolved spectroscopies. This study demonstrates the intriguing effect of alloying on activating STE emission as an effective approach to control and enhance the optical properties of metal halide perovskites.

An Ultrastable Metal Azolate Framework with Binding Pockets for Optimal Carbon Dioxide Capture.

In the evolution of metal-organic frameworks (MOFs) for carbon capture, a lasting challenge is to strike a balance between high uptake capacity/selectivity and low energy cost for regeneration. Meanwhile, these man-made materials have to survive from practical demands such as stability under harsh conditions and feasibility of scale-up synthesis. Reported here is a new MOF, Zn(imPim) (aka. MAF-stu-1), with an imidazole derivative ligand, featuring binding pockets that can accommodate CO2 molecules in a fit-like-a-glove manner. Such a high degree of shape complementarity allows direct observation of the loaded CO2 in the pockets, and warrants its optimal carbon capture performances exceeding the best-performing MOFs nowadays. Coupled with the record thermal (up to 680 °C) and chemical stability, as well as rapid large-scale production, both encoded in the material design, Zn(imPim) represents a most competitive candidate to tackle the immediate problems of carbon dioxide capture.

High Catalytic Activity of C60 Pdn Encapsulated in Metal-Organic Framework UiO-67, for Tandem Hydrogenation Reaction.

Metal nanoparticles (NPs) stabilized by MOFs are very promising for catalysis, whereas introduction of C60 into MOFs has been very rarely used, and there was no report for their cooperative catalysis in organic syntheses. In this work, C60 @UiO-67 was synthesized by a one-pot method, so that C60 is uniformly distributed on UiO-67 in molecular form. Pd NPs coordinating with C60 have been successfully embedded into the framework. The obtained multifunctional C60 Pdn @UiO-67 catalyst exhibits remarkable synergistic catalytic activity in cascade reactions under mild conditions, where UiO-67 affords Lewis acidity and C60 Pdn offers higher hydrogenation activity relative to solely Pd NPs.

A zeolite-like MOF based on a heterotritopic linker of imidazolyl, carboxyl and pyridine with a long-sought uks net on Schwarz's D-surface.

The title MOF features a potential uninodal zeolite net, uks, which has never been found for real zeolites or zeolite-like MOFs. This rare structure exhibits specific anion binding of N3- over SCN- in water, which reverses the Hofmeister series.

An Exceptionally Water Stable Metal-Organic Framework with Amide-Functionalized Cages: Selective CO2 /CH4 Uptake and Removal of Antibiotics and Dyes from Water.

As the main organic pollutants in wastewater, antibiotics and organic dyes are harmful to the environment and public health, and their removal is important but challenging. In this work, highly porous 3D metal-organic frameworks (MOFs) [M2 (PDAD)(H2 O)]n (PCN-124-stu; M=Cu, Zn; H4 PDAD = 5,5'-(pyridine-3,5-dicarbonyl)bis(azanediyl)diisophthalic acid) were synthesized, and PCN-124-stu(Cu) shows excellent chemical and thermal stability. PCN-124-stu(Cu) was used as a host for efficient extraction of various organic dyes, especially the large-molecule dye Coomassie brilliant blue, and fluoroquinolones from water, in comparison with five common MOFs, zeolite 13X, and activated carbon. PCN-124-stu(Cu) exhibits absolute predominance for fluoroquinolone adsorption among these microporous materials because of the H-bonds between fluoroquinolone molecules and the amide groups in the frameworks, except for MIL-100(Cr), which is a mesoporous MOF. Moreover, PCN-124-stu(Cu) could release fluoroquinolones slowly in physiological saline and retained its framework structure after four adsorption/desorption cycles. In addition, PCN-124-stu(Cu) can be used as a platform for selective adsorption of CO2 /CH4.

Ligand Induced Anionic Cuprous Cyanide Framework for Cupric Ion Turn on Luminescence Sensing and Photocatalytic Degradation of Organic Dyes.

A new microporous luminescent coordination polymer [(CH3)2NH2]·[Cu2(CN)3] (1) with channels occupied by dimethylamine cations was synthesized due to the inducing effect of 2-(2'-pyridyl)imidazole. Complex 1 exhibits bright-green emission in the solid state, and its emission intensity would be significantly enhanced, especially by DMAc and cupric ion after immersing the as-synthesized crystals of 1 into common organic solvents or methanol solutions of various metal ions. In addition, 1 exhibits photocatalytic activity for the degradation of RhB and MB under natural light and is stable during the photocatalysis process. Thus, 1 can act as a multifunctional material for selectively sensing of Cu(2+) and effectively photocatalytic degradation of dyes.

Spontaneous symmetry breaking of Co(II) metal-organic frameworks from achiral precursors via asymmetrical crystallization.

The racemic conglomerate (1P-NH3 + 1M-NH3) and enantioenriched bulk samples (1P-H2O or 1M-NH3) of Co(II) metal­organic frameworks were obtained from achiral precursors under different solvothermal conditions. The bulk homochirality was generated through asymmetrical crystallization in the absence of any chiral additives confirmed by single crystal X-ray diffraction and CD spectroscopy.

Spatial, Hysteretic, and Adaptive Host-Guest Chemistry in a Metal-Organic Framework with Open Watson-Crick Sites.

Biological and artificial molecules and assemblies capable of supramolecular recognition, especially those with nucleobase pairing, usually rely on autonomous or collective binding to function. Advanced site-specific recognition takes advantage of cooperative spatial effects, as in local folding in protein-DNA binding. Herein, we report a new nucleobase-tagged metal-organic framework (MOF), namely ZnBTCA (BTC=benzene-1,3,5-tricarboxyl, A=adenine), in which the exposed Watson-Crick faces of adenine residues are immobilized periodically on the interior crystalline surface. Systematic control experiments demonstrated the cooperation of the open Watson-Crick sites and spatial effects within the nanopores, and thermodynamic and kinetic studies revealed a hysteretic host-guest interaction attributed to mild chemisorption. We further exploited this behavior for adenine-thymine binding within the constrained pores, and a globally adaptive response of the MOF host was observed.