Bottom-Up Strategy to Enhance Long-Range Order of Poly(Heptazine Imide) Nanorods for Efficient Photocatalytic CO Methanation.

Poly(heptazine imide) (PHI), one of the crystalline or long-range ordered allotropes of polymeric carbon nitride, is a promising polymeric photocatalyst; however, preparation of highly crystalline PHI remains a challenge. Herein, through a bottom-up strategy involving repair of structural defects and increase of specific surface area of melon precursor, we prepared PHI nanorods with dramatically improved long-range order. The resulting PHI exhibited a shift of product selectivity in CO photoreduction from CO to CH with a high methanation activity in contrast to the pristine PHI with relatively low long-range order.

Understanding and Tuning the Effects of HO on Catalytic CO and CO Hydrogenation.

Catalytic CO (CO and CO) hydrogenation to valued chemicals is one of the promising approaches to address challenges in energy, environment, and climate change. HO is an inevitable side product in these reactions, where its existence and effect are often ignored. In fact, HO significantly influences the catalytic active centers, reaction mechanism, and catalytic performance, preventing us from a definitive and deep understanding on the structure-performance relationship of the authentic catalysts.

Efficient In/SSZ-39 catalysts for the selective catalytic reduction of NO with CH.

The M/SSZ-39 catalysts (M = In, Co, Cu, Fe) with different metal species and metal loadings were synthesized using the wet impregnation method on a small-pore SSZ-39 molecular sieve. X-ray diffraction (XRD), transmission electron microscopy (TEM), nitrogen adsorption-dehydrogenation and hydrogen temperature program reduction (H-TPR) were employed to characterize the effects of various metal components and metal loadings on the performance of CH selective catalytic reduction of NO reaction (CH-SCR). The characterization results showed that the In/SSZ-39 catalyst exhibited significantly higher catalytic activity compared to the Cu-, Co-, and Fe/SSZ-39 catalysts, suggesting that indium (In) is a more suitable active ingredient for the CH-SCR reaction.

Boosting Solar-Driven CO Conversion to Ethanol via Single-Atom Catalyst with Defected Low-Coordination Cu-N Motif.

Cu-based catalysts have been shown to selectively catalyze CO photoreduction to C solar fuels. However, they still suffer from poor activity and low selectivity. Herein, we report a high-performance carbon nitride supported Cu single-atom catalyst featuring defected low-coordination Cu-N motif (Cu-N-V).

Etching-Hydrolysis Strategy To Construct an In-Plane ZnInS/In(OH) Heterojunction with Enhanced CO Photoreduction Performance.

The in-plane heterojunctions with atomic-level thickness and chemical-bond-connected tight interfaces possess high carrier separation efficiency and fully exposed surface active sites, thus exhibiting exceptional photocatalytic performance. However, the construction of in-plane heterojunctions remains a significant challenge. Herein, we prepared an in-plane ZnInS/In(OH) heterojunction (ZISOH) by partial conversion of ZnInS to In(OH) through the addition of HO.

Fabrication of a ZIF-on-lamella-zeolite architecture as a highly efficient catalyst for aldol condensation.

Designing composite catalysts that harness the strengths of individual components while mitigating their limitations is a fascinating yet challenging task in catalyst engineering. In this study, we aimed to enhance the catalytic performance by anchoring ZIF-67 nanoparticles of precise sizes onto lamella Si-MWW zeolite surfaces through a stepwise regrowth process. Co ions were initially grafted onto the zeolite surface using ultrasonication, followed by a seed-assisted secondary growth method.

Confinement-Induced Indium Oxide Nanolayers Formed on Oxide Support for Enhanced CO Hydrogenation Reaction.

An enclosed nanospace often shows a significant confinement effect on chemistry within its inner cavity, while whether an open space can have this effect remains elusive. Here, we show that the open surface of TiO creates a confined environment for InO which drives spontaneous transformation of free InO nanoparticles in physical contact with TiO nanoparticles into In oxide (InO) nanolayers covering onto the TiO surface during CO hydrogenation to CO. The formed InO nanolayers are easy to create surface oxygen vacancies but are against over-reduction to metallic In in the H-rich atmospheres, which thus show significantly enhanced activity and stability in comparison with the pure InO catalyst.

Computational Design of Single-atom Modified Ti-MOFs for Photocatalytic CO Reduction to C Chemicals.

In this work, density functional theory (DFT) calculations were conducted to investigate a series of transition metals (Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Ru, Rh, Pd, Ag, Hf, Ta, Os, Ir, and Pt) as single-atom components introduced into Ti-BPDC (BPDC=2,2'-bipyridine-5,5'-dicarboxylic acid) as catalysts (M/Ti-BPDC) for the photocatalytic reduction of CO. The results show that Fe/Ti-BPDC is the most active candidate for CO reduction to HCOOH due to its small limiting potential (-0.40 V).

Heterostructured Bimetallic MOF-on-MOF Architectures for Efficient Oxygen Evolution Reaction.

Electron modulation presents a captivating approach to fabricate efficient electrocatalysts for the oxygen evolution reaction (OER), yet it remains a challenging undertaking. In this study, an effective strategy is proposed to regulate the electronic structure of metal-organic frameworks (MOFs) by the construction of MOF-on-MOF heterogeneous architectures. As a representative heterogeneous architectures, MOF-74 on MOF-274 hybrids are in situ prepared on 3D metal substrates (NiFe alloy foam (NFF)) via a two-step self-assembly method, resulting in MOF-(74 + 274)@NFF.

Oriented Ultrathin π-complexation MOF Membrane for Ethylene/Ethane and Flue Gas Separations.

Rational design and engineering of high-performance molecular sieve membranes towards C H /C H and flue gas separations remain a grand challenge to date. In this study, through combining pore micro-environment engineering with meso-structure manipulation, highly c-oriented sub-100 nm-thick Cu@NH -MIL-125 membrane was successfully prepared. Coordinatively unsaturated Cu ions immobilized in the NH -MIL-125 framework enabled high-affinity π-complexation interactions with C H , resulting in an C H /C H selectivity approaching 13.

Seed-Assisted Interzeolite Conversion Strategy for Fabricating Lewis Acid Sn-CHA Zeolites.

Small-pore Lewis acid zeolites have been showing increasing potential in shape-selective reactions regarding small-molecule conversion. In this study, Sn-CHA with tunable framework Sn contents was facilely prepared via a fluoride-free, seed-assisted interzeolite conversion (IZC) pathway. Commercially available dealuminated USY functioned as the parent sample, and seeding played a vital role in accelerating the transformation process, promoting the target zeolite yield, and guiding the attached-growth pathway.

Stabilizing CoC with HO and K promoter for CO hydrogenation to C hydrocarbons.

The decomposition of cobalt carbide (CoC) to metallic cobalt in CO hydrogenation results in a notable drop in the selectivity of valued C products, and the stabilization of CoC remains a grand challenge. Here, we report an in situ synthesized K-CoC catalyst, and the selectivity of C hydrocarbons in CO hydrogenation achieves 67.3% at 300°C, 3.

Machine learning-assisted crystal engineering of a zeolite.

It is shown that Machine Learning (ML) algorithms can usefully capture the effect of crystallization composition and conditions (inputs) on key microstructural characteristics (outputs) of faujasite type zeolites (structure types FAU, EMT, and their intergrowths), which are widely used zeolite catalysts and adsorbents. The utility of ML (in particular, Geometric Harmonics) toward learning input-output relationships of interest is demonstrated, and a comparison with Neural Networks and Gaussian Process Regression, as alternative approaches, is provided. Through ML, synthesis conditions were identified to enhance the Si/Al ratio of high purity FAU zeolite to the hitherto highest level (i.

Three-dimensional inhomogeneity of zeolite structure and composition revealed by electron ptychography.

Structural and compositional inhomogeneity is common in zeolites and considerably affects their properties. Thickness-limited lateral resolution, lack of depth resolution, and electron dose-constrained focusing limit local structural studies of zeolites in conventional transmission electron microscopy (TEM). We demonstrate that a multislice ptychography method based on four-dimensional scanning TEM (4D-STEM) data can overcome these limitations.

Engineering a Self-Grown TiO /Ti-MOF Heterojunction with Selectively Anchored High-Density Pt Single-Atomic Cocatalysts for Efficient Visible-Light-Driven Hydrogen Evolution.

A photocatalyst TiO /Ti-BPDC-Pt is developed with a self-grown TiO /Ti-metal-organic framework (MOF) heterojunction, i.e., TiO /Ti-BPDC, and selectively anchored high-density Pt single-atomic cocatalysts on Ti-BPDC for photocatalytic hydrogen evolution.

Better forbearance, lower depression: Evidence based on heart rate variability.

Background: The relationship between forbearance, a psychological resource, and depression has to date remained inconclusive. The present study investigated heart rate variability (HRV) reactivity to acute stressor tasks in participants with different levels of forbearance to discover how forbearance influences depressive emotions when facing adversity.

Method: The study examined the relationship between forbearance and depression, comparing HRV reactivity to stressor tasks in participants with different levels of forbearance.

One-step direct conversion of methane to methanol with water in non-thermal plasma.

Achieving methane-to-methanol is challenging under mild conditions. In this study, methanol is synthesized by one-step direction conversion of CH with HO at room temperature under atmospheric pressure in non-thermal plasma (NTP). This route is characterized by the use of methane and liquid water as the reactants, which enables the transfer of the methanol product to the liquid phase in time to inhibit its further decomposition and conversion.

Mechanistic Insight into Hydrocarbon Synthesis via CO Hydrogenation on χ-FeC Catalysts.

Converting CO into value-added chemicals and fuels is one of the promising approaches to alleviate CO emissions, reduce the dependence on nonrenewable energy resources, and minimize the negative environmental effect of fossil fuels. This work used density functional theory (DFT) calculations combined with microkinetic modeling to provide fundamental insight into the mechanisms of CO hydrogenation to hydrocarbons over the iron carbide catalyst, with a focus on understanding the energetically favorable pathways and kinetic controlling factors for selective hydrocarbon production. The crystal orbital Hamiltonian population analysis demonstrated that the transition states associated with O-H bond formation steps within the path are less stable than those of C-H bond formation, accounting for the observed higher barriers in O-H bond formation from DFT.

Atomically Dispersed Indium-Copper Dual-Metal Active Sites Promoting C-C Coupling for CO Photoreduction to Ethanol.

Photoreduction of CO to C solar fuel is a promising carbon-neutral technology for renewable energy. This strategy is challenged by its low productivity due to low efficiency in multielectron utilization and slow C-C coupling kinetics. This work reports a dual-metal photocatalyst consisting of atomically dispersed indium and copper anchored on polymeric carbon nitride (InCu/PCN), on which the photoreduction of CO delivered an excellent ethanol production rate of 28.

Defect-Guided Synthesis of Hierarchical Sn-B-Beta Zeolite with Highly Exposed Sn Sites.

Selectively anchoring active centers on the external surface for forming highly exposed acid sites is a highly desirable but challenging task in zeolite catalyst synthesis. Herein, a defect-guided etching-regrowth strategy is rationally designed for facilely positioning Sn Lewis acid sites on the outer surface of the Sn-B-Beta while fabricating a bifunctional hierarchical structure. The synthesis was conducted by hydrothermal treatment of the as-made B-Beta (uncalcined), which has intrinsic defects of the BEA structure, with Sn source and basic organic structure directing agent (SDA).

Minimal EEG channel selection for depression detection with connectivity features during sleep.

Background And Objectives: Sleeping cortical electroencephalogram (EEG) has the potential for depression detection, for different sleep structure and cortical connection have been proved in depressed patients. However, the operation of multi-channel sleep EEG recording is cumbersome and requires laboratory equipment and professional sleep technician. Here, we focus on the depression detection using minimal sleep EEG channels.

Synthesis of Silico-Phospho-Aluminum Nanosheets by Adding Amino Acid and its Catalysis in the Conversion of Furfuryl Alcohol to Fuel Additives.

Self-assembled spheres of silico-phospho-aluminum nanosheets were synthesized with the addition of l-arginine and evaluated as catalysts for the valorization of furfuryl alcohol to fuel additives. Adding the amino acid, a bio-derived additive, contributed to higher external specific surface area and more active sites, featuring a simple, environmentally friendly, and feasible strategy to regulate the growth of nanosheets. Herein, in the reaction of furfuryl alcohol with ethanol, the performance of silico-phospho-aluminum nanosheets was significantly improved compared with typical silicon phosphorus aluminum catalyst SAPO-34.

Plastering Sponge with Nanocarbon-Containing Slurry to Construct Mechanically Robust Macroporous Monolithic Catalysts for Direct Dehydrogenation of Ethylbenzene.

Nanocarbons have shown great potential as a sustainable alternative to metal catalysts, but their powder form limits their industrial applications. The preparation of nanocarbon-based monolithic catalysts is a practical approach for overcoming the resulting pressure drop associated with their powder form. In our previous work, a ploycation-mediated approach was used to successfully prepare nanocarbon-containing monoliths.