Understanding and Tuning the Effects of H2O on Catalytic CO and CO2 Hydrogenation.

Catalytic COx (CO and CO2) hydrogenation to valued chemicals is one of the promising approaches to address challenges in energy, environment, and climate change. H2O is an inevitable side product in these reactions, where its existence and effect are often ignored. In fact, H2O 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. It is necessary, although challenging, to clarify its effect and provide practical strategies to tune the concentration and distribution of H2O to optimize its influence. In this review, we focus on how H2O in COx hydrogenation induces the structural evolution of catalysts and assists in the catalytic processes, as well as efforts to understand the underlying mechanism. We summarize and discuss some representative tuning strategies for realizing the rapid removal or local enrichment of H2O around the catalysts, along with brief techno-economic analysis and life cycle assessment. These fundamental understandings and strategies are further extended to the reactions of CO and CO2 reduction under an external field (light, electricity, and plasma). We also present suggestions and prospects for deciphering and controlling the effect of H2O in practical applications.

Confinement-Induced Indium Oxide Nanolayers Formed on Oxide Support for Enhanced CO2 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 TiO2 creates a confined environment for In2O3 which drives spontaneous transformation of free In2O3 nanoparticles in physical contact with TiO2 nanoparticles into In oxide (InOx) nanolayers covering onto the TiO2 surface during CO2 hydrogenation to CO. The formed InOx nanolayers are easy to create surface oxygen vacancies but are against over-reduction to metallic In in the H2-rich atmospheres, which thus show significantly enhanced activity and stability in comparison with the pure In2O3 catalyst. The formation of interfacial In-O-Ti bonding is identified to drive the In2O3 dispersion and stabilize the metastable InOx layers. The InOx overlayers with distinct chemistry from their free counterpart can be confined on various oxide surfaces, demonstrating the important confinement effect at oxide/oxide interfaces.

Boosting Solar-Driven CO2 Conversion to Ethanol via Single-Atom Catalyst with Defected Low-Coordination Cu-N2 Motif.

Cu-based catalysts have been shown to selectively catalyze CO2 photoreduction to C2+ 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-N2 motif (Cu-N2-V). Lead many recently reported photocatalysts and its Cu-N3 and Cu-N4 counterparts, Cu-N2-V exhibits superior photocatalytic activity for CO2 reduction to ethanol and delivers 69.8 µmol g-1 h-1 ethanol production rate, 97.8 % electron-based ethanol selectivity, and a yield of ~10 times higher than Cu-N3 and Cu-N4. Revealed by the extensive experimental investigation combined with DFT calculations, the superior photoactivity of Cu-N2-V stems from its defected Cu-N2 configuration, in which the Cu sites are electron enriched and enhance electron delocalization. Importantly, Cu in Cu-N2-V exist in both Cu+ and Cu2+ valence states, although predominantly as Cu+. The Cu+ sites support the CO2 activation, while the co-existence of Cu+/Cu2+ sites are highly conducive for strong *CO adsorption and subsequent *CO-*CO dimerization enabling C-C coupling. Furthermore, the hollow microstructure of the catalyst also promotes light adsorption and charge separation efficiency. Collectively, these make Cu-N2-V an effective and high-performance catalyst for the solar-driven CO2 conversion to ethanol. This study also elucidates the C-C coupling reaction path via *CO-*CO to *COCOH and rate-determining step, and reveals the valence state change of partial Cu species from Cu+ to Cu2+ in Cu-N2-V during CO2 photoreduction reaction.

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. Notably, a proto-zeolite phase with a semi-constructed pore structure was captured during the IZC process, which represents a crucial intermediate stage for developing the complete CHA structure and ensuring a well-defined Sn status. The detailed synthesis mechanism was explored in multiscale by a series of techniques. The obtained Sn-CHA and proto-Sn-CHA exhibited excellent catalytic performance in converting 1,3-dihydroxyacetone to methyl lactate. Proto-Sn-CHA was proven to be a highly effective glucose isomerization catalyst owing to its larger pore size and Lewis acidic nature.

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

Rational design and engineering of high-performance molecular sieve membranes towards C2 H4 /C2 H6 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@NH2 -MIL-125 membrane was successfully prepared. Coordinatively unsaturated Cu ions immobilized in the NH2 -MIL-125 framework enabled high-affinity π-complexation interactions with C2 H4 , resulting in an C2 H4 /C2 H6 selectivity approaching 13.6, which was 9.4 times higher than that of pristine NH2 -MIL-125 membrane; moreover, benefiting from π-complexation interactions between CO2 and Cu(I) sites, our membrane displayed superior CO2 /N2 selectivity of 43.2 with CO2 permeance of 696 GPU, which far surpassed the benchmark of other pure MOF membranes. The above multi-scale structure optimization strategy is anticipated to present opportunities for significantly enhancing the separation performance of diverse molecular sieve membranes.

Engineering a Self-Grown TiO2 /Ti-MOF Heterojunction with Selectively Anchored High-Density Pt Single-Atomic Cocatalysts for Efficient Visible-Light-Driven Hydrogen Evolution.

A photocatalyst TiO2 /Ti-BPDC-Pt is developed with a self-grown TiO2 /Ti-metal-organic framework (MOF) heterojunction, i.e., TiO2 /Ti-BPDC, and selectively anchored high-density Pt single-atomic cocatalysts on Ti-BPDC for photocatalytic hydrogen evolution. This intimate heterojunction, growing from the surface pyrolytic reconstruction of Ti-BPDC, works in a direct Z-scheme, efficiently separating electrons and holes. Pt is selectively anchored on Ti-BPDC by ligands and is found in the form of single atoms with loading up to 1.8 wt %. The selective location of Pt is the electron-enriched domain of the heterojunction, which further enhances the utilization of the separated electrons. This tailored TiO2 /Ti-BPDC-Pt shows a significantly enhanced activity of 12.4 mmol g-1 h-1 compared to other TiO2 - or MOF-based catalysts. The structure-activity relationship further proves the balance of two simultaneously exposed domains of heterojunctions is critical to fulfilling this kind of catalyst.

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). Under a moderate SDA concentration, with blocked micropore channels, such SDA-triggered etching-regrowth will proceed along the defect defined pathway, which ensures Sn selectively anchored on the external surface. Moreover, this methodology has exclusively introduced tetrahedrally coordinated framework Sn with open Sn sites as the predominated species. Mono- and disaccharide isomerizations in ethanol over different Sn-Beta catalysts proved the prominent advantages of the hierarchical structure with highly exposed and synergetic acid sites.

Recent Advances in Carbon Dioxide Hydrogenation to Methanol via Heterogeneous Catalysis.

The utilization of fossil fuels has enabled an unprecedented era of prosperity and advancement of well-being for human society. However, the associated increase in anthropogenic carbon dioxide (CO2) emissions can negatively affect global temperatures and ocean acidity. Moreover, fossil fuels are a limited resource and their depletion will ultimately force one to seek alternative carbon sources to maintain a sustainable economy. Converting CO2 into value-added chemicals and fuels, using renewable energy, is one of the promising approaches in this regard. Major advances in energy-efficient CO2 conversion can potentially alleviate CO2 emissions, reduce the dependence on nonrenewable resources, and minimize the environmental impacts from the portions of fossil fuels displaced. Methanol (CH3OH) is an important chemical feedstock and can be used as a fuel for internal combustion engines and fuel cells, as well as a platform molecule for the production of chemicals and fuels. As one of the promising approaches, thermocatalytic CO2 hydrogenation to CH3OH via heterogeneous catalysis has attracted great attention in the past decades. Major progress has been made in the development of various catalysts including metals, metal oxides, and intermetallic compounds. In addition, efforts are also put forth to define catalyst structures in nanoscale by taking advantage of nanostructured materials, which enables the tuning of the catalyst composition and modulation of surface structures and potentially endows more promising catalytic performance in comparison to the bulk materials prepared by traditional methods. Despite these achievements, significant challenges still exist in developing robust catalysts with good catalytic performance and long-term stability. In this review, we will provide a comprehensive overview of the recent advances in this area, especially focusing on structure-activity relationship, as well as the importance of combining catalytic measurements, in situ characterization, and theoretical studies in understanding reaction mechanisms and identifying key descriptors for designing improved catalysts.

Solvothermal synthesis of 3D hierarchical Cu2FeSnS4 microspheres for photocatalytic degradation of organic pollutants.

In this work, we prepared Cu2FeSnS4 (CFTS) microspheres via solvothermal method and studied their photocatalytic performance towards the degradation of organic pollutants. With increasing solvothermal temperature from 160 °C to 180 °C, the morphology of CFTS changes from irregular 2D to hierarchical 3D shapes. Hierarchical 3D CFTS microspheres packed with 2D nanosheets were successfully prepared at 180 °C. During the solvothermal process, octadecyl amine (ODA) acts as a capping agent to prevent the aggregation of particles, while L-cystine functions as an environmentally friendly sulfur source and complexing reagent. The large surface area and mesoporous structure of the as-prepared 3D hierarchical CFTS microspheres provide more active sites, enhance visible light absorption and promote charge separation and transfer, leading to the improved photodegradation performance for RhB and MB compared to the samples prepared at the temperature lower than 180 °C. This work provides a simple and low-cost method for the synthesis of 3D hierarchical CFTS towards photocatalytic applications.

Interactions of central and autonomic nervous systems in patients with sleep apnea-hypopnea syndrome during sleep.

PURPOSE: Sleep apnea-hypopnea syndrome (SAHS) is an independent risk factor for various cardiovascular and cerebrovascular diseases, but the underlying relationship of its physiological subsystems remains unclear. Thus, we aimed to investigate the effect of SAHS on central and autonomic nervous system (CNS-ANS) interactions during sleep. METHODS: Thirty-five patients with SAHS and 19 healthy age-matched controls underwent overnight polysomnography. The absolute spectral powers of five frequency bands from six EEG channels and ECG morphological features (HR, PR interval, QT interval) were calculated. Multivariable transfer entropy was applied to analyze the differences of the CNS-ANS network interactions between patients with SAHS of different severities and healthy controls during deep, light, and rapid eye movement sleep. RESULTS: The CNS-ANS network interacted bidirectionally in all researched groups, with the cardiac information modulating the brain activity. The information strength from QT to most EEG components and PR to some EEG components was significantly affected by SAHS severity during light sleep, which indicates the coupling features of QT-brain nodes are important indicators. The driver effects from the ß-band significantly increased in patients with SAHS. CONCLUSIONS: Respiratory events may be the main reason for the CNS-ANS interaction changes in SAHS. These findings help explain the physiological regulation process of SAHS and provide valuable information for analysis of the development of SAHS-related cardiovascular and chronic diseases.

Atomically Dispersed Indium-Copper Dual-Metal Active Sites Promoting C-C Coupling for CO2 Photoreduction to Ethanol.

Photoreduction of CO2 to C2+ 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 CO2 delivered an excellent ethanol production rate of 28.5 µmol g-1 h-1 with a high selectivity of 92 %. Coupled experimental investigation and DFT calculations reveal the following mechanisms underpinning the high performance of this catalyst. Essentially, the In-Cu interaction enhances the charge separation by accelerating charge transfer from PCN to the metal sites. Indium also transfers electrons to neighboring copper via Cu-N-In bridges, increasing the electron density of copper active sites. Furthermore, In-Cu dual-metal sites promote the adsorption of *CO intermediates and lower the energy barrier of C-C coupling.

Characterization of specific spatial functional connectivity difference in depression during sleep.

Depression is a common mental illness and a large number of researchers have been still devoted to exploring effective biomarkers for the identification of depression. Few researches have been conducted on functional connectivity (FC) during sleep in depression. In this paper, a novel depression characterization is proposed using specific spatial FC features of sleep electroencephalography (EEG). Overnight polysomnography recordings were obtained from 26 healthy individuals and 25 patients with depression. The weighted phase lag indexes (WPLIs) of four frequency bands and five sleep periods were obtained from 16 EEG channels. The high discriminative connections extracted via feature evaluation and the cross-within variation (CW)-the spatial feature constructed to characterize the different performances in inter- and intra-hemispheric FC based on WPLIs, were utilized to classify patients and normal controls. The results showed that enhanced average FC and spatial differences, higher inter-hemispheric FC and lower intra-hemispheric FC, were found in patients. Furthermore, abnormalities in the inter-hemispheric connections of the temporal lobe in the theta band should be important indicators of depression. Finally, both CW and high discriminative WPLI features performed well in depression screening and CW was more specific for characterizing abnormal cortical EEG performance of depression. Our work investigated and characterized the abnormalities in sleep cortical activity in patients with depression, and may provide potential biomarkers for assisting with depression identification and new insights into the understanding of pathological mechanisms in depression.

A PET imaging study of the brain changes of glucose metabolism in patients with temporal lobe epilepsy and depressive disorder.

BACKGROUND: This study aims to compare the difference of the brain changes of glucose metabolism between temporal lobe epilepsy patients (TLE) with major depressive disorder and temporal TLE without major depressive disorder. METHODS: A total of 24 TLE patients, who met the inclusion criteria of our hospital, were enrolled in this study. They were divided into a TLE with depression group (n = 11) and a TLE without depression group (n = 13), according to the results of the HAMD-24 Scale. Two groups patients were examined using 18F-FDG PET brain imaging. RESULTS: The low metabolic regions of the TLE with depression group were mainly found in the left frontal lobe, temporal lobe and fusiform gyrus, while the high metabolic regions of the TLE with depression group were mainly located in the right frontal lobe, visual joint cortex and superior posterior cingulate cortex. Both of the TLE groups had high metabolic compensation in the non-epileptic area during the interictal period. CONCLUSIONS: There is an uptake difference of 18F-FDG between TLE patients with depression and TLE patients without depression in multiple encephalic regions.

Crystal Facet Induced Single-Atom Pd/Cox Oy on a Tunable Metal-Support Interface for Low Temperature Catalytic Oxidation.

Atomic dispersed metal sites in single-atom catalysts are highly mobile and easily sintered to form large particles, which deteriorates the catalytic performance severely. Moreover, lack of criterion concerning the role of the metal-support interface prevents more efficient and wide application. Here, a general strategy is reported to synthesize stable single atom catalysts by crafting on a variety of cobalt-based nanoarrays with precisely controlled architectures and compositions. The highly uniform, well-aligned, and densely packed nanoarrays provide abundant oxygen vacancies (17.48%) for trapping Pd single atoms and lead to the creation of 3D configured catalysts, which exhibit very competitive activity toward low temperature CO oxidation (100% conversion at 90 °C) and prominent long-term stability (continuous conversion at 60 °C for 118 h). Theoretical calculations show that O vacancies at high-index {112} facet of Cox Oy nanocrystallite are preferential sites for trapping single atoms, which guarantee strong interface adhesion of Pd species to cobalt-based support and play a pivotal role in preventing the decrement of activity, even under moisture-rich conditions (≈2% water vapor). The progress presents a promising opportunity for tailoring catalytic properties consistent with the specific demand on target process, beyond a facile design with a tunable metal-support interface.

Polymorphous low-grade neuroepithelial tumor of the young: case report and review focus on the radiological features and genetic alterations.

BACKGROUND: A new type of epileptogenic tumor, the polymorphous low-grade neuroepithelial tumor of the young (PLNTY) was firstly reported by Jason T. Huse et al. at 2016. After that, only 1 case of PLNTY was reported by article. The radiological characteristics of PLNTY have not been concluded. The objective of our study was to report 3 cases of PLNTYs in details and to analyze the image characteristics and genetic alterations of PLNTYs by reviewing our cases and articles. CASE PRESENTATION: There were 3 cases diagnosed as PLNTY by pathology in our hospital during the last 10 years, with the average age of 15. They were all suffered from different degrees of epilepsy. All of them underwent magnetic resonance (MR) imaging and 2 of them underwent computer tomography (CT) imaging. The PLNTYs are all appearing as a solid or solid-cystic cortical mass with little mass effect and unclear boundary with normal brain tissue. They are all shown as hyperintensity in T2WI and iso-/hypointensity in T1WI with slight or no enhancement after contract enhanced in MR imaging. The "salt and pepper sign" in T2WI and grit calcification in CT images might be specific characteristics of PLNTY. All of them recovered after excision of the tumors. The gene tests revealed fibroblast growth factor receptors 3 (FGFR3)-TACC3 fusion and FGFR3 amplification in one case, and the B-Raf proto-oncogene (BRAF) V600E mutation in another case. CONCLUSION: In the image, the partial ill-marginated cortical mass with "salt and pepper sign" in T2WI or grit calcification in CT imaging might be the typical imaging characteristics of PLNTY. We also prove that the BRAF V600E mutation as well as the FGFR2 and FGFR3 have a close relationship with PLNTY.

Defects Promote Ultrafast Charge Separation in Graphitic Carbon Nitride for Enhanced Visible-Light-Driven CO2 Reduction Activity.

Fundamental photocatalytic limitations of solar CO2 reduction remain due to low efficiency, serious charge recombination, and short lifetime of catalysts. Herein, two-dimensional graphitic carbon nitride nanosheets with nitrogen vacancies (g-C3 Nx ) located at both three-coordinate N atoms and uncondensed terminal NHx species were prepared by one-step tartaric acid-assistant thermal polymerization of dicyandiamide. Transient absorption spectra revealed that the defects in g-C3 N4 act as trapped states of charges to result in prolonged lifetimes of photoexcited charge carriers. Time-resolved photoluminescence spectroscopy revealed that the faster decay of charges is due to the decreased interlayer stacking distance in g-C3 Nx in favor of hopping transition and mobility of charge carriers to the surface of the material. Owing to the synergic virtues of strong visible-light absorption, large surface area, and efficient charge separation, the g-C3 Nx nanosheets with negligible loss after 15 h of photocatalysis exhibited a CO evolution rate of 56.9 µmol g-1 h-1 under visible-light irradiation, which is roughly eight times higher than that of pristine g-C3 N4 . This work presents the role of defects in modulating light absorption and charge separation, which opens an avenue to robust solar-energy conversion performance.

A Facile Strategy to Prepare Shaped ZSM-5 Catalysts with Enhanced Para-Xylene Selectivity and Stability for Toluene Methylation: The Effect of In Situ Modification by Attapulgite.

A general strategy for preparing shaped toluene methylation catalysts with enhanced para-selectivity and stability is developed by extruding ZSM-5 zeolite with attapulgite as a binder. The novel attapulgite/ZSM-5 extrudate exhibited significantly higher para-selectivity and stability in comparison to the conventional alumina-bound ZSM-5 extrudate. The catalyst samples have been characterized by in situ X-ray diffraction, scanning electron microscope (SEM), NH3 temperature programmed desorption (TPD), thermogravimetric analysis (TGA) as well as n-hexane/cyclohexane physical adsorption. The enhanced catalytic performance of attapulgite/ZSM-5 extrudate is correlated with the in-situ modification of acid sites in the catalyst by mobile alkaline species, which is introduced via extrusion with attapulgite. Moreover, a higher para-selectivity was obtained over attapulgite-bound modified ZSM-5 extrudate. Such facile and universal strategy of extruding ZSM-5 catalysts with attapulgite as binder could pave a way for preparation of shaped zeolite-base catalyst with enhanced catalytic performance.

Preassembly Strategy To Fabricate Porous Hollow Carbonitride Spheres Inlaid with Single Cu-N3 Sites for Selective Oxidation of Benzene to Phenol.

Developing single-atom catalysts with porous micro-/nanostructures for high active-site accessibility is of great significance but still remains a challenge. Herein, we for the first time report a novel template-free preassembly strategy to fabricate porous hollow graphitic carbonitride spheres with single Cu atoms mounted via thermal polymerization of supramolecular preassemblies composed of a melamine-Cu complex and cyanuric acid. Atomically dispersed Cu-N3 moieties were unambiguously confirmed by spherical aberration correction electron microscopy and extended X-ray absorption fine structure spectroscopy. More importantly, this material exhibits outstanding catalytic performance for selective oxidation of benzene to phenol at room temperature, especially showing phenol selectivity (90.6 vs 64.2%) and stability much higher than those of the supported Cu nanoparticles alone, originating from the isolated unique Cu-N3 sites in the porous hollow structure. An 86% conversion of benzene, with an unexpectedly high phenol selectivity of 96.7% at 60 °C for 12 h, has been achieved, suggesting a great potential for practical applications. This work paves a new way to fabricate a variety of single-atom catalysts with diverse graphitic carbonitride architectures.

Origin and Structural Characteristics of Tri-coordinated Extra-framework Aluminum Species in Dealuminated Zeolites.

Post-synthetic dealumination treatment is a common tactic adopted to improve the catalytic performance of industrialized zeolitic catalysts through enhancements in acidity and stability. However, among the possible extra-framework aluminum (EFAL) species in dealuminated zeolites such as Al3+, Al(OH)2+, Al(OH)2+, AlO+, AlOOH, and Al(OH)3, the presence of tri-coordinated EFAL-Al3+ species, which exhibit large quadrupolar effect due to the lack of hydrogen-bonding species, was normally undetectable by conventional one- and two-dimensional 1H and/or 27Al solid-state nuclear magnetic resonance (SSNMR) techniques. By combining density functional theory (DFT) calculations with experimental 31P SSNMR using trimethylphosphine (TMP) as the probe molecule, we report herein a comprehensive study to certify the origin, fine structure, and possible location of tri-coordinated EFAL-Al3+ species in dealuminated HY zeolite. The spatial proximities and synergies between the Brønsted and various Lewis acid sites were clearly identified, and the origin for the observed EFAL-Al3+ species with ultra-strong Lewis acidity was deduced to be at the expense of adjacent Brønsted acid sites. The excellent performance of such tri-coordinated EFAL species was furthermore confirmed by glucose isomerization reactions.

A 3D Covalent Organic Framework with Exceptionally High Iodine Capture Capability.

Using porous materials to cope with environmental issues is promising but remains a challenge especially for removing the radioactive vapor wastes in fission because of harsh adsorption conditions. Here we report a new, stable covalent organic framework (COF) as a porous platform for removing iodine vapor-a major radioactive fission waste. The three-dimensional COF consists of a diamond topology knotted by adamantane units, creates ordered one-dimensional pores and are highly porous. The COF enables the removal of iodine vapor via charge transfer complex formation with the pore walls to achieve exceptional capacity. Moreover, the 3D COF is "soft" to trigger structural fitting to iodine while retaining connectivity and enables cycle use for many times while retaining high uptake capacity. These results set a new benchmark for fission waste removal and suggest the great potential of COFs as a designable porous material for challenging world-threatening pollution issues.