The Preparation and Properties of Ti(Nb)-Si-C Coating on the Pre-Oxidized Ferritic Stainless Steel for Solid Oxide Fuel Cell Interconnect.

Cr2O3 scale growth and volatilization are the main cause of the performance degradation of solid oxide fuel cells (SOFCs) with an Fe-based ferritic stainless steel (FSS) interconnect. In this work, an amorphous Ti(Nb)-Si-C coating is prepared on the pre-oxidized SUS430 with D.C. magnetron sputtering as the protective coating. The amorphous Ti(Nb)-Si-C coated alloy exhibits significantly enhanced oxidation resistance, and the oxidation kinetics obey the parabolic law with a low parabolic rate of 9.36 × 10-15 g2·cm-4·s-1. A dual-layer oxide scale is formed composed of an inner layer rich in Cr2O3 and an outer layer rich in rutile TiO2 and amorphous SiO2. MnCr2O4 appears at the interface between the inner and outer oxide layers. Meanwhile, the amorphous Ti(Nb)-Si-C coating also effectively blocks the outward diffusion of Cr. In addition, the coated steel presents good electrical properties with an area-specific resistance (ASR) of 13.57 mΩ·cm2 at 800 °C after oxidation at 800 °C in air for 500 h.

Spatial engineering of single-atom Fe adjacent to Cu-assisted nanozymes for biomimetic O2 activation.

The precise design of single-atom nanozymes (SAzymes) and understanding of their biocatalytic mechanisms hold great promise for developing ideal bio-enzyme substitutes. While considerable efforts have been directed towards mimicking partial bio-inspired structures, the integration of heterogeneous SAzymes configurations and homogeneous enzyme-like mechanism remains an enormous challenge. Here, we show a spatial engineering strategy to fabricate dual-sites SAzymes with atomic Fe active center and adjacent Cu sites. Compared to planar Fe-Cu dual-atomic sites, vertically stacked Fe-Cu geometry in FePc@2D-Cu-N-C possesses highly optimized scaffolds, favorable substrate affinity, and fast electron transfer. These characteristics of FePc@2D-Cu-N-C SAzyme induces biomimetic O2 activation through homogenous enzymatic pathway, resembling functional and mechanistic similarity to natural cytochrome c oxidase. Furthermore, it presents an appealing alternative of cytochrome P450 3A4 for drug metabolism and drug-drug interaction. These findings are expected to deepen the fundamental understanding of atomic-level design in next-generation bio-inspired nanozymes.

Si3C Monolayer as an Efficient Metal-Free Catalyst for Nitrate Electrochemical Reduction: A Computational Study.

Nitrate electroreduction reaction to ammonia (NO3ER) holds great promise for both nitrogen pollution removal and valuable ammonia synthesis, which are still dependent on transition-metal-based catalysts at present. However, metal-free catalysts with multiple advantages for such processes have been rarely reported. Herein, by means of density functional theory (DFT) computations, in which the Perdew-Burke-Ernzerhof (PBE) functional is obtained by considering the possible van der Waals (vdW) interaction using the DFT+D3 method, we explored the potential of several two-dimensional (2D) silicon carbide monolayers as metal-free NO3ER catalysts. Our results revealed that the excellent synergistic effect between the three Si active sites within the Si3C monolayer enables the sufficient activation of NO3- and promotes its further hydrogenation into NO2*, NO*, and NH3, making the Si3C monolayer exhibit high NO3ER activity with a low limiting potential of -0.43 V. In particular, such an electrochemical process is highly dependent on the pH value of the electrolytes, in which acidic conditions are more favorable for NO3ER. Moreover, ab initio molecular dynamics (AIMD) simulations demonstrated the high stability of the Si3C monolayer. In addition, the Si3C monolayer shows a low formation energy, excellent electronic properties, a superior suppression effect on competing reactions, and high stability, offering significant advantages for its experimental synthesis and practical applications in electrocatalysis. Thus, a Si3C monolayer can perform as a promising NO3ER catalyst, which would open a new avenue to further develop novel metal-free catalysts for NO3ER.

Atomic Dispersed Hetero-Pairs for Enhanced Electrocatalytic CO2 Reduction.

Electrochemical carbon dioxide reduction reaction (CO2RR) involves a variety of intermediates with highly correlated reaction and ad-desorption energies, hindering optimization of the catalytic activity. For example, increasing the binding of the *COOH to the active site will generally increase the *CO desorption energy. Breaking this relationship may be expected to dramatically improve the intrinsic activity of CO2RR, but remains an unsolved challenge. Herein, we addressed this conundrum by constructing a unique atomic dispersed hetero-pair consisting of Mo-Fe di-atoms anchored on N-doped carbon carrier. This system shows an unprecedented CO2RR intrinsic activity with TOF of 3336 h-1, high selectivity toward CO production, Faradaic efficiency of 95.96% at - 0.60 V and excellent stability. Theoretical calculations show that the Mo-Fe diatomic sites increased the *COOH intermediate adsorption energy by bridging adsorption of *COOH intermediates. At the same time, d-d orbital coupling in the Mo-Fe di-atom results in electron delocalization and facilitates desorption of *CO intermediates. Thus, the undesirable correlation between these steps is broken. This work provides a promising approach, specifically the use of di-atoms, for breaking unfavorable relationships based on understanding of the catalytic mechanisms at the atomic scale.

Metal-Doped C3B Monolayer as the Promising Electrocatalyst for Hydrogen/Oxygen Evolution Reaction: A Combined Density Functional Theory and Machine Learning Study.

The development of high-efficiency electrocatalysts for hydrogen evolution reduction (HER)/oxygen evolution reduction (OER) is highly desirable. In particular, metal borides have attracted much attention because of their excellent performances. In this study, we designed a series of metal borides by doping of a transition metal (TM) in a C3B monolayer and further explored their potential applications for HER/OER via density functional theory (DFT) calculations and machine learning (ML) analysis. Our results revealed that the |ΔG*H| values of Fe-, Ag-, Re-, and Ir-doped C3B are approximately 0.00 eV, indicating their excellent HER performances. On the other hand, among all the considered TM atoms, the Ni- and Pt-doped C3B exhibit excellent OER activities with the overpotentials smaller than 0.44 V. Together with their low overpotentials for HER (<0.16 V), we proposed that Ni/C3B and Pt/C3B could be the potential bifunctional electrocatalysts for water splitting. In addition, the ML method was employed to identify the important factors to affect the performance of the TM/C3B electrocatalyst. Interestingly, the results showed that the OER performance is closely related to the inherent properties of TM atoms, i.e., the number of d electrons, electronegativity, atomic radius, and first ionization energy; all these values could be directly obtained without DFT calculations. Our results not only proposed several promising electrocatalysts for HER/OER but also suggested a guidance to design the potential TM-boron (TM-B)-based electrocatalysts.

Interface engineering of transition metal-nitrogen-carbon by graphdiyne for boosting the oxygen reduction/evolution reactions: A computational study.

Exploring high-efficiency electrocatalysts to boost the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is pivotal to the large-scale applications for clean and renewable energy technologies, such as fuel cells, water splitting, and metal-air batteries. Herein, by means of density functional theory (DFT) computations, we proposed a strategy to modulate the catalytic activity of transition metal-nitrogen-carbon catalysts through their interface engineering with graphdiyne (TMNC/GDY). Our results revealed that these hybrid structures exhibit good stability and excellent electrical conductivity. Especially, CoNC/GDY was identified as a promising bifunctional catalyst for ORR/OER with rather low overpotentials in acidic conditions according to the constant-potential energy analysis. Moreover, the volcano plots were established to describe the activity trend of the ORR/OER on TMNC/GDY using the adsorption strength of the oxygenated intermediates. Remarkably, the d-band center and charge transfer of the TM active sites can be utilized to correlate the ORR/OER catalytic activity and their electronic properties. Our findings not only suggested an ideal bifunctional oxygen electrocatalyst, but also provided a useful strategy to obtain highly efficient catalysts by interface engineering of two-dimensional heterostructures.

Machine-learning-accelerated screening of single metal atoms anchored on MnPS3 monolayers as promising bifunctional oxygen electrocatalysts.

Searching for bifunctional oxygen electrocatalysts with good catalytic performance to promote the oxygen evolution/reduction reactions (OER/ORR) is of great significance to the development of sustainable and renewable clean energy. Herein, we performed density functional theory (DFT) and machine-learning (DFT-ML) hybrid computations to investigate the potential of a series of single transition metal atoms anchored on the experimentally available MnPS3 monolayer (TM/MnPS3) as the bifunctional electrocatalysts for the ORR/OER. The results revealed that the interactions of these metal atoms with MnPS3 are rather strong, thus guaranteeing their high stability for practical applications. Remarkably, the highly efficient ORR/OER can be achieved on Rh/MnPS3 and Ni/MnPS3 with lower overpotentials than those of metal benchmarks, which can be further rationalized by establishing the volcano and contour plots. Furthermore, the ML results showed that the bond length of TM atoms with the adsorbed O species (dTM-O), the number of d electrons (Ne), the d-center (εd), the radius (rTM) and the first ionization energy (Im) of the TM atoms are the primary descriptors featuring the adsorption behavior. Our findings not only suggest novel highly efficient bifunctional oxygen electrocatalysts, but also provide cost-effective opportunities for the design of single-atom catalysts using the DFT-ML hybrid method.

Axial optimization of biomimetic nanoenzyme catalysts applied to oxygen reduction reactions.

Inspired by the bio-oxygen oxidation/reduction processes of hemoglobin, iron-based transition metal-like enzyme catalysts have been explored as oxygen reduction reaction (ORR) electrocatalysts. We synthesized a chlorine-coordinated monatomic iron material (FeN4Cl-SAzyme) via a high temperature pyrolysis method as a catalyst for the ORR. The half-wave potential (E1/2) was 0.885 V, which exceeded those of Pt/C and the other FeN4X-SAzyme (X = F, Br, I) catalysts. Furthermore, through density functional theory (DFT) calculations, we systematically explored the better performance reason of FeN4Cl-SAzyme. This work offers a promising approach toward high-performance single atom electrocatalysts.

Computational Design of a Two-Dimensional Copper Carbide Monolayer as a Highly Efficient Catalyst for Carbon Monoxide Electroreduction to Ethanol.

Rationally designing stable and low-cost electrocatalysts with high efficiency is of great significance for the large-scale electrochemical reduction of carbon monoxide (eCOR) to high-value-added multicarbon products. Inspired by the tunable atomic structures, abundant active sites, and excellent properties of two-dimensional (2D) materials, in this work, we designed several novel 2D C-rich copper carbide materials as eCOR electrocatalysts by performing an extensive structural search and comprehensive first-principles computations. According to the computed phonon spectra, formation energies, and ab initio molecular dynamics simulations, we screened out two highly stable candidates, i.e., CuC2 and CuC5 monolayers with metallic features. Interestingly, the predicted 2D CuC5 monolayer exhibits superior eCOR performance for C2H5OH synthesis with high catalytic activity (low limiting potential of -0.29 V and small activation energy for C-C coupling of 0.35 eV) and high selectivity (significant suppressing effect on the side reactions). Thus, we predicted that the CuC5 monolayer holds great potential as an eligible electrocatalyst for CO conversion to multicarbon products, which could motivate more study to develop highly efficient electrocatalysts in similar binary noble-metal compounds.

Unprecedented Prediction of a B160 Cluster Stuffed by Dual-Icosahedron B12.

Serving as the premise to understand bulk allotropes, boron clusters have been intriguing experimentalists and theoreticians to study their geometries and chemical bonding. Here, we designed a complete core-shell B160 cluster stuffed by two B12 cores, which is energetically preferable over the bilayer structure of the same size. The unprecedented peanutlike structure with Ci symmetry has superior stability and exhibits superatomic electronic configuration and spherical aromaticity. Our theoretical work not only proposed the core-shell structure of dual icosahedrons for the first time but also indicated the multi-B12 core-shell structural pattern in boron particles, bridging to boron crystalline structures.

Adaptive Posture-Balance Cardiac Rehabilitation Exercise Significantly Improved Physical Tolerance in Patients with Cardiovascular Diseases.

Cardiac rehabilitation (CR) requires more professional exercise modalities to improve the efficiency of treatment. Adaptive posture-balance cardiac rehabilitation exercise (APBCRE) is an emerging, balance-based therapy from clinical experience, but lacks evidence of validity. Our study aimed to observe and assess the rehabilitation effect of APBCRE on patients with cardiovascular diseases (CVDs). All participants received one-month APBCRE therapy evenly three times per week and two assessments before and after APBCRE. Each assessment included cardiopulmonary exercise testing (CPET), resting metabolic rate (RMR) detection, and three questionnaires about general health. The differences between two assessments were analyzed to evaluate the therapeutic effects of APBCRE. A total of 93 participants (80.65% male, 53.03 ± 12.02 years) were included in the analysis. After one-month APBCRE, oxygen uptake (VO2, 11.16 ± 2.91 to 12.85 ± 3.17 mL/min/kg, p < 0.01) at anaerobic threshold (AT), ventilation (VE, 28.87 ± 7.26 to 32.42 ± 8.50 mL/min/kg, p < 0.01) at AT, respiratory exchange ratio (RER, 0.93 ± 0.06 to 0.95 ± 0.05, p < 0.01) at AT and oxygen uptake efficiency slope (OUES, 1426.75 ± 346.30 to 1547.19 ± 403.49, p < 0.01) significantly improved in CVD patients. The ≤55-year group had more positive improvements (VO2 at AT, 23% vs. 16%; OUES, 13% vs. 6%) compared with the >55-year group. Quality of life was also increased after APBCRE (47.78 ± 16.74 to 59.27 ± 17.77, p < 0.001). This study proved that APBCRE was a potentially available exercise rehabilitation modality for patients with CVDs, which performed significant increases in physical tolerance and quality of life, especially for ≤55-year patients.

N-Doped CrS2 Monolayer as a Highly-Efficient Catalyst for Oxygen Reduction Reaction: A Computational Study.

Searching for low-cost and highly-efficient oxygen reduction reaction (ORR) catalysts is crucial to the large-scale application of fuel cells. Herein, by means of density functional theory (DFT) computations, we proposed a new class of ORR catalysts by doping the CrS2 monolayer with non-metal atoms (X@CrS2, X = B, C, N, O, Si, P, Cl, As, Se, and Br). Our results revealed that most of the X@CrS2 candidates exhibit negative formation energy and large binding energy, thus ensuring their high stability and offering great promise for experimental synthesis. Moreover, based on the computed free energy profiles, we predicted that N@CrS2 exhibits the best ORR catalytic activity among all considered candidates due to its lowest overpotential (0.41 V), which is even lower than that of the state-of-the-art Pt catalyst (0.45 V). Remarkably, the excellent catalytic performance of N@CrS2 for ORR can be ascribed to its optimal binding strength with the oxygenated intermediates, according to the computed linear scaling relationships and volcano plot, which can be well verified by the analysis of the p-band center as well as the charge transfer between oxygenated species and catalysts. Therefore, by carefully modulating the incorporated non-metal dopants, the CrS2 monolayer can be utilized as a promising ORR catalyst, which may offer a new strategy to further develop eligible electrocatalysts in fuel cells.

Decoupling layer metal-organic frameworks via ligand regulation to achieve ultra-thin carbon nanosheets for oxygen reduction electrocatalysis.

2D imidazole MOFs are considered to be ideal carbon precursors for oxygen reduction reactions owing to their adjustable ligand components and durable coordination mode. Due to the massive electron delocalization in the lamella, the conjugative effect among 2D MOF layers immensely restricts the exposure of catalytic sites after carbonization, which makes the decoupling layer extremely important on the premise of ensuring activity. Herein, atomic thickness ultra-thin zinc-imidazole MOF precursors were prepared through a bottom-up ligand regulated strategy to achieve the aim of lamellar decoupling. The introduction of heterologous ligands excites stable delocalized electrons, resulting in a decrease in the interlayer force of 2D zinc-imidazole MOF precursors. Subsequent salt template-supported ammonia pyrolysis assisted the MOF-derived carbon sheets to grow along the transverse direction and optimize pore size distribution as did the doping nitrogen type. The MOF-derived carbon sheets demonstrated increasing mesopores and fringe graphitic N which could significantly promote the mass transfer and electron transfer speed during the oxygen reduction reaction. In addition, the obtained ultra-thin carbon delivered an outstanding onset potential (0.98 V vs. RHE) and durability (retaining 91% of the initial current after 12000 s of operation), showing tremendous commercial prospects in sustainable energy.

Engineering d-band center of iron single atom site through boron incorporation to trigger the efficient bifunctional oxygen electrocatalysis.

Modulating the microenvironment of single-metal active sites holds excellent promises for developing highly efficiently oxygen electrocatalysts. Herein, by combining theoretical predictions and experiments, we reported a general strategy to engineer the electronic properties of iron-nitrogen-carbon (FeN4/C) catalysts via the incorporation of the boron (B) atom for achieving improved catalytic activity in oxygen electrocatalysis. Our theoretical results revealed that B modulation effectively tunes the d-band center of the iron (Fe) active site to optimize its adsorption strength with oxygenated species, greatly enhancing oxygen reduction reaction (ORR) and oxygen evolution reactions (OER) activity. Our experimental measurements then confirmed the above theoretical predictions: the as-synthesized B-doped FeN4/C (Fe-N4-B) material can perform as an eligible bifunctional catalyst for ORR and OER in alkaline media, and its catalytic activity even outperforms the commercial noble metal benchmarks. The present findings provide a promising strategy to further design the advanced catalysts for a wide range of electrochemical applications.

Quantitative Proteomics Explore the Potential Targets and Action Mechanisms of Hydroxychloroquine.

Hydroxychloroquine (HCQ) is an autophagy inhibitor that has been used for the treatment of many diseases, such as malaria, rheumatoid arthritis, systemic lupus erythematosus, and cancer. Despite the therapeutic advances in these diseases, the underlying mechanisms have not been well determined and hinder the rational use of this drug in the future. Here, we explored the possible mechanisms and identified the potential binding targets of HCQ by performing quantitative proteomics and thermal proteome profiling on MIA PaCa-2 cells. This study revealed that HCQ may exert its functions by targeting some autophagy-related proteins such as ribosyldihydronicotinamide dehydrogenase (NQO2) and transport protein Sec23A (SEC23A), or regulating the expression of galectin-8 (LGALS8), mitogen-activated protein kinase 8 (MAPK8), and so on. Furthermore, HCQ may prevent the progression of pancreatic cancer by regulating the expression of nesprin-2 (SYNE2), protein-S-isoprenylcysteine O-methyltransferase (ICMT), and cotranscriptional regulator FAM172A (FAM172A). Together, these findings not only identified potential binding targets for HCQ but also revealed the non-canonical mechanisms of HCQ that may contribute to pancreatic cancer treatment.

Understanding the CH4 Conversion over Metal Dimers from First Principles.

Inspired by the advantages of bi-atom catalysts and recent exciting progresses of nanozymes, by means of density functional theory (DFT) computations, we explored the potential of metal dimers embedded in phthalocyanine monolayers (M2-Pc), which mimics the binuclear centers of methane monooxygenase, as catalysts for methane conversion using H2O2 as an oxidant. In total, 26 transition metal (from group IB to VIIIB) and four main group metal (M = Al, Ga, Sn and Bi) dimers were considered, and two methane conversion routes, namely *O-assisted and *OH-assisted mechanisms were systematically studied. The results show that methane conversion proceeds via an *OH-assisted mechanism on the Ti2-Pc, Zr2-Pc and Ta2-Pc, a combination of *O- and *OH-assisted mechanism on the surface of Sc2-Pc, respectively. Our theoretical work may provide impetus to developing new catalysts for methane conversion and help stimulate further studies on metal dimer catalysts for other catalytic reactions.

Identification and evaluation of a lipid-lowering small compound in preclinical models and in a Phase I trial.

Developing non-statin-based small compounds to battle the global epidemic of hyperlipidemia remains challenging. Here, we report the discovery of DC371739, an indole-containing tetrahydroisoquinoline compound with promising lipid-lowering effects, both in vitro and in vivo, and with good tolerability in a Phase I clinical trial (NCT04927221). DC371739 significantly reduced the plasma levels of total cholesterol, low-density lipoprotein cholesterol, and triglycerides simultaneously in several animal models and showed preliminary positive results in the Phase I trial. Mechanistically, DC371739 acts in a distinct manner from other known lipid-lowering reagents. We show that it physically binds HNF-1α, impeding the transcription of both PCSK9 and ANGPTL3, two genes that are known to contribute to hypercholesterolemia and dyslipidemia. Moreover, the distinct mechanism of action of DC371739 allows its combination with atorvastatin treatment to additively improve dyslipidemia, while providing a potential alternative therapeutic strategy for individuals with statin intolerance.

Computational screening of single-atom catalysts supported by VS2 monolayers for electrocatalytic oxygen reduction/evolution reactions.

The development of highly efficient bifunctional electrocatalysts to boost oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is highly desirable for energy conversion and storage devices. Herein, by means of comprehensive first-principles computations, we systematically explored the catalytic activities of a series of single transition metal atoms anchored on two-dimensional VS2 monolayers (TM@VS2) for ORR/OER. Our results revealed that Ni@VS2 exhibits low overpotentials for both ORR (0.45 V) and OER (0.31 V), suggesting its great potential as a bifunctional catalyst, which is mainly induced by its moderate interaction with oxygenated intermediates according to the established scaling relationship and volcano plot. Interestingly, the substituted doping of nitrogen heteroatoms into the VS2 substrate can further effectively improve the ORR/OER activity of the active metal atom to achieve more eligible ORR/OER bifunctional catalysts. Our results not only propose a new class of potential bifunctional oxygen catalysts but also offer a feasible strategy for further tuning their catalytic activity.

Multi-interface MoS2/Ni3S4/Mo2S3 composite as an efficient electrocatalyst for hydrogen evolution reaction over a wide pH range.

The exploitation of cost-efficiently electrocatalysts for hydrogen evolution reaction (HER) over a wide pH range remains a challenge. Herein, we prepared a novel multi-interface MoS2/Ni3S4/Mo2S3 composite on carbon cloth (CC) that acts as an efficient electrocatalyst over a wide pH range through a facile one-pot strategy, where (NH4)4[NiH6Mo6O24]·5H2O (abbreviated to NiMo6) as a bimetallic precursor and Ni(NO3)2·6H2O as one of the raw materials and salt are used together with thiourea (TU) for converting them into the MoS2/Ni3S4/Mo2S3 load on CC (abbreviated as MoS2/Ni3S4/Mo2S3/CC). MoS2/Ni3S4/Mo2S3/CC-24 h shows a distinguished electrocatalytic performance towards HER with long-term stability in acid and alkaline media. It presents low overpotentials of 38 mV and 51 mV in 0.5 M H2SO4 and 1.0 M KOH at 10 mA cm-2, respectively. This work can deliver a new idea to fabricate cost-efficient and long-term durability HER electrocatalysts over a broad pH range.

Single Ir atom anchored in pyrrolic-N4 doped graphene as a promising bifunctional electrocatalyst for the ORR/OER: a computational study.

The development of highly-efficient electrocatalysts with bifunctional catalytic activity for oxygen reduction reaction (ORR) and oxygen evolution reaction. (OER) still remains a great challenge for the large-scale application of renewable energy conversion and storage technologies. Herein, by means of comprehensive density functional theory (DFT) computations, we systematically explored the potential of pyrrolic-N doped graphene (pyrrolic-N4-G) supported various transition metal atoms (TM = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo, Ru, Pd, W, Os, Ir, and Pt) as electrocatalysts for the ORR and OER. Our results revealed that these TM/pyrrolic-N4-G candidates exhibit high electrochemical stability due to their positive dissolution potentials. Especially, the Ir/pyrrolic-N4-G can perform as a promising bifunctional electrocatalyst for both ORR and OER with the low overpotentials (ηORR = 0.34 V and ηOER = 0.32 V). Interestingly, multiple-level descriptors, including energy descriptor (ΔGOH* - ΔGO*), (ΔGOH*), structure descriptor (φ), and d-band center (ε) can well rationalize the origin of the high catalytic activity of Ir/pyrrolic-N4-G for the ORR/OER. Our findings not only further enrich the SACs, but also open a new avenue to develop novel 2D materials-based SACs for highly efficient oxygen electrocatalysts.