Electron Redistribution of Ru Site on MoO2@NiMoO4 Support for Efficient Ampere-Level Current Density Electrolysis of Alkaline Seawater.

Seawater electrolysis is a promising but challenging strategy to generate carbon-neutral hydrogen. A grand challenge for hydrogen evolution reaction (HER) from alkaline seawater electrolysis is the development of efficient and stable electrocatalysts to overcome the limitation of sluggish kinetics. Here, a 3D nanorod hybrid catalyst is reported, which comprises heterostructure MoO2@NiMoO4 supported Ru nanoparticles (Ru/ MoO2@NiMoO4) with a size of ≈5 nm. Benefitting from the effect of strongly coupled interaction, Ru/MoO2@NiMoO4 catalyst exhibits a remarkable alkaline seawater hydrogen evolution performance, featured by a low overpotential of 184 mV at a current density of 1.0 A cm-2, superior to commercial Pt/C (338 mV). Experimental observations demonstrate that the heterostructure MoO2@NiMoO4 as an electron-accepting support makes the electron transfer from the Ru nanoparticles to MoO2, and thereby implements the electron redistribution of Ru site. Mechanistic analysis elucidates that the electron redistribution of active Ru site enhances the ability of hydrogen desorption, thereby promoting alkaline seawater HER kinetics and finally leading to a satisfactory catalysis performance at ampere-level current density of alkaline seawater electrolysis.

Mechanistic insights into high-throughput screening of tandem catalysts for CO2 reduction to multi-carbon products.

In carbon dioxide electrochemical reduction (CO2ER), since isolated catalysts encounter challenges in meeting the demands of intricate processes for producing multi-carbon (C2+) products, tandem catalysis is emerging as a promising approach. Nevertheless, there remains an insufficient theoretical understanding of designing tandem catalysts. Herein, we utilized density functional theory (DFT) to screen 80 tandem catalysts for efficient CO2ER to C2 products systematically, which combines the advantages of nitrogen-doped carbon-supported transition metal single-atom catalysts (M-N-C) and copper clusters. Three crucial criteria were designed to select structures for generation and transfer of *CO and facilitate C-C coupling. The optimal Cu/RuN4-pl catalyst exhibited an excellent ethanol production capacity. Additionally, the relationship between CO adsorption strength and transfer energy barrier was established, and the influence of the electronic structure on its adsorption strength was studied. This provided a novel and well-considered solution and theoretical guidance for the design of rational composition and structurally superior tandem catalysts.

Electrochemical C-N coupling of CO2 and nitrogenous small molecules for the electrosynthesis of organonitrogen compounds.

Electrochemical C-N coupling reactions based on abundant small molecules (such as CO2 and N2) have attracted increasing attention as a new "green synthetic strategy" for the synthesis of organonitrogen compounds, which have been widely used in organic synthesis, materials chemistry, and biochemistry. The traditional technology employed for the synthesis of organonitrogen compounds containing C-N bonds often requires the addition of metal reagents or oxidants under harsh conditions with high energy consumption and environmental concerns. By contrast, electrosynthesis avoids the use of other reducing agents or oxidants by utilizing "electrons", which are the cleanest "reagent" and can reduce the generation of by-products, consistent with the atomic economy and green chemistry. In this study, we present a comprehensive review on the electrosynthesis of high value-added organonitrogens from the abundant CO2 and nitrogenous small molecules (N2, NO, NO2-, NO3-, NH3, etc.) via the C-N coupling reaction. The associated fundamental concepts, theoretical models, emerging electrocatalysts, and value-added target products, together with the current challenges and future opportunities are discussed. This critical review will greatly increase the understanding of electrochemical C-N coupling reactions, and thus attract research interest in the fixation of carbon and nitrogen.

Regulating Spin Polarization via Axial Nitrogen Traction at Fe-N5 Sites Enhanced Electrocatalytic CO2 Reduction for Zn-CO2 Batteries.

Single Fe sites have been explored as promising catalysts for the CO2 reduction reaction to value-added CO. Herein, we introduce a novel molten salt synthesis strategy for developing axial nitrogen-coordinated Fe-N5 sites on ultrathin defect-rich carbon nanosheets, aiming to modulate the reaction pathway precisely. This distinctive architecture weakens the spin polarization at the Fe sites, promoting a dynamic equilibrium of activated intermediates and facilitating the balance between *COOH formation and *CO desorption at the active Fe site. Notably, the synthesized FeN5, supported on defect-rich in nitrogen-doped carbon (FeN5@DNC), exhibits superior performance in CO2RR, achieving a Faraday efficiency of 99 % for CO production (-0.4 V vs. RHE) in an H-cell, and maintaining a Faraday efficiency of 98 % at a current density of 270 mA cm-2 (-1.0 V vs. RHE) in the flow cell. Furthermore, the FeN5@DNC catalyst is assembled as a reversible Zn-CO2 battery with a cycle durability of 24 hours. In situ IR spectroscopy and density functional theory (DFT) calculations reveal that the axial N coordination traction induces a transformation in the crystal field and local symmetry, therefore weakening the spin polarization of the central Fe atom and lowering the energy barrier for *CO desorption.

Accelerated Proton-Coupled Electron Transfer via Engineering Palladium Sub-Nanoclusters for Scalable Electrosynthesis of Hydrogen Peroxide.

Electrosynthesis of H2O2 from oxygen reduction reaction via a two-electron pathway is vital as an alternative for the energy-intensive anthraquinone process. However, this process is largely hindered in neutral and alkaline conditions due to sluggish kinetics associated with the transformation of intermediate O2* into OOH* via proton-coupled electron transfer sourced from slow water dissociation. Herein, we developed Pd sub-nanoclusters on the nickel ditelluride nanosheets (Pd SNCs/NiTe2) to enhance the performance of H2O2 electrosynthesis. The newly-developed Pd SNCs/NiTe2 exhibited a H2O2 selectivity of as high as 99 % and a positive shift of onset potential up to 0.81 V. Combined theoretical calculations and experimental studies (e.g., X-ray absorption and attenuated total reflectance-Fourier transform infrared spectra measurements) revealed that the Pd sub-nanoclusters supported by NiTe2 nanosheets efficiently reduced the energy barrier of water dissociation to generate more protons, facilitating the proton feeding kinetics. When used in a flow cell, Pd SNCs/NiTe2 cathode efficiently produced H2O2 with a maximum yield rate of 1.75 mmol h-1 cm-2 and a current efficiency of 95 % at 100 mA cm-2. Further, an accumulated H2O2 concentration of 1.43 mol L-1 was reached after 10 hours of continuous electrolysis, showing the potential for practical H2O2 electrosynthesis.

Designs of Tandem Catalysts and Cascade Catalytic Systems for CO2 Upgrading.

Upgrading CO2 into multi-carbon (C2+) compounds through the CO2 reduction reaction (CO2 RR) offers a practical approach to mitigate atmospheric CO2 while simultaneously producing high value chemicals. The reaction pathways for C2+ production involve multi-step proton-coupled electron transfer (PCET) and C-C coupling processes. By increasing the surface coverage of adsorbed protons (*Had ) and *CO intermediates, the reaction kinetics of PCET and C-C coupling can be accelerated, thereby promoting C2+ production. However, *Had and *CO are competitively adsorbed intermediates on monocomponent catalysts, making it difficult to break the linear scaling relationship between the adsorption energies of the *Had /*CO intermediate. Recently, tandem catalysts consisting of multicomponents have been developed to improve the surface coverage of *Had or *CO by enhancing water dissociation or CO2 -to-CO production on auxiliary sites. In this context, we provide a comprehensive overview of the design principles of tandem catalysts based on reaction pathways for C2+ products. Moreover, the development of cascade CO2 RR catalytic systems that integrate CO2 RR with downstream catalysis has expanded the range of potential CO2 upgrading products. Therefore, we also discuss recent advancements in cascade CO2 RR catalytic systems, highlighting the challenges and perspectives in these systems.

Accelerated Transfer and Spillover of Carbon Monoxide through Tandem Catalysis for Kinetics-boosted Ethylene Electrosynthesis.

Cu-based catalysts have been widely applied in electroreduction of carbon dioxide (CO2 ER) to produce multicarbon (C2+ ) feedstocks (e.g., C2 H4 ). However, the high energy barriers for CO2 activation on the Cu surface is a challenge for a high catalytic efficiency and product selectivity. Herein, we developed an in situ *CO generation and spillover strategy by engineering single Ni atoms on a pyridinic N-enriched carbon support with a sodalite (SOD) topology (Ni-SOD/NC) that acted as a donor to feed adjacent Cu nanoparticles (NPs) with *CO intermediate. As a result, a high C2 H4 selectivity of 62.5 % and an industrial-level current density of 160 mA cm-2 at a low potential of -0.72 V were achieved. Our studies revealed that the isolated NiN3 active sites with adjacent pyridinic N species facilitated the *CO desorption and the massive *CO intermediate released from Ni-SOD/NC then overflowed to Cu NPs surface to enrich the *CO coverage for improving the selectivity of CO2 ER to C2 H4 .

Single-atom Iron Catalyst with Biomimetic Active Center to Accelerate Proton Spillover for Medical-level Electrosynthesis of H2 O2 Disinfectant.

Electrosynthesis of H2 O2 has great potential for directly converting O2 into disinfectant, yet it is still a big challenge to develop effective electrocatalysts for medical-level H2 O2 production. Herein, we report the design and fabrication of electrocatalysts with biomimetic active centers, consisting of single atomic iron asymmetrically coordinated with both nitrogen and sulfur, dispersed on hierarchically porous carbon (FeSA -NS/C). The newly-developed FeSA -NS/C catalyst exhibited a high catalytic activity and selectivity for oxygen reduction to produce H2 O2 at a high current of 100 mA cm-2 with a record high H2 O2 selectivity of 90 %. An accumulated H2 O2 concentration of 5.8 wt.% is obtained for the electrocatalysis process, which is sufficient for medical disinfection. Combined theoretical calculations and experimental characterizations verified the rationally-designed catalytic active center with the atomic Fe site stabilized by three-coordinated nitrogen atoms and one-sulfur atom (Fe-N3 S-C). It was further found that the replacement of one N atom with S atom in the classical Fe-N4 -C active center could induce an asymmetric charge distribution over N atoms surrounding the Fe reactive center to accelerate proton spillover for a rapid formation of the OOH* intermediate, thus speeding up the whole reaction kinetics of oxygen reduction for H2 O2 electrosynthesis.

A rare case of bladder cancer that metastasized to brain, heart, and lung lymph nodes benefited from immunotherapy.

Bladder cancer is a common malignant tumor of the genitourinary system, with the primary cause of death being metastasis. The most common metastatic sites are the lymph nodes, liver, lung, bone, peritoneum, pleura, kidney, adrenal gland, and the intestine. Brain and heart metastases are rare. In this report, we describe a patient who had pulmonary lymph node metastases more than a year after being diagnosed with bladder cancer, followed by brain and cardiac metastases more than two years later. Following the failure of standard first-line chemotherapy, the patient accepted 6 cycles of tislelizumab immunotherapy. The re-examination revealed that the bilateral frontal brain metastases had vanished, the right temporal lobe metastases had been greatly decreased, the neurological symptoms had been alleviated, and the cardiac metastases had disappeared. This is a rare clinical case with encouraging effects of tislelizumab and can serve as a model for the treatment of similar patients.

Deciphering Single-Bacterium Adhesion Behavior Modulated by Extracellular Electron Transfer.

For bacterial adhesion and biofilm formation, a thorough understanding of the mechanism and effective modulating is lacking due to the complex extracellular electron transfer (EET) at bacteria-surface interfaces. Here, we explore the adhesion behavior of a model electroactive bacteria under various metabolic conditions by an integrated electrochemical single-cell force microscopy system. A nonlinear model between bacterial adhesion force and electric field intensity is established, which provides a theoretical foundation for precise tuning of bacterial adhesion strength by the surface potential and the direction and flux of electron flow. In particular, based on quantitative analyses with equivalent charge distribution modeling and wormlike chain numerical simulations, it is demonstrated that the chain conformation and unfolding events of outer membrane appendages are dominantly impacted by the dynamic bacterial EET processes. This reveals how the anisotropy of bacterial conductive structure can translate into the desired adhesion behavior in different scenarios.

Promoting CO2 Electroreduction Kinetics on Atomically Dispersed Monovalent ZnI Sites by Rationally Engineering Proton-Feeding Centers.

Electrocatalytic reduction of CO2 (CO2 RR) to value-added chemicals is of great significance for CO2 utilization, however the CO2 RR process involving multi-electron and proton transfer is greatly limited by poor selectivity and low yield. Herein, We have developed an atomically dispersed monovalent zinc catalyst anchored on nitrogenated carbon nanosheets (Zn/NC NSs). Benefiting from the unique coordination environment and atomic dispersion, the Zn/NC NSs exhibit a superior CO2 RR performance, featuring a high current density up to 50 mA cm-2 with an outstanding CO Faradaic efficiency of ≈95 %. The center ZnI atom coordinated with three N atoms and one N atom that bridges over two adjacent graphitic edges (Zn-N3+1 ) is identified as the catalytically active site. Experimental results reveal that the twisted Zn-N3+1 structure accelerates CO2 activation and protonation in the rate-determining step of *CO2 to *COOH, while theoretical calculations elucidate that atomically dispersed Zn-N3+1 moieties decrease the potential barriers for intermediate COOH* formation, promoting the proton-coupled CO2 RR kinetics and boosting the overall catalytic performance.

Graphene-modified graphite paper cathode for the efficient bioelectrochemical removal of chromium.

Metal-free electrocatalysts have been widely used as cathodes for the reduction of hexavalent chromium [Cr(VI)] in microbial fuel cells (MFCs). The electrocatalytic activity of such system needs to be increased due to the low anodic potential provided by bacteria. In this study, graphite paper (GP) was treated by liquid nitrogen to form three-dimensional graphite foam (3DGF), improving the Cr(VI) reduction by 17% and the total Cr removal by 81% at 30 h in MFCs. X-ray absorption spectroscopy confirmed the Cr(VI) reduction product as Cr(OH)3. Through the spectroscopy characterizations, electrochemical measurements, and density functional theory calculations, the porous structures, edges, and O-doped defects on the 3DGF surface resulted in a higher electroconducting rate and a lower mass transfer rate, which provide more active sites for the Cr(VI) reduction. Additionally, the scrolled graphene-like carbon nanosheets and porous structures on the 3DGF surface might limit the OH- diffusion and result in a high local pH, which accelerated the Cr(OH)3 formation. The results of this study are expected to provide a simple method to manipulate the carbon materials and insights into mechanisms of Cr(VI) reduction in MFCs by the 3DGF with in situ exfoliated edges and O-functionalized graphene.

Boosting Electroreduction Kinetics of Nitrogen to Ammonia via Tuning Electron Distribution of Single-Atomic Iron Sites.

Electrocatalytic nitrogen reduction reaction (NRR) plays a vital role for next-generation electrochemical energy conversion technologies. However, the NRR kinetics is still limited by the sluggish hydrogenation process on noble-metal-free electrocatalyst. Herein, we report the rational design and synthesis of a hybrid catalyst with atomic iron sites anchored on a N,O-doped porous carbon (FeSA -NO-C) matrix of an inverse opal structure, leading to a remarkably high NH3 yield rate of 31.9 µg NH 3 h-1 mg-1 cat. and Faradaic efficiency of 11.8 % at -0.4 V for NRR electrocatalysis, outperformed almost all previously reported atomically dispersed metal-nitrogen-carbon catalysts. Theoretical calculations revealed that the observed high NRR catalytic activity for the FeSA -NO-C catalyst stemmed mainly from the optimized charge-transfer between the adjacent O and Fe atoms homogenously distributed on the porous carbon support, which could not only significantly facilitate the transportation of N2 and ions but also effectively decrease the binding energy between the isolated Fe atom and *N2 intermediate and the thermodynamic Gibbs free energy of the rate-determining step (*N2 → *NNH).

Proton Capture Strategy for Enhancing Electrochemical CO2 Reduction on Atomically Dispersed Metal-Nitrogen Active Sites*.

Electrocatalysts play a key role in accelerating the sluggish electrochemical CO2 reduction (ECR) involving multi-electron and proton transfer. We now develop a proton capture strategy by accelerating the water dissociation reaction catalyzed by transition-metal nanoparticles (NPs) adjacent to atomically dispersed and nitrogen-coordinated single nickel (Ni-Nx ) active sites to accelerate proton transfer to the latter for boosting the intermediate protonation step, and thus the whole ECR process. Aberration-corrected scanning transmission electron microscopy, X-ray absorption spectroscopy, and calculations reveal that the Ni NPs accelerate the adsorbed H (Had ) generation and transfer to the adjacent Ni-Nx sites for boosting the intermediate protonation and the overall ECR processes. This proton capture strategy is universal to design and prepare for various high-performance catalysts for diverse electrochemical reactions even beyond ECR.

Dynamic Activation of Adsorbed Intermediates via Axial Traction for the Promoted Electrochemical CO2 Reduction.

Regulating the local environment and structure of metal center coordinated by nitrogen ligands (M-N4 ) to accelerate overall reaction dynamics of the electrochemical CO2 reduction reaction (CO2 RR) has attracted extensive attention. Herein, we develop an axial traction strategy to optimize the electronic structure of the M-N4 moiety and construct atomically dispersed nickel sites coordinated with four nitrogen atoms and one axial oxygen atom, which are embedded within the carbon matrix (Ni-N4 -O/C). The Ni-N4 -O/C electrocatalyst exhibited excellent CO2 RR performance with a maximum CO Faradic efficiency (FE) close to 100 % at -0.9 V. The CO FE could be maintained above 90 % in a wide range of potential window from -0.5 to -1.1 V. The superior CO2 RR activity is due to the Ni-N4 -O active moiety composed of a Ni-N4 site with an additional oxygen atom that induces an axial traction effect.

Determining the colorimetric attributes of multicolored materials based on a global correction and unsupervised image segmentation method.

Fast and accurate measurement of colors in multicolored prints using commercial instruments or existing computer vision systems remains a challenge due to limitations in image segmentation methods and the size and complexity of the colored patterns. To determine the colorimetric attributes (L*a*b*) of multicolored materials, an approach based on global color correction and an effective unsupervised image segmentation is presented. The colorimetric attributes of all patches in a ColorChecker chart were measured spectrophotometrically, and an image of the chart was also captured. Images were segmented using a modified Chan-Vese method, and the sRGB values of each patch were extracted and then transformed into L*a*b* values. In order to optimize the transformation process, the performance of 10 models was examined by minimizing the average color differences between measured and calculated colorimetric values. To assess the performance of the model, a set of printed samples was employed and the color differences between the predicted and measured L*a*b* values of samples were compared. The results show that the modified Chan-Vese method, with suitable settings, generates satisfactory segmentation of the printed images with mean and maximum ΔE00 values of 2.43 and 4.28 between measured and calculated values.

Depth recovery of hairy fibers for precise yarn hairiness measurement.

Hairiness is a concept describing the amount of hairy fibers (hairs) protruding from a yarn core in different spatial orientations and shapes. Most image-based hairiness assessment methods measure hairs by projecting a yarn on a 2D image plane, which suffers from two major problems: 1) not detecting defocused hairs (fuzzy hairs) when hairs are out of the field of view of the imaging system and 2) miscalculating real lengths of spatially curved hairs. The objective of this research was to develop a new image-based hairiness measurement method to mitigate these problems. The proposed method included two tasks: yarn image segmentation and hairiness assessment. The first task was to improve the detection rate of fuzzy hairs with a hybrid algorithm combining double homomorphic filtering and region-growing algorithms. The second task was to establish a width-depth mapping model for defocused hairs to compensate measurable lengths of defocused hairs based on their width information. The experiment results demonstrated that the proposed segmentation algorithm can detect fuzzy hairs usually missed by the previously used algorithm, and can produce more accurate hair length measurements than the previous algorithm when compared to the corresponding manual measurements, which were considered as the gold standard in this study.

Simultaneous measurement of pressure and temperature using dual-path distributed Brillouin sensor.

A sensing technique called a dual-path distributed Brillouin sensor (D-DBS) is proposed for simultaneous measurement of pressure and temperature. The D-DBS consists of a pair of sensing fibers, which are designed with different pressure and temperature coefficients of Brillouin frequency shift (BFS) by taking advantage of different fiber coatings. The highlight of this technique is to resolve the problem of the pressure-temperature cross sensitivity of the BFS within the optical fibers. The validation experiment shows satisfactory results, and it is indicated theoretically that the expected precisions of pressure and temperature are less than 0.25 MPa and 0.28°C, respectively.

[The characteristics of RR-Lorenz plot in persistent atrial fibrillation patients complicating with escape beats and rhythm].

OBJECTIVE: To explore the characteristics of RR-Lorenz plot in persistent atrial fibrillation (AF) patients complicating with escape beats and rhythm though ambulatory electrocardiogram. METHODS: The 24-hour ambulatory electrocardiogram of 291 persistent AF patients in second affiliated hospital of Zhengzhou university from July 2005 to April 2013 were retrospectively analyzed and the RR interval and the QRS wave were measured. Patients were divided into two groups according to the distribution of the RR-Lorenz point [AF without escape beats and rhythm group (Group A, n = 259) and AF with escape beats and rhythm group (Group B, n = 32)]. The characteristics of RR-Lorenz plot between the two groups were compared. RESULTS: (1) Fan-shaped RR-Lorenz plots were evidenced in Group A. (2)In Group B, 30 cases showed fan-shaped with L-shaped and a short dense rods along 45° line. The proportion of escape beats and rhythm was 0.28% (275/98 369) -14.06% (11 263/80 112) . The other 2 cases in group B showed no typical RR-Lorenz plots features. CONCLUSION: RR-Lorenz plot could help to quickly diagnose persistent AF complicating with escape beats and rhythm according to the typical RR-Lorenz plot characteristics in 24-hour ambulatory electrocardiogram.

Establishing CRISPRi for Programmable Gene Repression and Genome Evolution in Cupriavidus necator.

Cupriavidus necator H16 is a "Knallgas" bacterium with the ability to utilize various carbon sources and has been employed as a versatile microbial cell factory to produce a wide range of value-added compounds. However, limited genome engineering, especially gene regulation methods, has constrained its full potential as a microbial production platform. The advent of CRISPR/Cas9 technology has shown promise in addressing this limitation. Here, we developed an optimized CRISPR interference (CRISPRi) system for gene repression in C. necator by expressing a codon-optimized deactivated Cas9 (dCas9) and appropriate single guide RNAs (sgRNAs). CRISPRi was proven to be a programmable and controllable tool and could successfully repress both exogenous and endogenous genes. As a case study, we decreased the accumulation of polyhydroxyalkanoate (PHB) via CRISPRi and rewired the carbon fluxes to the synthesis of lycopene. Additionally, by disturbing the expression of DNA mismatch repair gene mutS with CRISPRi, we established CRISPRi-Mutator for genome evolution, rapidly generating mutant strains with enhanced hydrogen peroxide tolerance and robustness in microbial electrosynthesis (MES) system. Our work provides an efficient CRISPRi toolkit for advanced genetic manipulation and optimization of C. necator cell factories for diverse biotechnology applications.