Durable CO2 conversion in the proton-exchange membrane system.

Electrolysis that reduces carbon dioxide (CO2) to useful chemicals can, in principle, contribute to a more sustainable and carbon-neutral future1-6. However, it remains challenging to develop this into a robust process because efficient conversion typically requires alkaline conditions in which CO2 precipitates as carbonate, and this limits carbon utilization and the stability of the system7-12. Strategies such as physical washing, pulsed operation and the use of dipolar membranes can partially alleviate these problems but do not fully resolve them11,13-15. CO2 electrolysis in acid electrolyte, where carbonate does not form, has therefore been explored as an ultimately more workable solution16-18. Herein we develop a proton-exchange membrane system that reduces CO2 to formic acid at a catalyst that is derived from waste lead-acid batteries and in which a lattice carbon activation mechanism contributes. When coupling CO2 reduction with hydrogen oxidation, formic acid is produced with over 93% Faradaic efficiency. The system is compatible with start-up/shut-down processes, achieves nearly 91% single-pass conversion efficiency for CO2 at a current density of 600 mA cm-2 and cell voltage of 2.2 V and is shown to operate continuously for more than 5,200 h. We expect that this exceptional performance, enabled by the use of a robust and efficient catalyst, stable three-phase interface and durable membrane, will help advance the development of carbon-neutral technologies.

Self-Assembly Intermetallic PtCu3 Core with High-Index Faceted Pt Shell for High-Efficiency Oxygen Reduction.

Rational design of well-defined active sites is crucial for promoting sluggish oxygen reduction reactions. Herein, leveraging the surfactant-oriented and solvent-ligand effects, we develop a facile self-assembly strategy to construct a core-shell catalyst comprising a high-index Pt shell encapsulating a PtCu3 intermetallic core with efficient oxygen-reduction performance. Without undergoing a high-temperature route, the ordered PtCu3 is directly fabricated through the accelerated reduction of Cu2+, followed by the deposition of the remaining Pt precursor onto its surface, forming high-index steps oriented by the steric hindrance of surfactant. This approach results in a high half-wave potential of 0.911 V versus reversible hydrogen electrode, with negligible deactivation even after 15000-cycle operation. Operando spectroscopies identify that this core-shell catalyst facilitates the conversion of oxygen-involving intermediates and ensures antidissolution ability. Theoretical investigations rationalize that this improvement is attributed to reinforced electronic interactions around high-index Pt, stabilizing the binding strength of rate-determining OHads species.

Boosting Electrocatalytic Ammonia Synthesis via Synergistic Effect of Iron-Based Single Atoms and Clusters.

Electrocatalytic reduction of nitrate to ammonia (NO3RR) is gaining attention for low carbon emissions and environmental protection. However, low ammonia production rate and poor selectivity have remained major challenges in this multi-proton coupling process. Herein, we report a facile strategy toward a novel Fe-based hybrid structure composed of Fe single atoms and Fe3C atomic clusters that demonstrates outstanding performance for synergistic electrocatalytic NO3RR. By operando synchrotron Fourier transform infrared spectroscopy and theoretical computation, we clarify that Fe single atoms serve as the active site for NO3RR, while Fe3C clusters facilitate H2O dissociation to provide protons (*H) for continued hydrogenation reactions. As a result, the Fe-based electrocatalyst exhibits ammonia Faradaic efficiency of nearly 100%, with a corresponding production rate of 24768 µg h-1 cm-2 at -0.4 V vs RHE, exceeding most reported metal-based catalysts. This research provides valuable guidance toward multi-step reactions.

Visualization of the Distance-Dependent Synergistic Interaction in Heterogeneous Dual-Site Catalysis.

Understanding the characteristics of interfacial hydroxyl (OH) at the solid/liquid electrochemical interface is crucial for deciphering synergistic catalysis. However, it remains challenging to elucidate the influences of spatial distance between interfacial OH and neighboring reactants on reaction kinetics at the atomic level. Herein, we visualize the distance-dependent synergistic interaction in heterogeneous dual-site catalysis by using ex-situ infrared nanospectroscopy and in situ infrared spectroscopy techniques. These spectroscopic techniques achieve direct identification of the spatial distribution of synergistic species and reveal that OH facilitates the reactant deprotonation process depending on site distances in dual-site catalysts. Via modulating Ir-Co pair distances, we find that the dynamic equilibrium between generation and consumption of OH accounts for high-efficiency synergism at the optimized distance of 7.9 Å. At farther or shorter distances, spatial inaccessibility and resistance of OH with intermediates lead to OH accumulation, thereby diminishing the synergistic effect. Hence, a volcano-shaped curve has been established between the spatial distance and mass activity using formic acid oxidation as the probe reaction. This notion could also be extended to oxophilic metals, like Ir-Ru pairs, where volcano curves and dynamic equilibrium further evidence the universal significance of spatial distances.

Alleviating OH Blockage on the Catalyst Surface by the Puncture Effect of Single-Atom Sites to Boost Alkaline Water Electrolysis.

Nonprecious transition metal catalysts have emerged as the preferred choice for industrial alkaline water electrolysis due to their cost-effectiveness. However, their overstrong binding energy to adsorbed OH often results in the blockage of active sites, particularly in the cathodic hydrogen evolution reaction. Herein, we found that single-atom sites exhibit a puncture effect to effectively alleviate OH blockades, thereby significantly enhancing the alkaline hydrogen evolution reaction (HER) performance. Typically, after anchoring single Ru atoms onto tungsten carbides, the overpotential at 10 mA·cm-2 is reduced by more than 130 mV (159 vs 21 mV). Also, the mass activity is increased 16-fold over commercial Pt/C (MA100 = 17.3 A·mgRu-1 vs 1.1 A·mgPt-1, Pt/C). More importantly, such electrocatalyst-based alkaline anion-exchange membrane water electrolyzers can exhibit an ultralow potential (1.79 Vcell) and high stability at an industrial current density of 1.0 A·cm-2. Density functional theory (DFT) calculations reveal that the isolated Ru sites could weaken the surrounding local OH binding energy, thus puncturing OH blockage and constructing bifunctional interfaces between Ru atoms and the support to accelerate water dissociation. Our findings exhibit generality to other transition metal catalysts (such as Mo) and contribute to the advancement of industrial-scale alkaline water electrolysis.

Self-Optimized Ligand Effect of Single-Atom Modifier in Ternary Pt-Based Alloy for Efficient Hydrogen Oxidation.

Modifying the atomic and electronic structure of platinum-based alloy to enhance its activity and anti-CO poisoning ability is a vital issue in hydrogen oxidation reaction (HOR). However, the role of foreign modifier metal and the underlying ligand effect is not fully understood. Here, we propose that the ligand effect of single-atom Cu can dynamically modulate the d-band center of Pt-based alloy for boosting HOR performance. By in situ X-ray absorption spectroscopy, our research has identified that the potential-driven structural rearrangement into high-coordination Cu-Pt/Pd intensifies the ligand effect in Pt-Cu-Pd, leading to enhanced HOR performance. Thereby, modulating the d-band structure leads to near-optimal hydrogen/hydroxyl binding energies and reduced CO adsorption energies for promoting the HOR kinetics and the CO-tolerant capability. Accordingly, PtPdCu1/C exhibits excellent CO tolerance even at 1,000 ppm impurity.

Edge-Rich Pt-O-Ce Sites in CeO2 Supported Patchy Atomic-Layer Pt Enable a Non-CO Pathway for Efficient Methanol Oxidation.

Rational design of efficient methanol oxidation reaction (MOR) catalyst that undergo non-CO pathway is essential to resolve the long-standing poisoning issue. However, it remains a huge challenge due to the rather difficulty in maximizing the non-CO pathway by the selective coupling between the key *CHO and *OH intermediates. Here, we report a high-performance electrocatalyst of patchy atomic-layer Pt epitaxial growth on CeO2 nanocube (Pt ALs/CeO2) with maximum electronic metal-support interaction for enhancing the coupling selectively. The small-size monolayer material achieves an optimal geometrical distance between edge Pt-O-Ce sites and *OH absorbed on CeO2, which well restrains the dehydrogenation of *CHO, resulting in the non-CO pathway. Meanwhile, the *CHO/*CO intermediate generated at inner Pt-O-Ce sites can migrate to edge, inducing the subsequent coupling reaction, thus avoiding poisoning while promoting reaction efficiency. Consequently, Pt ALs/CeO2 exhibits exceptionally catalytic stability with negligible degradation even under 1000 s pure CO poisoning operation and high mass activity (14.87 A/mgPt), enabling it one of the best-performing alkali-stable MOR catalysts.

Coupling Single-Atom Sites and Ordered Intermetallic PtM Nanoparticles for Efficient Catalysis in Fuel Cells.

The design of an efficient catalytic system with low Pt loading and excellent stability for the acidic oxygen reduction reaction is still a challenge for the extensive application of proton-exchange membrane fuel cells. Here, a gas-phase ordered alloying strategy is proposed to construct an effective synergistic catalytic system that blends PtM intermetallic compounds (PtM IMC, M = Fe, Cu, and Ni) and dense isolated transition metal sites (M-N4 ) on nitrogen-doped carbon (NC). This strategy enables Pt nanoparticles and defects on the NC support to timely trap flowing metal salt without partial aggregation, which is attributed to the good diffusivity of gaseous transition metal salts with low boiling points. In particular, the resulting Pt1 Fe1 IMC cooperating with Fe-N4 sites achieves cooperative oxygen reduction with a half-wave potential up to 0.94 V and leads to a high mass activity of 0.51 A  mgPt -1 and only 23.5% decay after 30 k cycles, both of which exceed DOE 2025 targets. This strategy provides a method for reducing Pt loading in fuel cells by integrating Pt-based intermetallics and single transition metal sites to produce an efficient synergistic catalytic system.

Uncovering the Nature of Active Sites during Electrocatalytic Reactions by In Situ Synchrotron-Based Spectroscopic Techniques.

Catalysts can effectively accelerate the reaction kinetics process and are recognized as the core to realize the conversion and supply of carbon-free energy. However, the active sites of catalysts, especially nanocatalysts, usually undergo dynamic structural evolution under realistic working conditions, which may be induced by various reaction effects such as the applied voltages, electrolytes, or adsorbed intermediates. Therefore, in-depth and systemic insights into the nature of the active sites involved under the working conditions are prerequisites for correlating structure-performance relationships. However, uncovering and identifying active sites under operation conditions are still formidable scientific and technical challenges, which are severely hindered by the complex physical and chemical processes occurring on the active sites. Meanwhile, complementary and important information could be missed by conducting only the conventionally employed ex situ microscopic and spectroscopic measurements. Accordingly, it is highly desirable for us to develop the ever-increasing in situ synchrotron-based techniques to identify the nature of active sites, which renders the rational design of functional catalysts achievable.In this Account, we elaborately highlight the substantial achievements in cutting-edge in situ X-ray spectroscopy (XAS) techniques by presenting several representative carbon-neutral electrocatalytic examples performed in our group to broadcast the principles and virtues of identifying the active sites and tracing intermediate species during electrocatalytic water splitting and electrocatalytic CO2 reduction (ECR). Specifically, we believe that the interactions between the active sites and the support as well as the adsorption behaviors of intermediates are considered to be the important factors that govern the performance in the water splitting reaction. Meanwhile, the structural rearrangement of alloy catalysts driven by the cathodic potential significantly governs the activity and selectivity toward ECR. More importantly, the directions and suggestions for addressing the current limitations and pitfalls that we may encounter in the course of executing in situ experiments are also provided. Accordingly, it is necessary to use multiple in situ synchrotron-based techniques to obtain the comprehensive details. Furthermore, bridging the gap between the real energy devices and half-reactions could help us to approach the realistic mechanism. Beyond that, developing the rapid time resolution of in situ XAS will overcome the challenge of timescale mismatch to capture the faster structural kinetics of catalysts. Therefore, this Account is aimed to increase the awareness and appreciation of conducting in situ investigations on energy conversion reactions, which would be a guideline for us to explore catalytic scopes that remain challenging.

Tandem Addition/Cyclization/Halogenation Reaction of Difluoromethylated N-Acylhydrazones with Allyltrimethylsilanes.

As novel difluoromethyl building blocks, difluoromethylated N-acylhydrazones react with allyltrimethylsilanes and the halogen source via a tandem addition/cyclization/halogenation strategy, which produces various difluoromethylpyrazoline compounds in good yields. The method features mild reaction conditions, broad substrate scopes, and a transition metal-free process with easy operation. It also proves that difluoromethylated N-acylhydrazones are useful difluoromethyl building blocks for the construction of difluoromethylated nitrogen heterocycles.

Methodological Challenges in Spatial and Contextual Exposome-Health Studies.

The concept of the exposome encompasses the totality of exposures from a variety of external and internal sources across an individual's life course. The wealth of existing spatial and contextual data makes it appealing to characterize individuals' external exposome to advance our understanding of environmental determinants of health. However, the spatial and contextual exposome is very different from other exposome factors measured at the individual-level as spatial and contextual exposome data are more heterogenous with unique correlation structures and various spatiotemporal scales. These distinctive characteristics lead to multiple unique methodological challenges across different stages of a study. This article provides a review of the existing resources, methods, and tools in the new and developing field for spatial and contextual exposome-health studies focusing on four areas: (1) data engineering, (2) spatiotemporal data linkage, (3) statistical methods for exposome-health association studies, and (4) machine- and deep-learning methods to use spatial and contextual exposome data for disease prediction. A critical analysis of the methodological challenges involved in each of these areas is performed to identify knowledge gaps and address future research needs.

Chemical composition analysis of Angelica sinensis (Oliv.) Diels and its four processed products by ultra-high-performance liquid chromatography coupled with quadrupole-orbitrap mass spectrometry combining with nontargeted metabolomics.

Angelica sinensis (Oliv.) Diels. has been used for women to enrich the blood, prevent and treat blood deficiency syndrome in Traditional Chinese Medicine for thousands of years. Wine-processed Angelica sinensis, soil-processed Angelica sinensis, oil-processed Angelica sinensis, and charred-processed Angelica sinensis are the most significant four processed products used in Chinese clinic. However, there have been few studies aimed at comparing their chemical differences. Ultra-high-performance liquid chromatography coupled with quadrupole-orbitrap mass spectrometry combining with nontargeted metabolomics was applied to investigate the diversity of processed products of Angelica sinensis. A total of 74 compounds with the variable importance in the projection value more than 1.5 and P less than 0.05 in ANOVA were highlighted as the compounds that contribute most to the discrimination of Angelica sinensis and four processed products. The results showed the metabolic changes between Angelica sinensis and its four processed products, there were 19 metabolites, 3 metabolites, 6 metabolites, and 45 metabolites were tentatively assigned in soil-processed Angelica sinensis, wine-processed Angelica sinensis, oil-processed Angelica sinensis, and charred-processed Angelica sinensis, respectively. These results suggested that the proposed metabolomics approach was useful for the quality evaluation and control of processed products of Angelica sinensis.

Ligand Assisted Thermal Atomization of Palladium Clusters: An Inspiring Approach for the Rational Design of Atomically Dispersed Metal Catalysts.

The transformation from metal nanocluster catalysts to metal single-atom catalysts is an important procedure in the rational design of atomically dispersed metal catalysts (ADCs). However, the conversion methods often involve high annealing temperature as well as reducing atmosphere. Herein, we reported a continuous and convenient approach to transfer Pd nanocluster into Pd single-atom in a ligand assisted annealing procedure, by which means we reduced its activating temperature low to 400 °C. Using ex-situ microscopy and spectroscopy, we comprehensively monitored the structural evolution of Pd species though the whole atomization process. Theoretical calculation revealed that the structural instability caused by remaining Cl ligands was the main reason for this low-temperature transformation. The present atomization strategy and mechanistic knowledge for the conversion from cluster to atomic dispersion provides guidelines for the rational design of ADCs.

Understanding Synergistic Catalysis on Cu-Se Dual Atom Sites via Operando X-ray Absorption Spectroscopy in Oxygen Reduction Reaction.

The construction and understanding of synergy in well-defined dual-atom active sites is an available avenue to promote multistep tandem catalytic reactions. Herein, we construct a dual-hetero-atom catalyst that comprises adjacent Cu-N4 and Se-C3 active sites for efficient oxygen reduction reaction (ORR) activity. Operando X-ray absorption spectroscopy coupled with theoretical calculations provide in-depth insights into this dual-atom synergy mechanism for ORR under realistic device operation conditions. The heteroatom Se modulator can efficiently polarize the charge distribution around symmetrical Cu-N4 moieties, and serve as synergistic site to facilitate the second oxygen reduction step simultaneously, in which the key OOH*-(Cu1 -N4 ) transforms to O*-(Se1 -C2 ) intermediate on the dual-atom sites. Therefore, this designed catalyst achieves satisfied alkaline ORR activity with a half-wave potential of 0.905 V vs. RHE and a maximum power density of 206.5 mW cm-2 in Zn-air battery.

X-ray Compton backscattering imaging via structured light.

Compton backscattering imaging (CBI) is a technique that uses ionizing radiation to detect the presence of low atomic number materials on a given target. Unlike transmission x-ray imaging, the source and sensor are located on the same side, such that the photons of interest are scattered back after the radiation impinges on the body. Rather than scanning the target pixel by pixel with a pencil-beam, this paper proposes the use of cone-beam coded illumination to create the compressive x-ray Compton backscattering imager (CXBI). The concept was developed and tested using Montecarlo simulations through the Geant4 application for tomography emissions (GATE), with conditions close to the ones encountered in experiments, and posteriorly, a test-bed implementation was mounted in the laboratory. The CXBI was evaluated under several conditions and with different materials as target. Reconstructions were run using denoising-prior-based inverse problem algorithms. Finally, a preliminary dose analysis was done to evaluate the viability of CXBI for human scanning.

Multivariate log-contrast regression with sub-compositional predictors: Testing the association between preterm infants' gut microbiome and neurobehavioral outcomes.

To link a clinical outcome with compositional predictors in microbiome analysis, the linear log-contrast model is a popular choice, and the inference procedure for assessing the significance of each covariate is also available. However, with the existence of multiple potentially interrelated outcomes and the information of the taxonomic hierarchy of bacteria, a multivariate analysis method that considers the group structure of compositional covariates and an accompanying group inference method are still lacking. Motivated by a study for identifying the microbes in the gut microbiome of preterm infants that impact their later neurobehavioral outcomes, we formulate a constrained integrative multi-view regression. The neurobehavioral scores form multivariate responses, the log-transformed sub-compositional microbiome data form multi-view feature matrices, and a set of linear constraints on their corresponding sub-coefficient matrices ensures the sub-compositional nature. We assume all the sub-coefficient matrices are possible of low-rank to enable joint selection and inference of sub-compositions/views. We propose a scaled composite nuclear norm penalization approach for model estimation and develop a hypothesis testing procedure through de-biasing to assess the significance of different views. Simulation studies confirm the effectiveness of the proposed procedure. We apply the method to the preterm infant study, and the identified microbes are mostly consistent with existing studies and biological understandings.

Efficacy analysis of anterior debridement and bone graft fusion in the treatment of sacroiliac joint tuberculous arthritis: a retrospective analysis of 17 patients.

BACKGROUND: Sacroiliac joint tuberculous arthritis is a relatively rare site of tuberculosis infection, but it can lead to severe sacroiliac joint destruction and dysfunction. Since there are few studies on the surgical methods of sacroiliac joint tuberculosis (SJT), we adopted three different surgical methods based on different degrees of destruction of sacroiliac joint tuberculous arthritis. While revealing its clinical symptoms to improve the diagnostic accuracy, and to determine the safety and feasibility of this surgical approach in the treatment of sacroiliac joint tuberculous arthritis. METHODS: We retrospectively analyzed 17 patients with tuberculous arthritis of the sacroiliac joint treated by anterior debridement. All these patients underwent anterior debridement of tuberculosis with or without bone graft fusion. Mean postoperative follow-up was 17.2 months (12-25 months). The erythrocyte sedimentation rate (ESR) was used to judge the general situation after surgery, and the fusion of sacroiliac joints was observed by X-ray films and CT scans. And VAS and ODI were used to score to observe postoperative functional recovery. RESULTS: Anterior approach debridement is an effective surgical approach for sacroiliac joint tuberculous arthritis. All patients achieved effective relief of lower back and hip pain. The pain was significantly relieved 3 months after the operation, and the pain basically disappeared 6 months after the operation. The erythrocyte sedimentation rate was also significantly reduced after the operation, and it can basically return to the normal level 3 months after the operation. The VAS score and ODI index of the other 16 patients after surgery were significantly lower than those before surgery, except for 1 patient who died of severe type I respiratory failure and septic shock 3 months after surgery, The surviving patients were basically able to achieve stable fusion of the sacroiliac joint at 12 months postoperatively. None of the patients reported significant pain until the last follow-up visit. CONCLUSIONS: The anterior approach is a very effective surgical method for the treatment of sacroiliac joint tuberculous arthritis, and it is safe and feasible. A clear operative field of view facilitates complete debridement and reduces recurrence, and its function recovers well with stable arthrodesis.

Evaluation of complications associated with bifocal bone transport as treatment for either proximal, intermediate or distal femoral defects caused by infection: outcome analysis of 76 patients.

BACKGROUND: The purpose of this study was to evaluate the outcomes of bifocal bone transport in the treatment of femoral bone defects caused by infections. METHODS: Clinical and radiographic data of patients with infected femoral nonunion treated by the bifocal bone transport at our hospital were analyzed retrospectively, from January 2008 to December 2019. Depending on the location of bone defects, the patients were divided into three groups (proximal, intermediate, and distal). The Association for the Study and Application of the Method of Ilizarov (ASAMI) criteria was applied to assess the bone and functional outcomes. Postoperative complications of three groups were documented and compared. RESULTS: Seventy-six cases of infected femoral bone defects (31 cases of proximal, 19 cases of intermediate, and 26 cases of distal) were managed by bifocal bone transport successfully with a mean follow-up time of 30.8 months (range, 23 to 41 months). There were 58 men (76.3%) and 18 women (23.6%), with a mean age of 38.8 years (range, 23 to 60 years). The bone union was received in 76 cases with a mean of 6.9 months (range, 5 to 8 months). Pin tract infection was observed in twenty-nine cases (38.1%), 7 cases (9.2%) of muscle contractures, 3 cases (7.9%) of joint stiffness, 13 cases (17.1%) of axial deviation, 2 cases (2.6%) of delayed union, one case (1.3%) of nonunion, and none (0%) of transport gap re-fracture. One patient (1.3%) was scheduled for knee arthroplasty when bone transport treatment ended. CONCLUSIONS: Bone transport using an external rail fixator was a practical method to treat the femoral bone defects, since the satisfactory rate of bone union and limb function recovery. Complications of distal femoral bone transport were more severe than the proximal and intermedia, but the rate of complication was the least of the three groups. Soft-tissue-related complications were more likely to occur in the intermediate bone transport.

Exploring the Therapeutic Effects of Black Ginseng on Non-Alcoholic Fatty Liver Disease by Using Network Pharmacology and Molecular Docking.

This study aimed to investigate the therapeutic effect of black ginseng (BG) on non-alcoholic fatty liver disease (NAFLD) using network pharmacology combined with the molecular docking strategy. The saponin composition of BG was analyzed by liquid chromatography-mass spectrometry (LC/MS) instrument. Then the network pharmacology was applied to explore the potential targets and related mechanisms of BG in the treatment of NAFLD. After screening out key targets, molecular docking was used to predict the binding modes between ginsenoside and target. Finally, a methionine and choline deficiency (MCD) diet-induced NAFLD mice model was established to further confirm the therapeutic effect of BG on NAFLD. Twenty-four ginsenosides were annotated based on the MS and tandem MS information. Ten proteins were screened out as key targets closely related to BG treatment of NAFLD. The molecular docking showed that most of the ginsenosides had good binding affinities with AKT1. The validation experiment revealed that BG administration could reduce serum alanine aminotransferase (ALT) and aspartate aminotransferase (AST) levels and improve the MCD diet-induced histological changes in liver tissue. Moreover, BG could upregulate the phosphorylation level of AKT in the liver of NAFLD mice, thereby exerting the therapeutic effect on NAFLD. Further studies on the active ginsenosides as well as their synergistic action on NAFLD will be required to reveal the underlying mechanisms in-depth. This study demonstrates that network pharmacological prediction in conjunction with molecular docking is a viable technique for screening the active chemicals and related targets of BG, which can be applied to other herbal medicines.