Achieving over 90% Faradaic Efficiency in Cyclohexanone Oxime Electrosynthesis Using the Cu-Mo Dual-Site Catalyst.

Coupling with the nitrate electroreduction reaction (NitRR), the electrosynthesis of cyclohexanone oxime (CHO, the vital feedstock in the nylon-6 industry) from cyclohexanone provides a promising alternative to the traditional energy consumption process. However, it still suffers from low efficiency because selective production of *NH2OH intermediate from NitRR under large current densities is challenging. We here report a Cu1MoOx/nitrogen-doped carbon (NC) electrocatalyst with high-density Cu-Mo dual sites for NitRR to selectively produce and stabilize *NH2OH, with the subsequent cyclohexanone oximation achieving the highest CHO Faradaic efficiency of 94.5% and a yield rate of 3.0 mol g-1 h-1 at an industrially relevant current density of 0.5 A cm-2. Furthermore, in situ characterizations evidenced that the Cu-Mo dual sites in Cu1MoOx/NC effectively inhibited hydrodeoxygenation of hydroxyl-containing intermediates of NitRR, selectively producing *NH2OH and thus achieving cyclohexanone oximation with high efficiency. This work provides a high-performance catalyst for CHO electrosynthesis from nitrogenous waste, showing promising application potential in industrial production of CHO.

Unveiling the Interfacial Species Synergy in Promoting CO2 Tandem Electrocatalysis in Near-Neutral Electrolyte.

The interfacial species-built local environments on Cu surfaces impact the CO2 electroreduction process significantly in producing value-added multicarbon (C2+) products. However, intricate interfacial dynamics leads to a challenge in understanding how these species affect the process. Herein, with ab initio molecular dynamics (AIMD) and finite element method (FEM) simulations, we reveal that the highly concentrated interfacial species, including the *CO, hydroxide, and K+, could synergistically promote the C-C coupling on the one-dimensional (1D) porous hollow structure regulated interfacial environment. The Cu-Ag tandem catalyst was then synthesized with the as-designed structure, exhibiting a high C2+ Faradaic efficiency of 76.0% with a partial current density of 380.0 mA cm-2 in near-neutral electrolytes. Furthermore, in situ Raman spectra validate that the 1D porous structure regulates the concentration of interfacial CO intermediates and ions to increase *CO coverage, local pH value, and ionic field, promoting the CO2-to-C2+ activity. These results provide insights into the design of practical ECR electrocatalysts by regulating interfacial species-induced local environments.

Alkali Metal Cations Induce Structural Evolution on Au(111) During Cathodic Polarization.

The activity of the electrocatalytic CO2 reduction reaction (CO2RR) is substantially affected by alkali metal cations (AM+) in electrolytes, yet the underlying mechanism is still controversial. Here, we employed electrochemical scanning tunneling microscopy and in situ observed Au(111) surface roughening in AM+ electrolytes during cathodic polarization. The roughened surface is highly active for catalyzing the CO2RR due to the formation of surface low-coordinated Au atoms. The critical potential for surface roughening follows the order Cs+ > Rb+ > K+ > Na+ > Li+, and the surface proportion of roughened area decreases in the order of Cs+ > Rb+ > K+ > Na+ > Li+. Electrochemical CO2RR measurements demonstrate that the catalytic activity strongly correlates with the surface roughness. Furthermore, we found that AM+ is critical for surface roughening to occur. The results unveil the unrecognized effect of AM+ on the surface structural evolution and elucidate that the AM+-induced formation of surface high-activity sites contributes to the enhanced CO2RR in large AM+ electrolytes.

Modulating the electronic structure of ion phthalocyanine-based molecular catalysts for electrocatalytic nitrogen reduction: a DFT study.

The highly localized Fe d orbital in ion phthalocyanine (FePc)-based molecular catalysts significantly hinders their electrocatalytic nitrogen reduction reaction (eNRR) performance. Herein, we theoretically designed a series of FePc-based molecules with adjacent metal phthalocyanine sites to form an asymmetric delocalized electronic structure on Fe centers, promoting the catalytic activity and lowering the overpotential of the eNRR, as well as suppressing the hydrogen evolution reaction (HER) side reaction.

Facile Hydrogen-Bonding Assisted Crystallization Modulation for Large-area High-quality CsPbI2 Br Films and Efficient Solar Cells.

The thermally stable inorganic cesium-based perovskites promise efficient and stable photovoltaics. Unfortunately, the strong ionic bonds lead to uncontrollable rapid crystallization, making it difficult in fabricating large-area black-phase film for photovoltaics. Herein, we developed a facile hydrogen-bonding assisted strategy for modulating the crystallization of CsPbI2 Br to achieve uniform large-area phase-pure films with much-reduced defects. The simple addition of methylamine acetate in precursors not only promotes the formation of intermediate phase via hydrogen bonding to circumvent the direct crystallization of CsPbI2 Br from ionic precursors but also widens the film processing window, thus enabling to fabricate large-area high-quality phase-pure CsPbI2 Br film under benign conditions. Combining with stable dopant-free poly(3-hexylthiophene), the CsPbI2 Br solar cells achieve the record-high efficiencies of 18.14 % and 16.46 % for 0.1 cm2 and 1 cm2 active area, respectively. The obtained high efficiency of 38.24 % under 1000 lux illumination suggests its potential in indoor photovoltaics for powering the Internet of Things, etc.

Unconventional hcp/fcc Nickel Heteronanocrystal with Asymmetric Convex Sites Boosts Hydrogen Oxidation.

Developing non-platinum group metal catalysts for the sluggish hydrogen oxidation reaction (HOR) is critical for alkaline fuel cells. To date, Ni-based materials are the most promising candidates but still suffer from insufficient performance. Herein, we report an unconventional hcp/fcc Ni (u-hcp/fcc Ni) heteronanocrystal with multiple epitaxial hcp/fcc heterointerfaces and coherent twin boundaries, generating rugged surfaces with plenty of asymmetric convex sites. Systematic analyses discover that such convex sites enable the adsorption of *H in unusual bridge positions with weakened binding energy, circumventing the over-strong *H adsorption on traditional hollow positions, and simultaneously stabilizing interfacial *H2O. It thus synergistically optimizes the HOR thermodynamic process as well as reduces the kinetic barrier of the rate-determining Volmer step. Consequently, the developed u-hcp/fcc Ni exhibits the top-rank alkaline HOR activity with a mass activity of 40.6 mA mgNi -1 (6.3 times higher than fcc Ni control) together with superior stability and high CO-tolerance. These results provide a paradigm for designing high-performance catalysts by shifting the adsorption state of intermediates through configuring surface sites.

Unconventional Bilateral Compressive Strained Ni-Ir Interface Synergistically Accelerates Alkaline Hydrogen Oxidation.

The alkaline hydrogen oxidation reaction (HOR) involves the coupling of adsorbed hydrogen (Had) and hydroxyl (OHad) species and is thus orders of magnitude slower than that in acid media. According to the Sabatier principle, developing electrocatalysts with appropriate binding energy for both intermediates is vital to accelerating the HOR though it is still challenging. Herein, we propose an unconventional bilateral compressive strained Ni-Ir interface (Ni-Ir(BCS)) as efficient synergistic HOR sites. Density functional theory (DFT) simulations reveal that the bilateral compressive strain effect leads to the appropriate adsorption for both Had and OHad, enabling their coupling thermodynamically spontaneous and kinetically preferential. Such Ni-Ir(BCS) is experimentally achieved by embedding sub-nanometer Ir clusters in graphene-loaded high-density Ni nanocrystals (Ni-Ir(BCS)/G). As predicted, it exhibits a HOR mass activity of 7.95 and 2.88 times those of commercial Ir/C and Pt/C together with much enhanced CO tolerance, respectively, ranking among the most active state-of-the-art HOR catalysts. These results provide new insights into the rational design of advanced electrocatalysts involving coordinated adsorption and activation of multiple reactants.

Probing the Synergistic Effects of Mg2+ on CO2 Reduction Reaction on CoPc by In Situ Electrochemical Scanning Tunneling Microscopy.

We report herein the in situ electrochemical scanning tunneling microscopy (ECSTM) study on the synergistic effect of Mg2+ in CO2 reduction reaction (CO2RR) catalyzed by cobalt phthalocyanine (CoPc). ECSTM measurement molecularly resolves the self-assembled CoPc monolayer on the Au(111) substrate. In the CO2 environment, high-contrast species are observed in the adlayer and assigned to the CO2 adsorption on CoPc. Furthermore, the contrast of the CO2-bound complex is higher in Mg2+-containing electrolytes than in Mg2+-free electrolytes, indicating the formation of the CoPc-CO2-Mg2+ complex. The surface coverage of adsorbed CO2 is positively correlated with the Mg2+ concentration as the additive in electrolytes up to a plateau of 30.8 ± 2.7% when c(Mg2+) > 30 mM. The potential step experiment indicates the higher CO2 adsorption dynamics in Mg2+-containing electrolytes than without Mg2+. The rate constants of CO2 adsorption and dissociation in different electrolytes are extracted from the data fitting of statistical results from in situ ECSTM experiments.

Controlled Synthesis of EDTA-Modified Porous Hollow Copper Microspheres for High-Efficiency Conversion of CO2 to Multicarbon Products.

Electrochemical reduction of CO2 into value-added products is an effective approach to relieve environmental and energetic issues. Herein, EDTA anion-modified porous hollow copper microspheres (H-Cu MPs) were constructed by EDTA-2Na-assisted electrodeposition. The faradic efficiency (FE) of ethylene doubled from 23.3% to 50.1% at -0.82 V vs RHE in nearly neutral 0.1 M KHCO3 solution, one of the highest values among copper-based electrodeposited catalysts. Apart from the favorable influence from morphology regulated by EDTA-2Na, theoretical calculations revealed that the adsorbed EDTA anions were able to create a local charged copper surface to stabilize the transition state and dimer and to assist in the stabilization by interacting with OCCO adsorbate synergistically, which contributed to the outstanding catalytic performance together.

In Situ Imaging Facet-Induced Spatial Heterogeneity of Electrocatalytic Reaction Activity at the Subparticle Level via Electrochemiluminescence Microscopy.

Investigating catalytic behavior of heterogeneous catalysts, especially at the crystal facets level, is crucial for rational catalyst design in the energy and environmental fields. Here we demonstrate an efficient approach to in situ visualize and analyze the heterogeneity of electrocatalytic activity on different facets at the subparticle level via electrochemiluminescence (ECL) microscopy. ZnO crystals with various exposed facet proportions were synthesized, and the correlation between their electrocatalytic performance toward luminol analogue degradation and the exposed facets is established. It is clearly imaged that the ZnO (002) facet has superior catalytic performance compared to the ZnO (100) facet, which is supported by theoretical computation and electrochemical experiments as the facet-induced heterogeneity of the catalytic effect on oxygen reduction into the key reactant for ECL. Accordingly, the spatial heterogeneity of electrocatalytic activity at different facets on one particle is visualized for the first time. The realization of subparticle ECL imaging and kinetic analysis could provide a special approach to visualize facet-induced spatial heterogeneity of catalytic behavior and valuable information for the catalysis study and analysis.

Graphene Quantum Dots Wrapped Gold Nanoparticles with Integrated Enhancement Mechanisms as Sensitive and Homogeneous Substrates for Surface-Enhanced Raman Spectroscopy.

Rational engineering of highly stable and Raman-active nanostructured substrates is still urgently in demand for achieving sensitive and reliable surface-enhanced Raman spectroscopy (SERS) analysis in solution phase. Herein, monodisperse N-doping graphene quantum dots wrapped Au nanoparticles (Au-NGQD NPs) were facilely prepared, and further their applications as substrates in SERS-based detection and cellular imaging have been explored. The as-prepared Au-NGQD NPs exhibit superior long-term stability and biocompatibility, as well as large enhancement capability due to the integration of electromagnetic and chemical enhancements. The practical applicability of the Au-NGQD NPs was verified via the direct SERS tests of several kinds of aromatics in solution phase. Finite-difference time-domain simulations in combination with density functional theory calculation were also successfully used to explain the enhancement mechanism. Furthermore, the Au-NGQD NPs were conjugated with 4-nitrobenzenethiol (4-NBT, as reporter) and 4-mercaptophenylboronic acid (MPBA, as targeting element) to construct the MPBA/4-NBT@Au-NGQD probes, which could specifically recognize glycan-overexpressed cancer cells through SERS imaging on a cell surface. The prepared Au-NGQDs show great potential as superior SERS substrates in solution phase for on-site Raman detection.

Bipyridine-Assisted Assembly of Au Nanoparticles on Cu Nanowires To Enhance the Electrochemical Reduction of CO2.

We report a new strategy to prepare a composite catalyst for highly efficient electrochemical CO2 reduction reaction (CO2 RR). The composite catalyst is made by anchoring Au nanoparticles on Cu nanowires via 4,4'-bipyridine (bipy). The Au-bipy-Cu composite catalyzes the CO2 RR in 0.1 m KHCO3 with a total Faradaic efficiency (FE) reaching 90.6 % at -0.9 V to provide C-products, among which CH3 CHO (25 % FE) dominates the liquid product (HCOO- , CH3 CHO, and CH3 COO- ) distribution (75 %). The enhanced CO2 RR catalysis demonstrated by Au-bipy-Cu originates from its synergistic Au (CO2 to CO) and Cu (CO to C-products) catalysis which is further promoted by bipy. The Au-bipy-Cu composite represents a new catalyst system for effective CO2 RR conversion to C-products.

In Situ Visualization of Electrocatalytic Reaction Activity at Quantum Dots for Water Oxidation.

Exploring electrocatalytic reactions on the nanomaterial surface can give crucial information for the development of robust catalysts. Here, electrocatalytic reaction activity at single quantum dots (QDs) loaded silica microparticle involved in water oxidation is visualized using electrochemiluminescence (ECL) microscopy. Under positive potential, the active redox centers at QDs induce the generation of hydroperoxide surface intermediates as coreactants to remarkably enhance ECL emission from luminol derivative molecules for imaging. For the first time, in situ visualization of the catalytic activity of water oxidation with QDs catalyst was achieved, supported by a linear relation between ECL intensity and turn over frequency. A very slight diffusion trend attributed to only the luminol species proved in situ capture of hydroperoxide surface intermediates at catalytic active sites of QDs. This work provides tremendous potential in online imaging of electrocatalytic reactions and visual evaluation of catalyst performance.

Tuning Sn-Catalysis for Electrochemical Reduction of CO2 to CO via the Core/Shell Cu/SnO2 Structure.

Tin (Sn) is known to be a good catalyst for electrochemical reduction of CO2 to formate in 0.5 M KHCO3. But when a thin layer of SnO2 is coated over Cu nanoparticles, the reduction becomes Sn-thickness dependent: the thicker (1.8 nm) shell shows Sn-like activity to generate formate whereas the thinner (0.8 nm) shell is selective to the formation of CO with the conversion Faradaic efficiency (FE) reaching 93% at -0.7 V (vs reversible hydrogen electrode (RHE)). Theoretical calculations suggest that the 0.8 nm SnO2 shell likely alloys with trace of Cu, causing the SnO2 lattice to be uniaxially compressed and favors the production of CO over formate. The report demonstrates a new strategy to tune NP catalyst selectivity for the electrochemical reduction of CO2 via the tunable core/shell structure.

High-Density CuInS2 Quantum Dots for Efficient and Stable CO2 Electroreduction.

Electrochemically converting CO2 back into fuels and chemicals is promising in alleviating the greenhouse effect worldwide. Various high-efficiency catalysts have been achieved, yet the unsatisfied structural stability under CO2 electrolysis conditions restricts their practical application. Herein, a sub-5 nm sized CuInS2 quantum dots (CIS-QDs) based electrocatalyst for converting CO2 into CO are developed. Taking advantage of the stable M─Ch (metal-chalcogenide) covalent bonds, and unique p-block metal properties, the as-prepared catalyst exhibits excellent structural stability under large overpotentials and can achieve a high CO Faradaic efficiency (FE) of 86% (total CO2 reduction FE of 89%) at -0.65 V versus reversible hydrogen electrode with long-term durability of 40 h and outstanding current densities of 10.6 mA cm-2 simultaneously. Furthermore, detailed electrochemical analyses revealed that the excellent performance of the as-prepared catalysts shall be attributed to the high-density active sites and fast charge transfer brought by the ultrasmall size of CIS-QDs. This work provides insights into the design of high-density and stable catalytic sites for developing high-performance electrocatalysts.

Three-year field study on the temporal response of soil microbial communities and functions to PFOA exposure.

Contamination of per- and polyfluoroalkyl substances (PFAS) poses a significant threat to soil ecosystem health, yet there remains a lack of understanding regarding the responses of soil microbial communities to prolonged PFAS exposure in field conditions. This study involved a three-year field investigation to track changes in microbial communities and functions in soil subjected to the contamination of a primary PFAS, perfluorooctanoic acid (PFOA). Results showed that PFOA exposure altered soil bacterial and fungal communities in terms of diversity, composition, and structure. Notably, certain bacterial communities with a delayed reaction to PFOA contamination showed the most significant response after one year of exposure. Fungal communities were sensitive to PFOA in soil, exhibiting significant responses within just four months of exposure. After two years, the impact of PFOA on both bacterial and fungal communities was lessened, likely due to the long-term adaptation of microbial communities to PFOA. Moreover, PFOA exposure notably inhibited alkaline phosphatase activity and reduced certain phosphorus cycling-related functional genes after three years of exposure, suggesting potential disruptions in soil fertility. These new insights advance our understanding of the long-term effects of PFOA on soil microbial communities and functions at a field scale.

Developing Hypoxia-Sensitive System via Designing Tumor-Targeted Fullerene-Based Photosensitizer for Multimodal Therapy of Deep Tumor.

Photodynamic therapy (PDT) has been approved for clinic. However, powerless efficiency for deep hypoxic tumor therapy remains an enormous challenge for PDT. Herein, a hypoxia-sensitive nanotherapeutic system (FTCD-SRGD) based on fullerene (C70) and anoxic activating chemical prodrug tirapazamine (TPZ) is rationally designed for multimodal therapy of deep hypoxic tumors. To enhance the accumulation and achieve specific drug release in tumor, the FTCD-SRGD is modified with cyclo(Arg-Gly-Asp-d-Phe-Lys) (cRGDfK) peptide and disulfide bonds. With the exacerbated hypoxic microenvironment created by C70 consuming O2 for generating reactive oxygen species (ROS), TPZ is activated to produce toxic radical species to ablate deep tumors, which achieves a synergistic treatment of C70-mediated PDT and hypoxia-enhanced chemotherapy. Additionally, given this hypoxia-sensitive system-induced immunogenic cell death (ICD) activating anticancer cytotoxic T lymphocyte to result in more susceptible tumor to immunotherapy, FTCD-SRGD plus immune checkpoint inhibitor (anti-PD-L1) fully inhibit deep hypoxic tumors by promoting infiltration of effector T cells in tumors. Collectively, it is the first time to develop a multimodal therapy system with fullerene-based hypoxia-sensitive PS for deep tumors. The powerful multimodal nanotherapeutic system for combining hypoxia-enhanced PDT and immunotherapy to massacre deep hypoxic tumors can provide a paradigm to combat the present bottleneck of tumor therapy.

Ruxolitinib improves the inflammatory microenvironment, restores glutamate homeostasis, and promotes functional recovery after spinal cord injury.

JOURNAL/nrgr/04.03/01300535-202419110-00030/figure1/v/2024-03-08T184507Z/r/image-tiff The inflammatory microenvironment and neurotoxicity can hinder neuronal regeneration and functional recovery after spinal cord injury. Ruxolitinib, a JAK-STAT inhibitor, exhibits effectiveness in autoimmune diseases, arthritis, and managing inflammatory cytokine storms. Although studies have shown the neuroprotective potential of ruxolitinib in neurological trauma, the exact mechanism by which it enhances functional recovery after spinal cord injury, particularly its effect on astrocytes, remains unclear. To address this gap, we established a mouse model of T10 spinal cord contusion and found that ruxolitinib effectively improved hindlimb motor function and reduced the area of spinal cord injury. Transcriptome sequencing analysis showed that ruxolitinib alleviated inflammation and immune response after spinal cord injury, restored EAAT2 expression, reduced glutamate levels, and alleviated excitatory toxicity. Furthermore, ruxolitinib inhibited the phosphorylation of JAK2 and STAT3 in the injured spinal cord and decreased the phosphorylation level of nuclear factor kappa-B and the expression of inflammatory factors interleukin-1ß, interleukin-6, and tumor necrosis factor-α. Additionally, in glutamate-induced excitotoxicity astrocytes, ruxolitinib restored EAAT2 expression and increased glutamate uptake by inhibiting the activation of STAT3, thereby reducing glutamate-induced neurotoxicity, calcium influx, oxidative stress, and cell apoptosis, and increasing the complexity of dendritic branching. Collectively, these results indicate that ruxolitinib restores glutamate homeostasis by rescuing the expression of EAAT2 in astrocytes, reduces neurotoxicity, and effectively alleviates inflammatory and immune responses after spinal cord injury, thereby promoting functional recovery after spinal cord injury.

Nanoarchitectured electrochemical cytosensors for selective detection of leukemia cells and quantitative evaluation of death receptor expression on cell surfaces.

The variable susceptibility to the tumor necrosis factor-related apoptosis-inducing ligand (TRAIL) treatment observed in various types of leukemia cells is related to the difference in the expression levels of death receptors, DR4 and DR5, on the cell surfaces. Quantifying the DR4/DR5 expression status on leukemia cell surfaces is of vital importance to the development of diagnostic tools to guide death receptor-based leukemia treatment. Taking the full advantages of novel nanobiotechnology, we have developed a robust electrochemical cytosensing approach toward ultrasensitive detection of leukemia cells with detection limit as low as ~40 cells and quantitative evaluation of DR4/DR5 expression on leukemia cell surfaces. The optimization of electron transfer and cell capture processes at specifically tailored nanobiointerfaces and the incorporation of multiple functions into rationally designed nanoprobes provide unique opportunities of integrating high specificity and signal amplification on one electrochemical cytosensor. The high sensitivity and selectivity of this electrochemical cytosensing approach also allows us to evaluate the dynamic alteration of DR4/DR5 expression on the surfaces of living cells in response to drug treatments. Using the TRAIL-resistant HL-60 cells and TRAIL-sensitive Jurkat cells as model cells, we have further verified that the TRAIL susceptibility of various types of leukemia cells is directly correlated to the surface expression levels of DR4/DR5. This versatile electrochemical cytosensing platform is believed to be of great clinical value for the early diagnosis of human leukemia and the evaluation of therapeutic effects on leukemia patients after radiation therapy or drug treatment.

A novel aptamer-based competition strategy for ultrasensitive electrochemical detection of leukemia cells.

A robust, nanobiotechnology-based electrochemical cytosensing platform for the detection of acute leukemia cells was developed with high sensitivity, selectivity, acceptable rapidity and excellent extensibility. It utilized the competitive binding of cell-specific aptamers to acute leukemia cells and subsequent voltammetric quantification of the metal signature. Greatly enhanced sensitivity was achieved with dual signal amplification by using Fe3O4 magnetic nanoparticles (MNPs) as carriers to load a large amount of gold nanoparticles (AuNPs) and AuNP-catalyzed silver deposition. The proposed competitive cytosensor showed high sensitivity with a detection limit down to 10 cells. This simple and low-cost electrochemical cytosensing approach offers great promise to extend its application to early detection of human leukemia and possibly to other cancer cells.