Tuning Main Group Element-based Metal-Organic Framework to Boost Electrocatalytic Nitrogen Reduction Under Ambient Conditions.

Main group element-based materials are emerging catalysts for ammonia (NH3 ) production via a sustainable electrochemical nitrogen reduction reaction (N2 RR) pathway under ambient conditions. However, their N2 RR performances are less explored due to the limited active behavior and unclear mechanism. Here, an aluminum-based defective metal-organic framework (MOF), aluminum-fumarate (Al-Fum), is investigated. As a proof of concept, the pristine Al-Fum MOF is synthesized by the solvothermal reaction process, and the defect engineering method namely solvent-assisted linker exchange, is applied to create the defective Al sites. The defective Al sites play an important role in ensuring the N2 RR activity for defective Al-Fum. It is found that only the defective Al-Fum enables stable and effective electrochemical N2 RR, in terms of the highest production rate of 53.9 µg(NH3 ) h-1 mgcat -1 (in 0.4 m K2 SO4 ) and the Faradaic efficiency of 73.8% (in 0.1 m K2 SO4 ) at -0.15 V vs reversible hydrogen electrode) under ambient conditions. Density functional theory calculations confirm that the N2 activation can be achieved on the defective Al sites. Such sites also allow the subsequent protonation process via the alternating associative mechanism. This defect characteristic gives the main group Al-based MOFs the ability to serve as promising electrocatalysts for N2 RR and other attractive applications.

A Two-Dimensional van der Waals Heterostructure with Isolated Electron-Deficient Cobalt Sites toward High-Efficiency CO2 Electroreduction.

Electrochemical CO2 conversion is a promising way for sustainable chemical fuel production, yet the conversion efficiency is strongly limited by the sluggish kinetics and complex reaction pathways. Here we report the ultrathin conjugated metalloporphyrin covalent organic framework epitaxially grown on graphene as a two-dimensional van der Waals heterostructure to catalyze CO2 reduction. Operando X-ray absorption and density functional theory calculations reveal the strong interlayer coupling leads to electron-deficient metal centers and speeds up electrocatalysis. The Co(III)-N4 centers exhibit a CO Faradaic efficiency of 97% at a partial current density of 8.2 mA cm-2 in an H-cell, along with a stable running over 30 h. The selectivity of CO approached 99% with a partial current density of 191 mA cm-2 in a liquid flow cell, and the turnover frequency achieved 50 400 h-1 at -1.15 V vs RHE, outperforming most reported organometallic frameworks. This work highlights the key role of strong electronic coupling between van der Waals layers for accelerating the dynamics of CO2 conversion.

Reversible Al Metal Anodes Enabled by Amorphization for Aqueous Aluminum Batteries.

Aqueous aluminum metal batteries (AMBs) are regarded as one of the most sustainable energy storage systems among post-lithium-ion candidates, which is attributable to their highest theoretical volumetric capacity, inherent safe operation, and low cost. Yet, the development of aqueous AMBs is plagued by the incapable aluminum plating in an aqueous solution and severe parasitic reactions, which results in the limited discharge voltage, thus making the development of aqueous AMBs unsuccessful so far. Here, we demonstrate that amorphization is an effective strategy to tackle these critical issues of a metallic Al anode by shifting the reduction potential for Al deposition. The amorphous aluminum (a-Al) interfacial layer is triggered by an in situ lithium-ion alloying/dealloying process on a metallic Al substrate with low strength. Unveiled by experimental and theoretical investigations, the amorphous structure greatly lowers the Al nucleation energy barrier, which forces the Al deposition competitive to the electron-stealing hydrogen evolution reaction (HER). Simultaneously, the inhibited HER mitigates the passivation, promoting interfacial ion transfer kinetics and enabling steady aluminum plating/stripping for 800 h in the symmetric cell. The resultant multiple full cells using Al@a-Al anodes deliver approximately a 0.6 V increase in the discharge voltage plateau compared to that of bare Al-based cells, which far outperform all reported aqueous AMBs. In both symmetric cells and full cells, the excellent electrochemical performances are achieved in a noncorrosive, low-cost, and fluorine-free Al2(SO4)3 electrolyte, which is ecofriendly and can be easily adapted for sustainable large-scale applications. This work brings an intriguing picture of the design of metallic anodes for reversible and high-voltage AMBs.

Enhanced Electrochemical Methanation of Carbon Dioxide at the Single-Layer Hexagonal Boron Nitride/Cu Interfacial Perimeter.

The electrochemical conversion of CO2 to valuable fuels is a plausible solution to meet the soaring need for renewable energy sources. However, the practical application of this process is limited by its poor selectivity due to scaling relations. Here we introduce the rational design of the monolayer hexagonal boron nitride/copper (h-BN/Cu) interface to circumvent scaling relations and improve the electrosynthesis of CH4. This catalyst possesses a selectivity of >60% toward CH4 with a production rate of 15 µmol·cm-2·h-1 at -1.00 V vs RHE, along with a much smaller decaying production rate than that of pristine Cu. Both experimental and theoretical calculations disclosed that h-BN/Cu interfacial perimeters provide specific chelating sites to immobilize the intermediates, which accelerates the conversion of *CO to *CHO. Our work reports a novel Cu catalyst engineering strategy and demonstrates the prospect of monolayer h-BN contributing to the design of heterostructured CO2 reduction electrocatalysts for sustainable energy conversion.

Graphdiyne/Graphene Heterostructure: A Universal 2D Scaffold Anchoring Monodispersed Transition-Metal Phthalocyanines for Selective and Durable CO2 Electroreduction.

Electrochemical CO2 reduction (CO2R) is a sustainable way of producing carbon-neutral fuels, yet the efficiency is limited by its sluggish kinetics and complex reaction pathways. Developing active, selective, and stable CO2R electrocatalysts is challenging and entails intelligent material structure design and tailoring. Here we show a graphdiyne/graphene (GDY/G) heterostructure as a 2D conductive scaffold to anchor monodispersed cobalt phthalocyanine (CoPc) and reduce CO2 with an appreciable activity, selectivity, and durability. Advanced characterizations, e.g., synchrotron-based X-ray absorption spectroscopy (XAS), and density functional theory (DFT) calculation disclose that the strong electronic coupling between GDY and CoPc, together with the high surface area, abundant reactive centers, and electron conductivity provided by graphene, synergistically contribute to this distinguished electrocatalytic performance. Electrochemical measurements revealed a high FECO of 96% at a partial current density of 12 mA cm-2 in a H-cell and an FECO of 97% at 100 mA cm-2 in a liquid flow cell, along with a durability over 24 h. The per-site turnover frequency of CoPc reaches 37 s-1 at -1.0 V vs RHE, outperforming most of the reported phthalocyanine- and porphyrin-based electrocatalysts. The usage of the GDY/G heterostructure as a scaffold can be further extended to other organometallic complexes beyond CoPc. Our findings lend credence to the prospect of the GDY/G hybrid contributing to the design of single-molecule dispersed CO2R catalysts for sustainable energy conversion.

Dynamic Restructuring of Cu-Doped SnS2 Nanoflowers for Highly Selective Electrochemical CO2 Reduction to Formate.

With ever-increasing energy consumption and continuous rise in atmospheric CO2 concentration, electrochemical reduction of CO2 into chemicals/fuels is becoming a promising yet challenging solution. Sn-based materials are identified as attractive electrocatalysts for the CO2 reduction reaction (CO2 RR) to formate but suffer from insufficient selectivity and activity, especially at large cathodic current densities. Herein, we demonstrate that Cu-doped SnS2 nanoflowers can undergo in situ dynamic restructuring to generate catalytically active S-doped Cu/Sn alloy for highly selective electrochemical CO2 RR to formate over a wide potential window. Theoretical thermodynamic analysis of reaction energetics indicates that the optimal electronic structure of the Sn active site can be regulated by both S-doping and Cu-alloying to favor formate formation, while the CO and H2 pathways will be suppressed. Our findings provide a rational strategy for electronic modulation of metal active site(s) for the design of active and selective electrocatalysts towards CO2 RR.

First insight of the intergenerational effects of tri-n-butyl phosphate and polystyrene microplastics to Daphnia magna.

As an emerging organic pollutant, tributyl phosphate (TnBP) can be easily adsorbed by microplastics, resulting in compound toxic effects. In the present work, the effects of polystyrene microplastics (PS-MPs) and TnBP on the survival, growth, reproduction and oxidative stress of Daphnia magna (D. magna) have been evaluated through multigenerational test. Compared with the alone exposure groups, the somatic growth rate and the expression values of growth related genes rpa1, mre11, rnha, and rfc3_5 in the F1 generation of the combined exposure groups were significantly lower (p < 0.05), indicating synergistic effect of PS-MPs and TnBP on the growth toxicity and transgenerational effects. In addition, compared with the PS-MPs groups, significantly lower average number of offspring and expression values of reproduction related genes ccnb, mcm2, sgrap, and ptch1 were observed in the combined exposure group and TnBP group (p < 0.05), indicating TnBP might be the major factor causing reproductive toxicity to D. magna. Although PS-MPs and TnBP alone or in combination also had toxic impacts on the growth, survival and reproduction of D. magna in generations F0 and F2, the effects were less than F1 generation. Regarding oxidative stress, the activity of SOD, CAT and GSH-Px and MDA content in the generations F0 and F1 of combined exposure groups were higher than the TnBP group but lower than the PS-MPs groups, suggesting that PS-MPs might be the dominant cause of the oxidative damage in D. magna and the presence of TnBP would alleviate oxidative stress by reducing the bioaccumulation of PS-MPs. The present work will provide a theoretical basis for further understanding of the toxic effects and ecological risks of combined TnBP and microplastic pollution on aquatic organisms.

Alloying Pd with Ru enables electroreduction of nitrate to ammonia with ∼100% faradaic efficiency over a wide potential window.

Electrocatalytic nitrate (NO3-) reduction reaction (eNO3-RR) to ammonia under ambient conditions is deemed a sustainable route for wastewater treatment and a promising alternative to the Haber-Bosch process. However, there is still a lack of efficient electrocatalysts to achieve high NH3 production performance at wastewater-relevant low NO3- concentrations. Herein, we report a Pd74Ru26 bimetallic nanocrystal (NC) electrocatalyst capable of exhibiting an average NH3 FE of ∼100% over a wide potential window from 0.1 to -0.3 V (vs. reversible hydrogen electrode, RHE) at a low NO3- concentration of 32.3 mM. The average NH3 yield rate at -0.3 V can reach 16.20 mg h-1 cm-2. Meanwhile, Pd74Ru26 also demonstrates excellent electrocatalytic stability for over 110 h. Experimental investigations and density functional theory (DFT) calculations suggest that the electronic structure modulation between Pd and Ru favors the optimization of NO3- transport with respect to single components. Along the *NO3 reduction pathway, the synergy between Pd and Ru can also lower the energy barrier of the rate-determining steps (RDSs) on Ru and Pd, which are the protonation of *NO2 and *NO, respectively. Finally, this unique alloying design achieves a high-level dynamic equilibrium of adsorption and coupling between *H and various nitrogen intermediates during eNO3-RR.

Balanced NOx- and Proton Adsorption for Efficient Electrocatalytic NOx- to NH3 Conversion.

Electrocatalytic nitrate (NO3-)/nitrite (NO2-) reduction reaction (eNOx-RR) to ammonia under ambient conditions presents a green and promising alternative to the Haber-Bosch process. Practically available NOx- sources, such as wastewater or plasma-enabled nitrogen oxidation reaction (p-NOR), typically have low NOx- concentrations. Hence, electrocatalyst engineering is important for practical eNOx-RR to obtain both high NH3 Faradaic efficiency (FE) and high yield rate. Herein, we designed balanced NOx- and proton adsorption by properly introducing Cu sites into the Fe/Fe2O3 electrocatalyst. During the eNOx-RR process, the H adsorption is balanced, and the good NOx- affinity is maintained. As a consequence, the designed Cu-Fe/Fe2O3 catalyst exhibits promising performance, with an average NH3 FE of ∼98% and an average NH3 yield rate of 15.66 mg h-1 cm-2 under the low NO3- concentration (32.3 mM) of typical industrial wastewater at an applied potential of -0.6 V versus reversible hydrogen electrode (RHE). With low-power direct current p-NOR generated NOx- (23.5 mM) in KOH electrolyte, the Cu-Fe/Fe2O3 catalyst achieves an FE of ∼99% and a yield rate of 15.1 mg h-1 cm-2 for NH3 production at -0.5 V (vs RHE). The performance achieved in this study exceeds industrialization targets for NH3 production by exploiting two available low-concentration NOx- sources.

Efficient CO2 Electroreduction to Ethanol by Cu3 Sn Catalyst.

Electrochemical carbon dioxide reduction to ethanol suggests a potential strategy to reduce the CO2 level and generate valuable liquid fuels, while the development of low-cost catalysts with high activity and selectivity remains a major challenge. In this work, a bimetallic, low-entropy state Cu3 Sn catalyst featuring efficient electrocatalytic CO2  reduction to ethanol is developed. This low-entropy state Cu3 Sn catalyst allows a high Faradaic efficiency of 64% for ethanol production, distinctively from the high-entropy state Cu6 Sn5  catalyst with the main selectivity toward producing formate. At an industry-level current density of -900 mA cm-2 , the Cu3 Sn catalyst exhibited excellent stability for over 48 h in a membrane-electrode based electrolyzer. Theoretical calculations indicate that the high ethanol selectivity on Cu3 Sn is attributed to its enhanced adsorption of several key intermediates in the ethanol production pathway. Moreover, the life-cycle assessment reveals that using the Cu3 Sn electrocatalyst, an electrochemical CO2 -to-ethanol electrolysis system powered by wind electricity can lead to a global warming potential of 120 kgCO2-eq for producing 1 ton of ethanol, corresponding to a 55% reduction of carbon emissions compared to the conventional bio-ethanol process.

Machine Learning: An Advanced Platform for Materials Development and State Prediction in Lithium-Ion Batteries.

Lithium-ion batteries (LIBs) are vital energy-storage devices in modern society. However, the performance and cost are still not satisfactory in terms of energy density, power density, cycle life, safety, etc. To further improve the performance of batteries, traditional "trial-and-error" processes require a vast number of tedious experiments. Computational chemistry and artificial intelligence (AI) can significantly accelerate the research and development of novel battery systems. Herein, a heterogeneous category of AI technology for predicting and discovering battery materials and estimating the state of the battery system is reviewed. Successful examples, the challenges of deploying AI in real-world scenarios, and an integrated framework are analyzed and outlined. The state-of-the-art research about the applications of ML in the property prediction and battery discovery, including electrolyte and electrode materials, are further summarized. Meanwhile, the prediction of battery states is also provided. Finally, various existing challenges and the framework to tackle the challenges on the further development of machine learning for rechargeable LIBs are proposed.

A Defect Engineered Electrocatalyst that Promotes High-Efficiency Urea Synthesis under Ambient Conditions.

Synthesizing urea from nitrate and carbon dioxide through an electrocatalysis approach under ambient conditions is extraordinarily sustainable. However, this approach still lacks electrocatalysts developed with high catalytic efficiencies, which is a key challenge. Here, we report the high-efficiency electrocatalytic synthesis of urea using indium oxyhydroxide with oxygen vacancy defects, which enables selective C-N coupling toward standout electrocatalytic urea synthesis activity. Analysis by operando synchrotron radiation-Fourier transform infrared spectroscopy showcases that *CO2NH2 protonation is the potential-determining step for the overall urea formation process. As such, defect engineering is employed to lower the energy barrier for the protonation of the *CO2NH2 intermediate to accelerate urea synthesis. Consequently, the defect-engineered catalyst delivers a high Faradaic efficiency of 51.0%. In conjunction with an in-depth study on the catalytic mechanism, this design strategy may facilitate the exploration of advanced catalysts for electrochemical urea synthesis and other sustainable applications.

Metal-Ion Oligomerization Inside Electrified Carbon Micropores and its Effect on Capacitive Charge Storage.

Ion adsorption inside electrified carbon micropores is pivotal for the operation of supercapacitors. Depending on the electrolyte, two main mechanisms have been identified so far, the desolvation of ions in solvents and the formation of superionic states in ionic liquids. Here, it is shown that upon confinement inside negatively charged micropores, transition-metal cations dissolved in water associate to form oligomer species. They are identified using in situ X-ray absorption spectroscopy. The cations associate one with each other via hydroxo bridging, forming ionic oligomers under the synergic effect of spatial confinement and Coulombic screening. The oligomers display sluggish dissociation kinetics and accumulate upon cycling, which leads to supercapacitor capacitance fading. They may be dissolved by applying a positive potential, so an intermittent reverse cycling strategy is proposed to periodically evacuate micropores and revivify the capacitance. These results reveal new insights into ion adsorption and structural evolution with their effects on the electrochemical performance, providing guidelines for designing advanced supercapacitors.

Crystal phase effect upon O2 activation on gold surfaces through intrinsic strain.

Crystal phase engineering is a promising strategy to tune the catalytic performance of metal nanomaterials. Generally, the crystal phase effect on catalysis is ascribed to distinct surface atomic arrangements of catalysts with different crystal phases. Here we show that even for similar surfaces, such as the close-packed surfaces, different crystal phases have considerably different surface reactivities due to their distinct intrinsic surface strains. Using first-principles calculations, we find that the close-packed surfaces of hexagonal close-packed (HCP) and double HCP (4H) gold have significantly smaller intrinsic strains (∼1.3%) than those of face-centered cubic (FCC) gold (∼2.3%). These distinct intrinsic surface strains result in various oxygen adsorption energies and O2 dissociation barriers on these close-packed gold surfaces, and the dissociation of O2 on different crystal phases and surfaces follows the Brønsted-Evans-Polanyi principle.

Realizing Ultralow Concentration Gelation of Graphene Oxide with Artificial Interfaces.

Understanding the chemistry in the gelation (interfacial assembly) of graphene oxide (GO) is very essential for the practical uses of graphene-based materials. Herein, with the designed artificial interfaces due to the introduction of water-miscible isopropanol, the gelation of GO is achieved in water at an ultralow concentration (0.1 mg mL-1 , the lowest ever-reported) with a solvothermal treatment. Intrinsically, with a lower intercalation energy, water shows much stronger attraction with GO than isopropanol, inducing a microphase separation in the miscible mixture of isopropanol and water. In the solvothermal process, the partially reduced GO sheets interact with each other along the water-isopropanol interface and assemble into interconnected frameworks. In general, the formation of the artificial interface results in locally concentrated GO in the water phase, which is the final driving force for the gelation at ultralow concentration. Thus, the threshold for the GO gelation concentration is dependent upon the water fraction in the mixture and water acts as the spacer to facilitate the gelation and final control of the resulting materials microstructure. This study enriches interface/gelation chemistry of GO and indicates a practical way for precise structural control and scale-up preparation of graphene-based materials.

Interfacing Epitaxial Dinickel Phosphide to 2D Nickel Thiophosphate Nanosheets for Boosting Electrocatalytic Water Splitting.

Heterostructures with abundant phase boundaries are compelling for surface-mediated electrochemical applications. However, rational design of such bifunctional electrocatalysts for efficient hydrogen and oxygen evolution reactions (HER and OER) is still challenging. Here, due to the well-matched lattice parameters, we easily achieved the epitaxy of two-dimensional ternary nickel thiophosphate (NiPS3) nanosheets with in-grown dinickel phosphide (Ni2P) through an in situ growth strategy. Density functional theory calculations reveal that the NiPS3/Ni2P heterojunction significantly decreases the kinetic barrier for hydrogen adsorption and accelerates electron transfer due to the built-in electric field at the epitaxial interfaces. The significantly improved electrocatalytic performance is shown to be closely related to the epitaxial interfacial area rather than the amount of secondary phase. Notably, the resultant NiPS3/Ni2P heterostructures enable an overall water splitting electrolyzer to achieve 50 mA cm-2 at a lower bias of 1.65 V compared to that for the pristine NiPS3 alone (2.02 V) and even the benchmark Pt/C//IrO2 electrocatalysts (1.69 V).

Interfacial Lattice-Strain-Driven Generation of Oxygen Vacancies in an Aerobic-Annealed TiO2 (B) Electrode.

Oxygen vacancies play crucial roles in defining physical and chemical properties of materials to enhance the performances in electronics, solar cells, catalysis, sensors, and energy conversion and storage. Conventional approaches to incorporate oxygen defects mainly rely on reducing the oxygen partial pressure for the removal of product to change the equilibrium position. However, directly affecting reactants to shift the reaction toward generating oxygen vacancies is lacking and to fill this blank in synthetic methodology is very challenging. Here, a strategy is demonstrated to create oxygen vacancies through making the reaction energetically more favorable via applying interfacial strain on reactants by coating, using TiO2 (B) as a model system. Geometrical phase analysis and density functional theory simulations verify that the formation energy of oxygen vacancies is largely decreased under external strain. Benefiting from these, the obtained oxygen-deficient TiO2 (B) exhibits impressively high level of capacitive charge storage, e.g., ≈53% at 0.5 mV s-1 , far surpassing the ≈31% of the unmodified counterpart. Meanwhile, the modified electrode shows significantly enhanced rate capability delivering a capacity of 112 mAh g-1 at 20 C (≈6.7 A g-1 ), ≈30% higher than air-annealed TiO2 and comparable to vacuum-calcined TiO2 . This work heralds a new paradigm of mechanical manipulation of materials through interfacial control for rational defect engineering.

[Seasonal occurrence characteristics of different forms of nitrogen in the sediments of Chaohu Lake].

Seasonal characteristics of the free nitrogen (FN), the exchangeable nitrogen (EN), the acid hydrolysable nitrogen (HN) and the residual nitrogen (RN) in the surface sediment of Chaohu Lake were analyzed by sequential extraction method. The correlations among the nitrogen fractions with the total nitrogen (TN) and the mineralizable nitrogen (MN) were discussed considering the seasonal variations of the TN and MN. The results show that the concentrations of FN, EN and TN are lower in summer and higher in autumn and winter, NH4(+)-N is the main fraction of FN and EN. TN concentrations are much higher in West Chaohu Lake with the maximum concentration of 2280.47 mg/kg in the west lake center than in the East Chaohu Lake. The seasonal order of mineralizable nitrogen (MN) content is winter> spring > autumn > summer. The bio-available nitrogen fraction varies with different seasons, which is the amino acid nitrogen (AAN) in spring, EN in summer and autumn, FN in winter. The study about seasonal occurrence characteristics of nitrogen fractions in sediment provided foundational data for lake ecological security evaluation and nitrogen release evaluation.

[Seasonal variation characteristics of algae biomass in Chaohu Lake].

The biomass and distribution of algae community in Chaohu Lake were investigated in 2008. At the same time, the seasonal variations of algae translocation between the sediment and overlying water were also quantitative studied by self-made "algae up/down trap". Chaohu Lake was dominated by Cyanobacteria all the year, and dominant Cyanobacteria species changed in different seasons. In spring, Anabaena was the dominant species, and Microcystis was the subdominant species; In the whole summer and autumn, the dominant species is Microcystis. Algae biomass increased significantly from May and the maximum appeared in August, was 146.37 mg x m(-3) with Chl-a. The value of algae biomass were 9.75-16.24 mg x kg(-1) in the surface sediments, and the minimum appeared in Summer, then the algae biomass increased gradually with the maximum value in winter. Translocation process between the sediment and the overlying water occurred throughout the study period. The recruitment rates increased at first with the maximum rates in early August, was 0.036 8 mg x (m2 x d) (-1), and then had a downward tendency. However the sedimentation rates increased slowly firstly with the maximum rate in early September, then it decreased sharply, was 0.032 1 mg x (m2 x d)(-1). Multiple stepwise regression showed that temperature was the most significant factor for the algae biomass in Chaohu Lake, Total nitrogen (TN) and Total phosphorus(TP) are sub-important factors.