N and OH-Immobilized Cu3 Clusters In Situ Reconstructed from Single-Metal Sites for Efficient CO2 Electromethanation in Bicontinuous Mesochannels.

Cu-based catalysts hold promise for electrifying CO2 to produce methane, an extensively used fuel. However, the activity and selectivity remain insufficient due to the lack of catalyst design principles to steer complex CO2 reduction pathways. Herein, we develop a concept to design carbon-supported Cu catalysts by regulating Cu active sites' atomic-scale structures and engineering the carbon support's mesoscale architecture. This aims to provide a favorable local reaction microenvironment for a selective CO2 reduction pathway to methane. In situ X-ray absorption and Raman spectroscopy analyses reveal the dynamic reconstruction of nitrogen and hydroxyl-immobilized Cu3 (N,OH-Cu3) clusters derived from atomically dispersed Cu-N3 sites under realistic CO2 reduction conditions. The N,OH-Cu3 sites possess moderate *CO adsorption affinity and a low barrier for *CO hydrogenation, enabling intrinsically selective CO2-to-CH4 reduction compared to the C-C coupling with a high energy barrier. Importantly, a block copolymer-derived carbon fiber support with interconnected mesopores is constructed. The unique long-range mesochannels offer an H2O-deficient microenvironment and prolong the transport path for the CO intermediate, which could suppress the hydrogen evolution reaction and favor deep CO2 reduction toward methane formation. Thus, the newly developed catalyst consisting of in situ constructed N,OH-Cu3 active sites embedded into bicontinuous carbon mesochannels achieved an unprecedented Faradaic efficiency of 74.2% for the CO2 reduction to methane at an industry-level current density of 300 mA cm-2. This work explores effective concepts for steering desirable reaction pathways in complex interfacial catalytic systems via modulating active site structures at the atomic level and engineering pore architectures of supports on the mesoscale to create favorable microenvironments.

Metal Selenide-Based Superstructure Nanoarrays with Ultrahigh Capacity for Alkaline Zn Batteries.

Transition metal selenides (TMSs) have great potential as cathode materials for alkaline Zn batteries (AZBs) owing to their high theoretical capacity and metallic conductivity. However, achieving a high specific capacity remains a formidable challenge due to the low structural stability and sluggish reaction kinetics of single-phase TMS. Herein, a facile method for fabricating a robust CoSe2 @Ni3 Se4 @Ni(OH)2 superstructure nanoarray (CNSNA) as an AZB cathode is presented. The sophisticated design enables structural stability and abundant active surface sites for efficient charge storage. Furthermore, the redox mediator K3 [Fe(CN)6 ] is employed to expedite the reaction kinetics and introduce supplementary redox reactions, further enhancing the charge storage capability. Consequently, the CNSNA electrode delivers an exceptional specific capacitance (609.08 mAh g-1 at 1 A g-1 ), surpassing all previously reported selenide-based materials. High-rate capability (239.37 mAh g-1 at 20 A g-1 ) and long cycling stability have also been achieved. The comprehensive charge storage mechanism studies confirmed the structural integrity, kinetic improvement, and high reactivity of the CNSNA superstructure. Moreover, the corresponding AZB based on CNSNA demonstrates an extraordinarily high energy density of 516.58 Wh kg-1 . The work offers guidance in the construction of superstructure-based TMS electrode materials, paving the way for the development of high-performance AZBs.

Facile and Scalable Synthesis of Metal- and Nitrogen-Doped Carbon Nanotubes for Efficient Electrochemical CO2 Reduction.

Metal- and nitrogen-doped carbon (M-N-C) is a promising material to catalyze electrochemical CO2 reduction reaction (CO2RR). However, most M-N-C catalysts in the literature require complicated synthesis procedures and produce small quantities per batch, limiting the commercialization potential. In this work, we developed a simple and scalable synthesis method to convert metal-impurity-containing commercial carbon nanotubes (CNTs) and nitrogen-containing organic precursors into M-N-C via one-step moderate-temperature (650 °C) pyrolysis without any other treatment nor the need to add metal precursors. Batches of catalysts in varied mass up to 10 g (150 mL in volume) per batch were synthesized, and repeatable catalytic performances were demonstrated. To the best of our knowledge, the 10 g batch is one of the largest batches of CO2RR catalysts synthesized in the literature while requiring minimal synthesis steps. The catalyst possessed single-atomic iron-nitrogen (Fe-N) sites, enabling a high performance of >95% CO product selectivity at a high current density of 400 mA/cm2 and high stability for 45 h at 100 mA/cm2 in a flow cell testing. The catalyst outperformed a benchmark noble-metal nanoparticle catalyst and achieved longer stability than many other reported M-N-C catalysts in the literature. The scalable and cost-effective synthesis developed in this work paves a pathway toward practical CO2RR applications. The direct utilization of metal impurities from raw CNTs for efficient catalyst synthesis with minimal treatment is a green and sustainable engineering approach.

Cascade degradation and upcycling of polystyrene waste to high-value chemicals.

Plastic waste represents one of the most urgent environmental challenges facing humankind. Upcycling has been proposed to solve the low profitability and high market sensitivity of known recycling methods. Existing upcycling methods operate under energy-intense conditions and use precious-metal catalysts, but produce low-value oligomers, monomers, and common aromatics. Herein, we report a tandem degradation-upcycling strategy to exploit high-value chemicals from polystyrene (PS) waste with high selectivity. We first degrade PS waste to aromatics using ultraviolet (UV) light and then valorize the intermediate to diphenylmethane. Low-cost AlCl3 catalyzes both the reactions of degradation and upcycling at ambient temperatures under atmospheric pressure. The degraded intermediates can advantageously serve as solvents for processing the solid plastic wastes, forming a self-sustainable circuitry. The low-value-input and high-value-output approach is thus substantially more sustainable and economically viable than conventional thermal processes, which operate at high-temperature, high-pressure conditions and use precious-metal catalysts, but produce low-value oligomers, monomers, and common aromatics. The cascade strategy is resilient to impurities from plastic waste streams and is generalizable to other high-value chemicals (e.g., benzophenone, 1,2-diphenylethane, and 4-phenyl-4-oxo butyric acid). The upcycling to diphenylmethane was tested at 1-kg laboratory scale and attested by industrial-scale techno-economic analysis, demonstrating sustainability and economic viability without government subsidies or tax credits.

Approaches to Enhancing Electrical Conductivity of Pristine Metal-Organic Frameworks for Supercapacitor Applications.

Metal-organic frameworks (MOFs), known as porous coordination polymers, have attracted intense interest as electrode materials for supercapacitors (SCs) owing to their advantageous features including high surface area, tunable porous structure, structural diversity, etc. However, the insulating nature of most MOFs has impeded their further electrochemical applications. A common solution for this issue is to transform pristine MOFs into more stable and conductive metal compounds/porous carbon materials through pyrolysis, which however losses the inherent merits of MOFs. To find a consummate solution, recently a surge of research devoted to improving the electrical conductivity of pristine MOFs for SCs has been carried out. In this review, the most related research work on pristine MOF-based materials is reviewed and three effective strategies (chemical structure design of conductive MOFs (c-MOFs), composite design, and binder-free structure design) which can significantly increase their conductivity and consequently the electrochemical performance in SCs are proposed. The conductivity enhancement mechanism in each approach is well analyzed. The representative research works on using pristine MOFs for SCs are also critically discussed. It is hoped that the new insights can provide guidance for developing high-performance electrode materials based on pristine MOFs with high conductivity for SCs in the future.

Atomically Dispersed Iron-Nitrogen Sites on Hierarchically Mesoporous Carbon Nanotube and Graphene Nanoribbon Networks for CO2 Reduction.

Atomically dispersed metal and nitrogen co-doped carbon (M-N/C) catalysts hold great promise for electrochemical CO2 conversion. However, there is a lack of cost-effective synthesis approaches to meet the goal of economic mass production of single-atom M-N/C with desirable carbon support architecture for efficient CO2 reduction. Herein, we report facile transformation of commercial carbon nanotube (CNT) into isolated Fe-N4 sites anchored on carbon nanotube and graphene nanoribbon (GNR) networks (Fe-N/CNT@GNR). The oxidization-induced partial unzipping of CNT results in the generation of GNR nanolayers attached to the remaining fibrous CNT frameworks, which reticulates a hierarchically mesoporous complex and thus enables a high electrochemical active surface area and smooth mass transport. The Fe residues originating from CNT growth seeds serve as Fe sources to form isolated Fe-N4 moieties located at the CNT and GNR basal plane and edges with high intrinsic capability of activating CO2 and suppressing hydrogen evolution. The Fe-N/CNT@GNR delivers a stable CO Faradaic efficiency of 96% with a partial current density of 22.6 mA cm-2 at a low overpotential of 650 mV, making it one of the most active M-N/C catalysts reported. This work presents an effective strategy to fabricate advanced atomistic catalysts and highlights the key roles of support architecture in single-atom electrocatalysis.

An integrated electrocoagulation - Electrocatalysis water treatment process using stainless steel cathodes coated with ultrathin TiO2 nanofilms.

Anodic electrocoagulation processes can remove broad varieties of pollutants in industrial wastewater. However, some stubborn contaminants may still remain in effluents after the treatment and cause environmental issues. To further improve the efficiency of pollutant removal, we have coupled electrocatalysis with electrocoagulation and applied an atomic layer deposition (ALD) enabled TiO2 ultrathin overcoating at a nanometer scale on a stainless steel cathode. The electrocatalytic overcoating increased the elimination efficiency of organics and microorganisms, likely due to the electro-generation of adequate reactive oxygen species (ROS). The thickness of TiO2 nanofilm was controlled by the number of ALD cycles, and it was found that nanofilms processed with 50-100 cycles led to the maximum benefit of pollutant removal. By using the novel electrocoagulation-electrocatalysis cell to treat synthetic wastewater, a remarkable removal of 99.92% of E. Coli, 92.1% of suspended solids, 98.3% of heavy metal ions, and 88.8% of methylene blue was observed. This hybrid electrochemical treatment process may have the potential to treat wastewater at a larger scale.

Visible-Light-Driven Photocatalytic Degradation of Organic Water Pollutants Promoted by Sulfite Addition.

Solar-driven heterogeneous photocatalysis has been widely studied as a promising technique for degradation of organic pollutants in wastewater. Herein, we have developed a sulfite-enhanced visible-light-driven photodegradation process using BiOBr/methyl orange (MO) as the model photocatalyst/pollutant system. We found that the degradation rate of MO was greatly enhanced by sulfite, and the enhancement increased with the concentration of sulfite. The degradation rate constant was improved by 29 times in the presence of 20 mM sulfite. Studies using hole scavengers suggest that sulfite radicals generated by the reactions of sulfite (sulfite anions or bisulfite anions) with holes or hydroxyl radicals are the active species for MO photodegradation using BiOBr under visible light. In addition to the BiOBr/MO system, the sulfite-assisted photocatalysis approach has been successfully demonstrated in BiOBr/rhodamine B (RhB), BiOBr/phenol, BiOI/MO, and Bi2O3/MO systems under visible light irradiation, as well as in TiO2/MO system under simulated sunlight irradiation. The developed method implies the potential of introducing external active species to improve photodegradation of organic pollutants and the beneficial use of air pollutants for the removal of water pollutants since sulfite is a waste from flue gas desulfurization process.

Direct synthesis of nitrogen-doped carbon nanosheets with high surface area and excellent oxygen reduction performance.

Graphene-like nitrogen-doped carbon nanosheets (NCN) have become a fascinating carbon-based material for advanced energy storage and conversion devices, but its easy, cheap, and environmentally friendly synthesis is still a grand challenge. Herein we directly synthesized porous NCN material via the facile pyrolysis of chitosan and urea without the requirement of any catalyst or post-treatment. As-prepared material exhibits a very large BET surface area of ~1510 m(2) g(-1) and a high ratio of graphitic/pyridinic nitrogen structure (2.69 at. % graphitic N and 1.20 at. % pyridinic N). Moreover, compared to a commercial Pt/C catalyst, NCN displays excellent electrocatalytic activity, better long-term stability, and methanol tolerance ability toward the oxygen reduction reaction, indicating a promising metal-free alternative to Pt-based cathode catalysts in alkaline fuel cells. This scalable fabrication method supplies a low-cost, high-efficiency metal-free oxygen reduction electrocatalyst and also suggests an economic and sustainable route from biomass-based molecules to value-added nanocarbon materials.

Efficient oxygen reduction electrocatalyst based on edge-nitrogen-rich graphene nanoplatelets: toward a large-scale synthesis.

The large-scale synthesis of nitrogen doped graphene (N-graphene) with high oxygen reduction reaction (ORR) performance has received a lot of attention recently. In this work, we have developed a facile and economical procedure for mass production of edge-nitrogen-rich graphene nanoplatelets (ENR-GNPs) by a combined process of ball milling of graphite powder (GP) in the presence of melamine and subsequent heat treatment. It is found that the ball milling process can not only crack and exfoliate pristine GP into edge-expanded nanoplatelets but also mechanically activate GP to generate appropriate locations for N-doping. Analysis results indicate that the doped N atoms mainly locate on the edge of the graphitic matrix, which contains ca. 3.1 at.% nitrogen content and can be well-dispersed in aqueous to form multilayer nanoplatelets. The as-prepared ENR-GNPs electrocatalyst exhibits highly electrocatalytic activity for ORR due to the synergetic effects of edge-N-doping and nanosized platelets. Besides, the stability and methanol tolerance of ENR-GNPs are superior to that of the commercial Pt/C catalyst, which makes the nanoplatelets a promising candidate for fuel cell cathode catalysts. The present approach opens up the possibility for simple and mass production of N-graphene based electrocatalysts in practice.

Catalyst-free synthesis of crumpled boron and nitrogen co-doped graphite layers with tunable bond structure for oxygen reduction reaction.

Two-dimensional materials based on ternary system of B, C and N are useful ranging from electric devices to catalysis. The bonding arrangement within these BCN nanosheets largely determines their electronic structure and thus chemical and (or) physical properties, yet it remains a challenge to manipulate their bond structures in a convenient and controlled manner. Recently, we developed a synthetic protocol for the synthesis of crumpled BCN nanosheets with tunable B and N bond structure using urea, boric acid and polyethylene glycol (PEG) as precursors. By carefully selecting the synthesis condition, we can tune the structure of BCN sheets from s-BCN with B and N bond together to h-BCN with B and N homogenously dispersed in BCN sheets. Detailed experiments suggest that the final bond structure of B and N in graphene depends on the preferentially doped N structure in BCN nanosheets. When N substituted the in-plane carbon atom with all its electrons configured into the π electron system of graphene, it facilitates the formation of h-BCN with B and N in separated state. On the contrary, when nitrogen substituted the edge-plane carbon with the nitrogen dopant surrounded with the lone electron pairs, it benefits for the formation of B-N structure. Specially, the compound riched with h-BCN shows excellent ORR performance in alkaline solution due to the synergistic effect between B and N, while s-BCN dominant BCN shows graphite-like activity for ORR, suggesting the intrinsic properties differences of BCN nanosheets with different dopants bond arrangement.

Advanced oxygen reduction electrocatalyst based on nitrogen-doped graphene derived from edible sugar and urea.

Designing and fabricating advanced oxygen reduction reaction (ORR) electrocatalysts is critical importance for the sake of promoting widespread application of fuel cells. In this work, we report that nitrogen-doped graphene (NG), synthesized via one-step pyrolysis of naturally available sugar in the presence of urea, can serve as metal-free ORR catalyst with excellent electrocatalytic activity, outstanding methanol crossover resistance as well as long-term operation stability in alkaline medium. The resultant NG1000 (annealed at 1000 °C) exhibits a high kinetic current density of 21.33 mA/cm(2) at -0.25 V (vs Ag/AgCl) in O2-saturated 0.1 M KOH electrolyte, compared with 16.01 mA/cm(2) at -0.25 V for commercial 20 wt % Pt/C catalyst. Notably, the NG1000 possesses comparable ORR half-wave potential to Pt/C. The effects of pyrolysis temperature on the physical prosperity and ORR performance of NG are also investigated. The obtained results demonstrate that high activation temperature (1000 °C) results in low nitrogen doping level, high graphitization degree, enhanced electrical conductivity, and high surface area and pore volume, which make a synergetic contribution to enhancing the ORR performance for NG.