One-Pot Direct Mechanochemical Silicon Replacement of Sodium Fluorosilicate into Sodium Fluorozirconate and Functionalization of Graphite for Enhanced Sodium-Ion Storage.

Efficient sodium ion storage in graphite is as yet unattainable, because of the thermodynamic instability of sodium ion intercalates-graphite compounds. In this work, sodium fluorozirconate (Na3ZrF7, SFZ) functionalized graphite (SFZ-G) is designed and prepared by the in situ mechanochemical silicon (Si) replacement of sodium fluorosilicate (Na2SiF6, SFS) and functionalization of graphite at the same time. During the mechanochemical process, the atomic Si in SFS is directly replaced by atomic zirconium (Zr) from the zirconium oxide (ZrO2) balls and container in the presence of graphite, forming SFZ-G. The resulting SFZ-G, working as an anode material for sodium ion storage, shows a significantly enhanced capacity of 418.7 mAh g-1 at 0.1 C-rate, compared to pristine graphite (35 mAh g-1) and simply ball-milled graphite (BM-G, 200 mAh g-1). In addition, the SFZ-G exhibits stable sodium-ion storage performance with 86% of its initial capacity retention after 1000 cycles at 2.0 C-rate.

Direct Electroplating Ruthenium Precursor on the Surface Oxidized Nickel Foam for Efficient and Stable Bifunctional Alkaline Water Electrolysis.

Water electrolysis to produce hydrogen (H2) using renewable energy is one of the most promising candidates for realizing carbon neutrality, but its reaction kinetics is hindered by sluggish anodic oxygen evolution reaction (OER). Ruthenium (Ru) in its high-valence state (oxide) provides one of the most active OER sites and is less costly, but thermodynamically unstable. The strong interaction between Ru nanoparticles (NPs) and nickel hydroxide (Ni(OH)2) is leveraged to directly form Ru-Ni(OH)2 on the surface of a porous nickel foam (NF) electrode via spontaneous galvanic replacement reaction. The formation of Ru─O─Ni bonds at the interface of the Ru NPs and Ni(OH)2 (Ru-Ni(OH)2) on the surface oxidized NF significantly enhance stability of the Ru-Ni(OH)2/NF electrode. In addition to OER, the catalyst is active enough for the hydrogen evolution reaction (HER). As a result, it is able to deliver overpotentials of 228 and 15 mV to reach 10 mA cm-2 for OER and HER, respectively. An industry-scale evaluation using Ru-Ni(OH)2/NF as both OER and HER electrodes demonstrates a high current density of 1500 mA cm-2 (OER: 410 mV; HER: 240 mV), surpassing commercial RuO2 (OER: 600 mV) and Pt/C based performance (HER: 265 mV).

Scalable Design of Ru-Embedded Carbon Fabric Using Conventional Carbon Fiber Processing for Robust Electrocatalysts.

Metal-carbon composites are extensively utilized as electrochemical catalysts but face critical challenges in mass production and stability. We report a scalable manufacturing process for ruthenium surface-embedded fabric electrocatalysts (Ru-SFECs) via conventional fiber/fabric manufacturing. Ru-SFECs have excellent catalytic activity and stability toward the hydrogen evolution reaction, exhibiting a low overpotential of 11.9 mV at a current density of 10 mA cm-2 in an alkaline solution (1.0 M aq KOH solution) with only a slight overpotential increment (6.5%) after 10,000 cycles, whereas under identical conditions, that of commercial Pt/C increases 6-fold (from 1.3 to 7.8 mV). Using semipilot-scale equipment, a protocol is optimized for fabricating continuous self-supported electrocatalytic electrodes. Tailoring the fiber processing parameters (tension and temperature) can optimize the structural development, thereby achieving good catalytic performance and mechanical integrity. These findings underscore the significance of self-supporting catalysts, offering a general framework for stable, binder-free electrocatalytic electrode design.

Out-of-Plane Single-Copper-Site Catalysts for Room-Temperature Benzene Oxidation.

Crafting single-atom catalysts (SACs) that possess "just right" modulated electronic and geometric structures, granting accessible active sites for direct room-temperature benzene oxidation is a coveted objective. However, achieving this goal remains a formidable challenge. Here, we introduce an innovative in situ phosphorus-immitting strategy using a new phosphorus source (phosphorus nitride, P3N5) to construct the phosphorus-rich copper (Cu) SACs, designated as Cu/NPC. These catalysts feature locally protruding metal sites on a nitrogen (N)-phosphorus (P)-carbon (C) support (NPC). Rigorous analyses, including X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS), validate the coordinated bonding of nitrogen and phosphorus with atomically dispersed Cu sites on NPC. Crucially, systematic first-principles calculations, coupled with the climbing image nudged-elastic-band (CI-NEB) method, provide a comprehensive understanding of the structure-property-activity relationship of the distorted Cu-N2P2 centers in Cu/NPC for selective oxidation of benzene to phenol production. Interestingly, Cu/NPC has shown more energetically favorable C-H bond activation compared to the benchmark Cu/NC SACs in the direct oxidation of benzene, resulting in outstanding benzene conversion (50.3 %) and phenol selectivity (99.3 %) at room temperature. Furthermore, Cu/NPC achieves a remarkable turnover frequency of 263 h-1 and mass-specific activity of 35.2 mmol g-1 h-1, surpassing the state-of-the-art benzene-to-phenol conversion catalysts to date.

Simple Functionalization of a Donor Monomer to Enhance Charge Transfer in Porous Polymer Networks for Photocatalytic Hydrogen Evolution.

Porous polymer networks (PPNs) are promising candidates as photocatalysts for hydrogen production. Constructing a donor-acceptor structure is known to be an effective approach for improving photocatalytic activity. However, the process of how a functional group of a monomer can ensure photoexcited charges transfer and improve the hydrogen evolution rate (HER) has not yet been studied on the molecular level. Herein, we design and synthesize two kinds of triazatruxene (TAT)-based PPNs: TATR-PPN with a hexyl (R) group and TAT-PPN without the hexyl group, to understand the relationship between the presence of the functional group and charge transfer. The hexyl group on the TAT unit was found to ensure the transfer of photoexcited electrons from a donor unit to an acceptor unit and endowed the TATR-PPN with stable hydrogen production.

Triboelectric Energy Harvesting from Highly Conjugated Fused Aromatic Ladder Structure Under Extreme Environmental Conditions.

Practical application of triboelectric nanogenerators (TENGs) has been challenging, particularly, under harsh environmental conditions. This work proposes a novel 3D-fused aromatic ladder (FAL) structure as a tribo-positive material for TENGs, to address these challenges. The 3D-FAL offers a unique materials engineering platform for tailored properties, such as high specific surface area and porosity, good thermal and mechanical stability, and tunable electronic properties. The fabricated 3D-FAL-based TENG reaches a maximum peak power density of 451.2 µW cm-2 at 5 Hz frequency. More importantly, the 3D-FAL-based TENG maintains stable output performance under harsh operating environments, over wide temperature (-45-100 °C) and humidity ranges (8.3-96.7% RH), representing the development of novel FAL for sustainable energy generation under challenging environmental conditions. Furthermore, the 3D-FAL-based TENG proves to be a promising device for a speed monitoring system engaging reconstruction in virtual reality in a snowy environment.

Recent Advances in Iridium-based Electrocatalysts for Acidic Electrolyte Oxidation.

Ongoing research to develop advanced electrocatalysts for the oxygen evolution reaction (OER) is needed to address demand for efficient energy conversion and carbon-free energy sources. In the OER process, acidic electrolytes have higher proton concentration and faster response than alkaline ones, but their harsh strongly acidic environment requires catalysts with greater corrosion and oxidation resistance. At present, iridium oxide (IrO2) with its strong stability and excellent catalytic performance is the catalyst of choice for the anode side of commercial PEM electrolysis cells. However, the scarcity and high cost of iridium (Ir) and the unsatisfactory activity of IrO2 hinder industrial scale application and the sustainable development of acidic OER catalytic technology. This highlights the importance of further research on acidic Ir-based OER catalysts. In this review, recent advances in Ir-based acidic OER electrocatalysts are summarized, including fundamental understanding of the acidic OER mechanism, recent insights into the stability of acidic OER catalysts, highly efficient Ir-based electrocatalysts, and common strategies for optimizing Ir-based catalysts. The future challenges and prospects of developing highly effective Ir-based catalysts are also discussed.

CO2 Enrichment Boosts Highly Selective Infrared-Light-Driven CO2 Conversion to CH4 by UiO-66/Co9S8 Photocatalyst.

Photocatalytic CO2 reduction to high-value chemicals is an attractive approach to mitigate climate change, but it remains a great challenge to produce a specific product selectively by IR light. Hence, UiO-66/Co9S8 composite is designed to couple the advantages of metallic photocatalysts and porous CO2 adsorbers for IR-light-driven CO2-to-CH4 conversion. The metallic nature of Co9S8 endows UiO-66/Co9S8 with exceptional IR light absorption, while UiO-66 dramatically enhances its local CO2 concentration, revealed by finite-element method simulations. As a result, Co9S8 or UiO-66 alone does not show observable IR-light photocatalytic activity, whereas UiO-66/Co9S8 exhibits exceptional activity. The CH4 evolution rate over UiO-66/Co9S8 reaches 25.7 µmol g-1 h-1 with ca.100% selectivity under IR light irradiation, outperforming most reported catalysts under similar reaction conditions. The X-ray absorption fine structure spectroscopy spectra verify the presence of two distinct Co sites and confirm the existence of metallic Co─Co bond in Co9S8. Energy diagrams analysis and transient absorption spectra manifest that CO2 reduction mainly occurs on Co9S8 for UiO-66/Co9S8, while density functional theory calculations demonstrate that high-electron-density Co1 sites are the key active sites, possessing lower energy barriers for further protonation of *CO, leading to the ultra-high selectivity toward CH4.

Rhodium and Carbon Sites with Strong d-p Orbital Interaction for Efficient Bifunctional Catalysis.

Efficient and stable catalysts are highly desired for the electrochemical conversion of hydrogen, oxygen, and water molecules, processes which are crucial for renewable energy conversion and storage technologies. Herein, we report the development of hollow nitrogenated carbon sphere (HNC) dispersed rhodium (Rh) single atoms (Rh1HNC) as an efficient catalyst for bifunctional catalysis. The Rh1HNC was achieved by anchoring Rh single atoms in the HNC matrix with an Rh-N3C1 configuration, via a combination of in situ polymerization and carbonization approach. Benefiting from the strong metal atom-support interaction (SMASI), the Rh and C atoms can collaborate to achieve robust electrochemical performance toward both the hydrogen evolution and oxygen reduction reactions in acidic media. This work not only provides an active site with favorable SMASI for bifunctional catalysis but also brings a strategy for the design and synthesis of efficient and stable bifunctional catalysts for diverse applications.

Hexaazatriphenylene-Based Two-Dimensional Conductive Covalent Organic Framework with Anisotropic Charge Transfer.

The development of covalent organic frameworks (COFs) with efficient charge transport is of immense interest for applications in optoelectronic devices. To enhance COF charge transport properties, electroactive building blocks and dopants can be used to induce extended conduction channels. However, understanding their intricate interplay remains challenging. We designed and synthesized a tailor-made COF structure with electroactive hexaazatriphenylene (HAT) core units and planar dioxin (D) linkages, denoted as HD-COF. With the support of theoretical calculations, we found that the HAT units in the HD-COF induce strong, eclipsed π-π stacking. The unique stacking of HAT units and the weak in-plane conjugation of dioxin linkages leads to efficient anisotropic charge transport. We fabricated HD-COF films to minimize the grain boundary effect of bulk COFs, which resulted in enhanced conductivity. As a result, the HD-COF films showed an electrical conductivity as high as 1.25 S cm-1 after doping with tris(4-bromophenyl)ammoniumyl hexachloroantimonate.

Cobalt-Porphyrin-Based Covalent Organic Frameworks with Donor-Acceptor Units as Photocatalysts for Carbon Dioxide Reduction.

Covalent organic frameworks (COFs) have emerged as a promising platform for photocatalysts. Their crystalline porous nature allows comprehensive mechanistic studies of photocatalysis, which have revealed that their general photophysical parameters, such as light absorption ability, electronic band structure, and charge separation efficiency, can be conveniently tailored by structural modifications. However, further understanding of the relationship between structure-property-activity is required from the viewpoint of charge-carrier transport, because the charge-carrier property is closely related to alleviation of the excitonic effect. In the present study, COFs composed of a fixed cobalt (Co) porphyrin (Por) centered tetraamine as an acceptor unit with differently conjugated di-carbaldehyde based donor units, such as benzodithiophene (BDT), thienothiophene (TT), or phenyl (TA), were synthesized to form Co-Por-BDT, Co-Por-TT, or Co-Por-TA, respectively. Their photocatalytic activity for reducing carbon dioxide into carbon monoxide was in the order of Co-Por-BDT>Co-Por-TT>Co-Por-TA. The results indicated that the excitonic effect, associated with their charge-carrier densities and π-conjugation lengths, was a significant factor in photocatalysis performance.

Olefin-Linked Covalent Organic Frameworks with Electronegative Channels as Cationic Highways for Sustainable Lithium Metal Battery Anodes.

Despite the enormous interest in Li metal as an ideal anode material, the uncontrollable Li dendrite growth and unstable solid electrolyte interphase have plagued its practical application. These limitations can be attributed to the sluggish and uneven Li+ migration towards Li metal surface. Here, we report olefin-linked covalent organic frameworks (COFs) with electronegative channels for facilitating selective Li+ transport. The triazine rings and fluorinated groups of the COFs are introduced as electron-rich sites capable of enhancing salt dissociation and guiding uniform Li+ flux within the channels, resulting in a high Li+ transference number (0.85) and high ionic conductivity (1.78 mS cm-1 ). The COFs are mixed with a polymeric binder to form mixed matrix membranes. These membranes enable reliable Li plating/stripping cyclability over 700 h in Li/Li symmetric cells and stable capacity retention in Li/LiFePO4 cells, demonstrating its potential as a viable cationic highway for accelerating Li+ conduction.

Mechanochemical Ammonia Synthesis: Old is New Again.

Hydrogen is a promising clean energy source, an alternative to fossil fuels, and can potentially play a crucial role in reducing carbon emissions. The transportation and storage of hydrogen are the biggest hurdles to realizing a hydrogen economy. Ammonia is considered to be one of the most promising hydrogen carriers, because of its high hydrogen content and easy liquefaction in mild conditions. To date, ammonia is mostly produced by the 'thermocatalytic' Haber-Bosch process, which requires high temperature and pressure. As a result, it can only produce ammonia in 'centralized' manufacturing systems. Mechanochemistry, a newly emerging method for efficient ammonia synthesis, offers potential advantages over the Haber-Bosch process. Mechanochemical ammonia synthesis under near ambient conditions can be connected with 'localized' sustainable energy systems. In this perspective, the state-of-the-art mechanochemical ammonia synthesis processes will be introduced. Challenges and opportunities are also discussed in relation to its role in a hydrogen economy.

Achieving volatile potassium promoted ammonia synthesis via mechanochemistry.

Potassium oxide (K2O) is used as a promotor in industrial ammonia synthesis, although metallic potassium (K) is better in theory. The reason K2O is used is because metallic K, which volatilizes around 400 °C, separates from the catalyst in the harsh ammonia synthesis conditions of the Haber-Bosch process. To maximize the efficiency of ammonia synthesis, using metallic K with low temperature reaction below 400 °C is prerequisite. Here, we synthesize ammonia using metallic K and Fe as a catalyst via mechanochemical process near ambient conditions (45 °C, 1 bar). The final ammonia concentration reaches as high as 94.5 vol%, which was extraordinarily higher than that of the Haber-Bosch process (25.0 vol%, 450 °C, 200 bar) and our previous work (82.5 vol%, 45 °C, 1 bar).

Self-Accommodation Induced Electronic Metal-Support Interaction on Ruthenium Site for Alkaline Hydrogen Evolution Reaction.

Tuning the metal-support interaction of supported metal catalysts has been found to be the most effective approach to modulating electronic structure and improving catalytic performance. But practical understanding of the charge transfer mechanism at the electronic level of catalysis process has remained elusive. Here, it is reported that ruthenium (Ru) nanoparticles can self-accommodate into Fe3 O4 and carbon support (Ru-Fe3 O4 /C) through the electronic metal-support interaction, resulting in robust catalytic activity toward the alkaline hydrogen evolution reaction (HER). Spectroscopic evidence and theoretical calculations demonstrate that electronic perturbation occurred in the Ru-Fe3 O4 /C, and that charge redistribution directly influenced adsorption behavior during the catalytic process. The RuO bond formed by orbital mixing changes the charge state of the surface Ru site, enabling more electrons to flow to H intermediates (H* ) for favorable adsorption. The weak binding strength of the RuO bond also reinforces the anti-bonding character of H* with a more favorable recombination of H* species into H2 molecules. Because of this satisfactory catalytic mechanism, the Ru-Fe3 O4 /C supported nanoparticle catalyst demonstrated better HER activity and robust stability than the benchmark commercial Pt/C benchmark in alkaline media.

Tuning the Coordination Environment of Carbon-Based Single-Atom Catalysts via Doping with Multiple Heteroatoms and Their Applications in Electrocatalysis.

Carbon-based single-atom catalysts (SACs) are considered to be a perfect platform for studying the structure-activity relationship of different reactions due to the adjustability of their coordination environment. Multi-heteroatom doping has been demonstrated as an effective strategy for tuning the coordination environment of carbon-based SACs and enhancing catalytic performance in electrochemical reactions. Herein, recently developed strategies for multi-heteroatom doping, focusing on the regulation of single-atom active sites by heteroatoms in different coordination shells, are summarized. In addition, the correlation between the coordination environment and the catalytic activity of carbon-based SACs are investigated through representative experiments and theoretical calculations for various electrochemical reactions. Finally, concerning certain shortcomings of the current strategies of doping multi-heteroatoms, some suggestions are put forward to promote the development of carbon-based SACs in the field of electrocatalysis.

Merging Platinum Single Atoms to Achieve Ultrahigh Mass Activity and Low Hydrogen Production Cost.

Single atom catalysts (SACs) with isolated active sites exhibit the highest reported mass activity for hydrogen evolution catalysis, which is crucial for practical applications. Here, we demonstrate that ultrahigh mass activity can also be achieved by rationally merging the isolated platinum (Pt) active sites in SAC. The catalyst was obtained by the thermodynamically driven diffusing and merging phosphorus-doped carbon (PC) supported Pt single atoms (Pt1@PC) into Pt nanoclusters (PtM@PC). X-ray absorption spectroscopy analysis revealed that the merged nanoclusters exhibit much stronger interactions with the support than the traditional method, enabling more efficient electron transfer. The optimized PtM@PC exhibited an order of magnitude higher mass activity (12.7 A mgPt-1) than Pt1@PC (0.9 A mgPt-1) at an overpotential of 10 mV in acidic media, which is the highest record to date, far exceeding reports for other outstanding SACs. Theoretical study revealed that the collective active sites in PtM@PC exhibit both favorable hydrogen binding energy and fast reaction kinetics, leading to the significantly enhanced mass activity. Despite its low Pt content (2.2 wt %), a low hydrogen production cost of ∼3 USD kg-1 was finally achieved in the full-water splitting at a laboratory scale.

Benzotrithiophene-based Covalent Organic Framework Photocatalysts with Controlled Conjugation of Building Blocks for Charge Stabilization.

Covalent organic frameworks have recently shown high potential for photocatalytic hydrogen production. However, their structure-property-activity relationship has not been sufficiently explored to identify a research direction for structural design. Herein, we report the design and synthesis of four benzotrithiophene (BTT)-based covalent organic frameworks (COFs) with different conjugations of building units, and their photocatalytic activity for hydrogen production. All four BTT-COFs had slipped parallel stacking patterns with high crystallinity and specific surface areas. The change in the degree of conjugation was found to rationally tune the rate of photocatalytic hydrogen evolution. Based on the experimental and calculation results, the tunable photocatalytic performance could be mainly attributed to the electron affinity and charge trapping of the electron accepting units. This study provides important insights for designing covalent organic frameworks for efficient photocatalysts.

Conductive and Ultrastable Covalent Organic Framework/Carbon Hybrid as an Ideal Electrocatalytic Platform.

Developing covalent organic frameworks (COFs) with good electrical conductivity is essential to widen their range of practical applications. Thermal annealing is known to be a facile approach for enhancing conductivity. However, at higher temperatures, most COFs undergo amorphization and/or thermal degradation because of the lack of linker rigidity and physicochemical stability. Here, we report the synthesis of a conductive benzoxazole-linked COF/carbon hybrid material (BCOF-600C) by simple thermal annealing. The fused-aromatic benzoxazole and biphenyl building units endow the resulting COF with excellent physicochemical stability against high temperatures and strong acids/bases. This allows heat treatment to further enhance electrical conductivity with minimal structural alteration. The robust crystalline structure with periodically incorporated nitrogen atoms allowed platinum (Pt) atoms to be atomically integrated into the channel walls of BCOF-600C. The resulting electrocatalyst with well-defined active sites exhibited superior catalytic performance toward hydrogen evolution in acidic media.

Tin Nanoclusters Confined in Nitrogenated Carbon for the Oxygen Reduction Reaction.

The oxygen reduction reaction is essential for fuel cells and metal-air batteries in renewable energy technologies. Developing platinum-group-metal (PGM)-free catalysts with comparable catalytic performance is highly desired for cost efficiency. Here, we report a tin (Sn) nanocluster confined catalyst for the electrochemical oxygen reduction. The catalyst was fabricated by confining 1-1.5 nm sized Sn nanoclusters in situ in microporous nitrogen-doped carbon polyhedra (SnxNC) with an average pore size of 0.7 nm. SnxNC exhibited high catalytic performance in acidic media, including positive onset and half-wave potentials, comparable to those of the state-of-the-art Pt/C and far exceeding those of the Sn single-atom catalyst. Combined structural and theoretical analyses reveal that the confined Sn nanoclusters, which have favorable oxygen adsorption behaviors, are responsible for the high catalytic performance, but not Sn single atoms.