Atomic Molybdenum Nanomaterials for Electrocatalysis.

As a sustainable energy technology, electrocatalytic energy conversion requires electrocatalysts, which greatly motivates the exploitation of high-performance electrocatalysts based on nonprecious metals. Molybdenum-based nanomaterials have demonstrated promise as electrocatalysts because of their unique physiochemical and electronic properties. Among them, atomic Mo catalysts, also called Mo-based single-atom catalysts (Mo-SACs), have the most accessible active sites and tunable microenvironments and are thrivingly explored in various electrochemical conversion reactions. A timely review of such rapidly developing topics is necessary to provide guidance for further exploration of optimized Mo-SACs toward electrochemical energy technologies. In this review, recent advances in the synthetic strategies for Mo-SACs are highlighted, focusing on the microenvironment engineering of Mo atoms. Then, the representative achievements of their applications in various electrocatalytic reactions involving the N2, H2O, and CO2 cycles are summarized by combining experimental and computational results. Finally, prospects for the future development of Mo-SACs in electrocatalysis are provided and the key challenges that require further investigation and optimization are highlighted.

Curved Structure Regulated Single Metal Sites for Advanced Electrocatalytic Reactions.

Curved surface with defined local electronic structures and regulated surface microenvironments is significant for advanced catalytic engineering. Since single-atom catalysts are highly efficient and active, they have attracted much attention in recent years. The curvature carrier has a significant effect on the electronic structure regulation of single-atom sites, which effectively promote the catalytic efficiency. Here, the effect of the curvature structure with exposed metal atoms for catalysis is comprehensively summarized. First, the substrates with curvature features are reviewed. Second, the applications of single-atom catalysts containing curvature in a variety of different electrocatalytic reactions are discussed in depth. The impact of curvature effects in catalytic reactions is further analyzed. Finally, prospects and suggestions for their application and future development are presented. This review paves the way for the construction of high curvature-containing surface carriers, which is of great significance for single-atom catalysts development.

Tetra-Coordinated W2 S3 for Efficient Dual-pH Hydrogen Production.

Two-dimensional (2D) transition-metal dichalcogenides (TMDs) have emerged as promising catalysts for the hydrogen evolution reaction (HER) that play a crucial role in renewable energy technologies. Breaking the inherent structural paradigm limitations of 2D TMDs is the key to exploring their fascinating physical and chemical properties, which is expected to develop a revolutionary HER catalyst. Herein, we unambiguously present metallic W2 S3 instead of energetically favorable WS2 via a unique stoichiometric growth strategy. Benefiting from the excellent conductivity and hydrophilicity of the tetra-coordinated structure, as well as an appropriate Gibbs free energy value and an enough low energy barrier for water dissociation, the W2 S3 as catalyst achieves Pt-like HER activity and high long-term stability in both acidic and alkaline electrolytes. For application in proton exchange membrane (PEM) and anion exchange membrane (AEM) electrolysers, W2 S3 as the cathode catalyst yields excellent bifunctionality index (ɳ @ 1 A cm - 2 , PEM ${_{{\rm{@1 {\rm A} cm}}^{{\rm{ - }}{\rm{2}}} {\rm{, PEM}}} }$ =1.73 V, ɳ @ 1 A cm - 2 , AEM ${_{{\rm{@1 {\rm A} cm}}^{{\rm{ - }}{\rm{2}}} {\rm{, AEM}}} }$ =1.77 V) and long-term stability (471 h@PEM with a decay rate of 85.7 µV h-1 , 360 h@AEM with a decay rate of 27.1 µV h-1 ). Our work provides significant insight into the tetra-coordinated W2 S3 and facilitates the development of advanced electrocatalysts for sustainable hydrogen production.

Tuning Electron Density Endows Fe1-xCoxP with Exceptional Capability of Electrooxidation of Organic Pollutants.

The good performance of base metal catalysts for the electrooxidation of organic pollutants has attracted great attention. However, base metal phosphides for electrooxidation are seldom studied owing to the sluggish water adsorption and dissociation dynamics, which will hinder the production of the sorbed hydroxyl radicals (M(•OH)) and thus inhibit the electrooxidation of organic pollutants. Herein, we proposed a universal strategy to improve the electrooxidation capability of metal phosphides by modulating the surface electron densities. The electron interactions between cobalt (Co) and phosphorus (P) are modulated after iron doping, resulting in more positively charged Co and more negatively charged P, which can promote the adsorption and activation of water molecules and produce large quantities of M(•OH). Meanwhile, the experimental results show that the iron-modulated Fe0.53Co0.47P nanosheet arrays exhibit higher removal efficiency of tetracycline than the boron-doped diamond and Pt anode at low current intensity. Based on experimental results and density functional theory + U calculations (DFT + U), it is found that Fe0.53Co0.47P has lower barrier (0.45 eV) to form the sorbed hydroxyl radicals (M(•OH)) and higher overpotential to produce O2 than its counterparts, suggesting that Fe0.53Co0.47P can produce more M(•OH) instead of O2. The above results highlighted the feasibility of these base metal phosphides for electrooxidation for advanced water purification.

Exceptional Catalytic Activities of Iron Tungstophosphoric Acid Pillared Montmorillonite Photo-Fenton Catalyst for Organic Pollutant Decomposition.

Iron tungstophosphoric acid pillared montmorillonite (TPAFe-Mt) as a highly efficient, stable and visible-light-responsive photo-Fenton catalyst have successfully been prepared via an impregnation method. The TPAFe-Mt catalyst exhibits exceptional visible-light photo-Fenton catalytic activities for azo-dye methyl orange, phenol and 2,4-dinitrophenol in a wide pH range from 1.0 to 5.0. Especially, 40 mg/L of methyl orange could be completely degraded in 40 min, and the TOC removal rate was as high as 73.3%. The high catalytic performance arises from the following reasons: (i) The support of TPAFe rendered a significant increase in specific surface area and a slight increase in interlayer spacing of montmorillonite, thus improving the adsorption performance. (ii) The incorporation of tungstophosphoric acid (TPA) not only effectively anchor iron but also improved visible light absorption capacity, which greatly promoted the Fenton reaction. Moreover, the catalyst showed excellent chemical stability. After ten consecutive degradation cycles, the degradation efficiency still reached about 99% due to the good fixation iron of TPA. The possible mechanism involving in photo-Fenton process is proposed mainly based on the experimental result. This work opens up a new feasible route to synthesize visible-light-responsive high-activity photo-Fenton catalyst for efficient environmental remediation.

Ultrastable Potassium Storage Performance Realized by Highly Effective Solid Electrolyte Interphase Layer.

Potassium ion-batteries (PIBs) have attracted tremendous attention recently due to the abundance of potassium resources and the low standard electrode potential of potassium. Particularly, the solid-electrolyte interphase (SEI) in the anode of PIBs plays a vital role in battery security and battery cycling performance due to the highly reactive potassium. However, the SEI in the anode for PIBs with traditional electrolytes is mainly composed of organic compositions, which are highly reactive with air and water, resulting in inferior cycle performance and safety hazards. Herein, a highly stable and effective inorganic SEI layer in the anode is formed with optimized electrolyte. As expected, the PIBs exhibit an ultralong cycle performance over 14 000 cycles at 2000 mA g-1 and an ultrahigh average coulombic efficiency over 99.9%.

Self-Optimization of the Active Site of Molybdenum Disulfide by an Irreversible Phase Transition during Photocatalytic Hydrogen Evolution.

The metallic 1T-MoS2 has attracted considerable attention as an effective catalyst for hydrogen evolution reactions (HERs). However, the fundamental mechanism about the catalytic activity of 1T-MoS2 and the associated phase evolution remain elusive and controversial. Herein, we prepared the most stable 1T-MoS2 by hydrothermal exfoliation of MoS2 nanosheets vertically rooted into rigid one-dimensional TiO2 nanofibers. The 1T-MoS2 can keep highly stable over one year, presenting an ideal model system for investigating the HER catalytic activities as a function of the phase evolution. Both experimental studies and theoretical calculations suggest that 1T phase can be irreversibly transformed into a more active 1T' phase as true active sites in photocatalytic HERs, resulting in a "catalytic site self-optimization". Hydrogen atom adsorption is the major driving force for this phase transition.

Design Strategies of Hydrogen Evolution Reaction Nano Electrocatalysts for High Current Density Water Splitting.

Hydrogen is now recognized as the primary alternative to fossil fuels due to its renewable, safe, high-energy density and environmentally friendly properties. Efficient hydrogen production through water splitting has laid the foundation for sustainable energy technologies. However, when hydrogen production is scaled up to industrial levels, operating at high current densities introduces unique challenges. It is necessary to design advanced electrocatalysts for hydrogen evolution reactions (HERs) under high current densities. This review will briefly introduce the challenges posed by high current densities on electrocatalysts, including catalytic activity, mass diffusion, and catalyst stability. In an attempt to address these issues, various electrocatalyst design strategies are summarized in detail. In the end, our insights into future challenges for efficient large-scale industrial hydrogen production from water splitting are presented. This review is expected to guide the rational design of efficient high-current density water electrolysis electrocatalysts and promote the research progress of sustainable energy.

The spin polarization strategy regulates heterogeneous catalytic activity performance: from fundamentals to applications.

In recent years, there has been significant attention towards the development of catalysts that exhibit superior performance and environmentally friendly attributes. This surge in interest is driven by the growing demands for energy utilization and storage as well as environmental preservation. Spin polarization plays a crucial role in catalyst design, comprehension of catalytic mechanisms, and reaction control, offering novel insights for the design of highly efficient catalysts. However, there are still some significant research gaps in the current study of spin catalysis. Therefore, it is urgent to understand how spin polarization impacts catalytic reactions to develop superior performance catalysts. Herein, we present a comprehensive summary of the application of spin polarization in catalysis. Firstly, we summarize the fundamental mechanism of spin polarization in catalytic reactions from two aspects of kinetics and thermodynamics. Additionally, we review the regulation mechanism of spin polarization in various catalytic applications and several approaches to modulate spin polarization. Moreover, we discuss the future development of spin polarization in catalysis and propose several potential avenues for further progress. We aim to improve current catalytic systems through implementing a novel and distinctive spin engineering strategy.

Flexible tungsten disulfide superstructure engineering for efficient alkaline hydrogen evolution in anion exchange membrane water electrolysers.

Anion exchange membrane (AEM) water electrolysis employing non-precious metal electrocatalysts is a promising strategy for achieving sustainable hydrogen production. However, it still suffers from many challenges, including sluggish alkaline hydrogen evolution reaction (HER) kinetics, insufficient activity and limited lifetime of non-precious metal electrocatalysts for ampere-level-current-density alkaline HER. Here, we report an efficient alkaline HER strategy at industrial-level current density wherein a flexible WS2 superstructure is designed to serve as the cathode catalyst for AEM water electrolysis. The superstructure features bond-free van der Waals interaction among the low Young's modulus nanosheets to ensure excellent mechanical flexibility, as well as a stepped edge defect structure of nanosheets to realize high catalytic activity and a favorable reaction interface micro-environment. The unique flexible WS2 superstructure can effectively withstand the impact of high-density gas-liquid exchanges and facilitate mass transfer, endowing excellent long-term durability under industrial-scale current density. An AEM electrolyser containing this catalyst at the cathode exhibits a cell voltage of 1.70 V to deliver a constant catalytic current density of 1 A cm-2 over 1000 h with a negligible decay rate of 9.67 µV h-1.

π-electron injection activated dormant ligands in graphitic carbon nitride for efficient and stable uranium extraction.

Graphitic carbon nitride (CN) as an adsorbent exhibit promising potential for the removal of uranium in water. However, the lack of active sites seriously restricts its practical application. In contrast to the traditional method of introducing new ligands, we propose a strategy to activate original ligands on CN by injecting π electrons, which can be realized by grafting 4-phenoxyphenol (PP) on CN (PCN). Compared with CN, the maximum adsorption capacity of PCN for uranium increased from 150.9 mg/g to 380.6 mg/g. Furthermore, PCN maintains good adsorption properties over a wide range of uranium concentrations (1 ∼ 60 mg/L) and pH (4 ∼ 8). After 5 consecutive cycles, PCN exhibited sustained uranium removal performance with a little of losses. The experimental and theoretical results show that the enhancement of adsorption performance is mainly due to the ligands activation of CN by delocalization of π electrons from PP. Furthermore, this activation can be enhanced by irradiation, as the CN can be photoexcited to provide additional photoelectrons for PP. As a result, dormant ligands such as N-CN, C-O-C, C-N-H and N-(C)3 can be activated to participate in coordination with uranium. This work provides theoretical guidance for the design and preparation of high efficiency uranium adsorbent.

Revisited Catalytic Hydrogen Evolution Reaction Mechanism of MoS2.

MoS2 has long been considered a promising catalyst for hydrogen production. At present, there are many strategies to further improve its catalytic performance, such as edge engineering, defect engineering, phase engineering, and so on. However, at present, there is still a great deal of controversy about the mechanism of MoS2 catalytic hydrogen production. For example, it is generally believed that the base plane of MoS2 is inert; however, it has been reported that the inert base plane can undergo a transient phase transition in the catalytic process to play the catalytic role, which is contrary to the common understanding that the catalytic activity only occurs at the edge. Therefore, it is necessary to further understand the mechanism of MoS2 catalytic hydrogen production. In this article, we summarized the latest research progress on the catalytic hydrogen production of MoS2, which is of great significance for revisiting the mechanism of MoS2 catalytic hydrogen production.

A covalency-aided electrochemical mechanism for CO2 reduction: the synergistic effect of copper and boron dual active sites drives the formation of a high-efficiency ethanol product.

Electrocatalytic carbon dioxide (CO2) conversion into high-value multi-carbon products is of great significance for CO2 utilization, but the chemical inertness, low yields, and poor product selectivity hinder the application prospects of the electrocatalytic conversion methods. In this work, a covalency-aided electrochemical mechanism for CO2 reduction is proposed for the first time by embedding the nonmetallic element boron (B) on copper surfaces, in which p-block dopants have a significant impact on modifying the adsorbent intermediates and improving the catalytic activity. Herein, B atoms not only provide empty and occupied orbitals to adsorb and activate CO, but also afford a large amount of charge to stabilize the C2 intermediates. In addition, B atoms can also adjust the oxidation state of nearby copper (namely, Cu+), and the synergistic Cu+ and B dual active sites act as O* adsorption and C* adsorption sites, respectively, leading to strong adsorption and activation of CO2. First-principles calculations reveal that CO2 can be reduced into C2H5OH with an ultralow potential of -0.26 V. Overall, this study provides new insights into CO2 reduction, which offers a promising way for achieving an efficient ethanol product.

Bond modulation of MoSe2+x driving combined intercalation and conversion reactions for high-performance K cathodes.

The urgent demand for large-scale global energy storage systems and portable electronic devices is driving the need for considerable energy density and stable batteries. Here, Se atoms are introduced between MoSe2 layers (denoted as MoSe2+x ) by bond modulation to produce a high-performance cathode for potassium-ion batteries. The introduced Se atoms form covalent Se-Se bonds with the Se in MoSe2, and the advantages of bond modulation are as follows: (i) the interlayer spacing is enlarged which increases the storage space of K+; (ii) the system possesses a dual reaction mechanism, and the introduced Se can provide an additional conversion reaction when discharged to 0.5 V, which improves the capacity further; (iii) the Se atoms confined between MoSe2 layers do not give rise to the shuttle effect. MoSe2+x is compounded with rGO (MoSe2+x -rGO) as a cathode for potassium-ion batteries and displays an ultrahigh capacity (235 mA h g-1 at 100 mA g-1), a long cycle life (300 cycles at 100 mA g-1) and an extraordinary rate performance (135 mA h g-1 at 1000 mA g-1 and 89 mA h g-1 at 2000 mA g-1). Pairing the MoSe2+x -rGO cathode with graphite, the full cell delivers considerable energy density compared to other K cathode materials. The MoSe2+x -rGO cathode also exhibits excellent electrochemical performance for lithium-ion batteries. This study on bond modulation driving combined intercalation and conversion reactions offers new insights into the design of high-performance K cathodes.

Deformable Catalytic Material Derived from Mechanical Flexibility for Hydrogen Evolution Reaction.

Deformable catalytic material with excellent flexible structure is a new type of catalyst that has been applied in various chemical reactions, especially electrocatalytic hydrogen evolution reaction (HER). In recent years, deformable catalysts for HER have made great progress and would become a research hotspot. The catalytic activities of deformable catalysts could be adjustable by the strain engineering and surface reconfiguration. The surface curvature of flexible catalytic materials is closely related to the electrocatalytic HER properties. Here, firstly, we systematically summarized self-adaptive catalytic performance of deformable catalysts and various micro-nanostructures evolution in catalytic HER process. Secondly, a series of strategies to design highly active catalysts based on the mechanical flexibility of low-dimensional nanomaterials were summarized. Last but not least, we presented the challenges and prospects of the study of flexible and deformable micro-nanostructures of electrocatalysts, which would further deepen the understanding of catalytic mechanisms of deformable HER catalyst.

Selective degradation of antibiotic in a novel Cu7S4/peroxydisulfate system via heterogeneous Cu(III) formation: Performance, mechanism and toxicity evaluation.

Efficient degradation of antibiotic by peroxydisulfate (PDS)-based advanced oxidation processes in complex water environment is challenging due to the interference of impurities and the low activation efficiency of PDS caused by its symmetric structure. Herein, a novel Cu7S4/PDS system was developed, which can selectively remove tetracycline hydrochloride (TC) without interference of inorganic ions (e.g., Cl- and HCO3-) and natural organic matter (e.g., humic acid). The results of quenching and probe experiments demonstrated that surface high-valent copper species (Cu(III)), rather than radicals and 1O2, are main active species for TC degradation. Cu(III) can be generated via Cu(I)/O2 and Cu(II)/Cu(I)/PDS systems and the S species on the surface of Cu7S4 promotes the cycle of Cu(II)/Cu(I) and Cu(III)/Cu(II), resulting in continuous generation of Cu(III). In addition, the degradation pathways of TC were proposed based on product analysis and DFT theory calculations. The acute toxicity, developmental toxicity and mutagenicity of treated TC were significantly reduced according to the results of toxicity estimation software tool. This study shows a promising Cu7S4/PDS system for the degradation and detoxication of antibiotic in complex water environment, while also providing a comprehensive understanding of PDS activation by Cu7S4 to generate active Cu(III) species.

High S-doped amorphous carbon/carbon quantum dots coupled micro-frame for highly efficient potassium storage.

Anode materials with excellent rate capability, capacity, and cycle life have been a challenge in obtaining cost-effective K-ion batteries (KIBs). Based on the concept of waste recycling, we prepared the S-doped (21.5%) amorphous carbon/carbon quantum dots coupled micro-frame (SCMF) by combining chemical exfoliation and S/Se-assisted carbonization. SCMF exhibited the advantages of integrating amorphous carbon and carbon quantum dots (CQDs). The CQDs serve as fast electron channels, while amorphous carbon can accommodate more large-size K-ions and mitigate volume expansion. In KIBs, SCMF maintained a high reversible capacity (414.0 mAh g-1, after 100 cycles at 100 mA g-1), a good rate capability (224.0 mAh g-1, 2000 mA g-1), and excellent capacity retention (208.9 mAh g-1, after 2000 cycles at 1000 mA g-1). The molecular dynamic simulation revealed that CQDs provided fast electron transport channels and that C, O and S atoms had suitable interactions with K, facilitating potassium storage. Moreover, the potassium-ion capacitor (PIC) assembled from SCMF and activated carbon exhibited stable electrochemical performance, proving its potential for application. The research provided valuable insights into the reuse of biomass waste in new secondary batteries.

The Potential Strategies of ZnIn2S4-Based Photocatalysts for the Enhanced Hydrogen Evolution Reaction.

Photocatalysis is a potential strategy to solve energy and environmental problems. The development of new sustainable photocatalysts is a current topic in the field of photocatalysis. ZnIn2S4, a visible light-responsive photocatalyst, has attracted extensive research interest in recent years. Due to its suitable band gap, strong chemical stability, durability, and easy synthesis, it is expected to become a new hot spot in the field of photocatalysis in the near future. This mini-review presents a comprehensive summary of the modulation strategies to effectively improve the photocatalytic activity of ZnIn2S4 such as morphology and structural engineering, defects engineering, doping engineering, and heterojunction engineering. This review aims to provide reference to the proof-of-concept design of highly active ZnIn2S4-based photocatalysts for the enhanced hydrogen evolution reaction.

WS2 moiré superlattices derived from mechanical flexibility for hydrogen evolution reaction.

The discovery of moiré superlattices (MSLs) opened an era in the research of 'twistronics'. Engineering MSLs and realizing unique emergent properties are key challenges. Herein, we demonstrate an effective synthetic strategy to fabricate MSLs based on mechanical flexibility of WS2 nanobelts by a facile one-step hydrothermal method. Unlike previous MSLs typically created through stacking monolayers together with complicated method, WS2 MSLs reported here could be obtained directly during synthesis of nanobelts driven by the mechanical instability. Emergent properties are found including superior conductivity, special superaerophobicity and superhydrophilicity, and strongly enhanced electro-catalytic activity when we apply 'twistronics' to the field of catalytic hydrogen production. Theoretical calculations show that such excellent catalytic performance could be attributed to a closer to thermoneutral hydrogen adsorption free energy value of twisted bilayers active sites. Our findings provide an exciting opportunity to design advanced WS2 catalysts through moiré superlattice engineering based on mechanical flexibility.

Rapid removal of organic pollutants by a novel persulfate/brochantite system: Mechanism and implication.

Using natural minerals as persulfate activators can develop effective and economical in situ chemical oxidation technology for environmental remediation. Yet, few natural minerals can provide a high activation efficiency. Here, we demonstrate that brochantite (Cu4SO4(OH)6), a natural mineral, can be used as a persulfate activator for the rapid degradation of tetracycline hydrochloride (TC-H). Approximately 70% of TC-H was removed in Cu4SO4(OH)6/PDS within 5 min, which much higher than that of Cu3P (61.99%), CuO (29.75%), CNT (25.83%), Fe2O3, (14.48%) and MnO2 (9.76%). Experiments and theoretical calculations suggested that surface copper acts as active sites induce the production of free radicals. The synergistic effect of Cu/S promotes the cycle between Cu+/Cu2+. Sulfate radicals and hydroxyl radicals are the main reactive oxygen species that are responsible for the rapid removal of TC-H. The findings of this work show a novel persulfate/brochantite system and provide useful information for the environmental remediation.