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.

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.

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.

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.

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.

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.

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.

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.

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.

Co3O4 Nanocrystals with an Oxygen Vacancy-Rich and Highly Reactive (222) Facet on Carbon Nitride Scaffolds for Efficient Photocatalytic Oxygen Evolution.

Oxygen evolution reaction (OER) with sluggish kinetics is the rate-determining step of water splitting, which dominates the solar-to-hydrogen fuel conversion efficiency. Herein, we constructed an oxygen vacancy-rich and highly reactive (222) facet in Co3O4 nanocrystals anchored on carbon nitride nanofiber (CNF) by a solvothermal reduction method. The resulting Co3O4 nanocrystals/CNF (COCNF) demonstrated a dramatically enhanced OER with a rate of 24.9 µmol/h under visible light, which is 124 times higher than that of CNF. This excellent catalytic activity of COCNF is based on a synergistic effect between its binary components for charge separation, oxygen vacancies for enhanced conductivity, and facet (222) exposure of Co3O4 nanocrystals for improved heterogeneous kinetics. Density functional theory (DFT) calculations revealed the water oxidation mechanism at different facets and found that the formed oxygen vacancies lead to a reduction of the materials' bandgap. The correlation between Co3O4 crystal facets and the inherent OER catalytic activities under acidic solution was in the order of (222) > (220) > (311).

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.

Accessible COF-Based Functional Materials for Potassium-Ion Batteries and Aluminum Batteries.

The porous structure composed of non-metal elements of covalent organic frameworks (COFs) contributes to a large surface area and multifunction, rendering COFs a brilliant material for energy storage. Unfortunately, the low conductivity of most COFs limits their application in batteries. Herein, we fabricate COF-derived nitrogen-doped porous carbon (NPC) using nitrogen-rich COF-JLU2 as precursors by a simple carbonization for potassium-ion batteries (PIBs) and aluminum (Al) batteries for the first time. The computational results suggest that NPC has an enhanced conductivity and optimized electron density distribution. NPC could overcome the low conductivity of COF and thus further optimize its electrochemical performance in PIBs and Al batteries. It displays an excellent stability even after 2500 cycles (as the anode for PIBs) and 30000 cycles (as the cathode for Al batteries) with a high Coulombic efficiency. This fascinating study may be extended in other COFs for energy storage applications.

Nature of Bimetallic Oxide Sb2MoO6/rGO Anode for High-Performance Potassium-Ion Batteries.

Potassium-ion batteries (KIBs) are one of the most appealing alternatives to lithium-ion batteries, particularly attractive in large-scale energy storage devices considering the more sufficient and lower cost supply of potassium resources in comparison with lithium. To achieve more competitive KIBs, it is necessary to search for anode materials with a high performance. Herein, the bimetallic oxide Sb2MoO6, with the presence of reduced graphene oxide, is reported as a high-performance anode material for KIBs in this study, achieving discharge capacities as high as 402 mAh g-1 at 100 mA g-1 and 381 mAh g-1 at 200 mA g-1, and reserving a capacity of 247 mAh g-1 after 100 cycles at a current density of 500 mA g-1. Meanwhile, the potassiation/depotassiation mechanism of this material is probed in-depth through the electrochemical characterization, operando X-ray diffraction, transmission electron microscope, and density functional theory calculation, successfully unraveling the nature of the high-performance anode and the functions of Sb and Mo in Sb2MoO6. More importantly, the phase development and bond breaking sequence of Sb2MoO6 are successfully identified, which is meaningful for the fundamental study of metal-oxide based electrode materials for KIBs.

Boosting Photocatalytic Performance in Mixed-Valence MIL-53(Fe) by Changing FeII/FeIII Ratio.

One of vital issues that inhibit photoactivity of metal-organic frameworks is the poor electrical conductivity. In this work, one-dimensional mixed-valence iron chains are used to improve this poor situation in MIL-53(Fe). A series of mixed-valence MIL-53(Fe) photocatalysts were obtained through heating at different temperatures in vacuum. The effect of FeII coordinatively unsaturated metal sites (CUS) and one-dimensional mixed-valence iron chains on their photocatalytic property was discussed. The experimental results indicated that mixed-valence MIL-53(Fe) with a reference FeII/FeIII ratio of 0.2725 displayed the best photocatalytic performance, which showed 96.28 and 95.01% removal efficiencies of RhB and TC-H in 100 min, respectively. Moreover, MIL-53(Fe) heated in vacuum displayed better catalytic activity than MIL-53(Fe) heated in air for RhB and TC-H degradation. Based on the analysis of various characterizations, the reinforced catalytic activity can be attributed to the charge mobilities in mixed-valence FeII/FeIII chains. It is worth mentioning that the method is also applicable to MIL-88(Fe) and MIL-101(Fe). Additionally, mixed-valence MIL-53(Fe) can also perform the catalysis reaction in the nighttime by activating persulfate (PS) to produce free radicals. Interestingly, it was found that the FeII CUS lost in activating PS can be supplemented by self-reduction of photogenerated electrons during illumination in the daytime, so as to achieve a more stable cycle. This work demonstrated that the photoactivity of MIL-53(Fe) can be improved by adjusting the ratio of FeII/FeIII and the feasibility of using as an all-day-active catalyst.

The individual and Co-exposure degradation of benzophenone derivatives by UV/H2O2 and UV/PDS in different water matrices.

Benzophenone derivatives, including benzophenone-1 (C13H10O3, BP1), benzophenone-3 (C14H12O3, BP3) and benzophenone-8 (C14H12O4, BP8), that used as UV filters are currently viewed as emerging contaminants. Degradation behaviors on co-exposure benzophenone derivatives using UV-driven advanced oxidation processes under different aqueous environments are still unknown. In this study, the degradation behavior of mixed benzophenone derivatives via UV/H2O2 and UV/peroxydisulfate (PDS), in different water matrices (surface water, hydrolyzed urine and seawater) were systematically examined. In surface water, the attack of BP3 by hydroxyl radicals (HO∙) or carbonate radicals (CO3∙-) in UV/H2O2 can generate BP8, which was responsible for the relatively high degradation rate of BP3. Intermediates from BP3 and BP8 in UV/PDS were susceptible to CO3∙-, bringing inhibition of BP1 degradation. In hydrolyzed urine, Cl- was shown the negligible effect for benzophenone derivatives degradation due to low concentration of reactive chlorine species (RCS). Meanwhile, BP3 abatement was excessively inhibited during co-exposure pattern. In seawater, non-first-order kinetic behavior for BP3 and BP8 was found during UV/PDS treatment. Based on modeling, Br- was the sink for HO∙, and the co-existence of Br- and Cl- was the sink for SO4∙-. The cost-effective treatment toward target compounds removal in different water matrices was further evaluated using EE/O. In most cases, UV/H2O2 process is more economically competitive than UV/PDS process.

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.

In Situ Alloying Strategy for Exceptional Potassium Ion Batteries.

We report an in situ alloying strategy for obtaining homogeneous (Bi,Sb) alloy nanoparticles from (Bi,Sb)2S3 nanotubes for the exceptional anode of potassium ion batteries (KIBs). The operando X-ray diffraction results, along with transmission electron microscopy and energy-dispersive X-ray spectroscopy mappings, successfully reveal the phase evolution of this material, which is (Bi,Sb)2S3 → (Bi,Sb) → K(Bi,Sb) → K3(Bi,Sb) during the initial discharge and K3(Bi,Sb) → K(Bi,Sb) → (Bi,Sb) in the charging process. The in situ alloying strategy produces a synergistic effect and brings an outstanding electrochemical performance. It achieves ultrahigh discharge capacities of 611 mAh g-1 at 100 mA g-1 (0.135C) and 300 mAh g-1 at 1000 mA g-1 (1.35C) and retains a capacity as high as 353 mAh g-1 after 1000 cycles at 500 mA g-1 (0.675C) with a Coulombic efficiency close to 100%. In addition, the KIBs full cell, which is composed of this anode and a perylenetetracarboxylic dianhydride cathode, reaches an initial discharge capacity as high as 276 mAh g-1 at 500 mA g-1 and maintains 207 mAh g-1 after 100 cycles.