Electrochemical Oxidation of Furfural on NiMoP/NF: Boosting Current Density with Enhanced Adsorption of Oxygenates.

Substituting the low-value oxygen evolution reaction (OER) with thermodynamically more favored organic oxidation such as furfural oxidation reaction (FOR) is regarded as a perspective approach to decrease energy cost of hydrogen evolution from water splitting. However, the kinetic of FOR can be even more sluggish than OER under large current density. In this work, a strategy is proposed to accelerate FOR by enhancing the adsorption of oxygenates on active sites. Over the prepared NiMoP/NF anode, only 1.46 V versus RHE is required in furfural solution to achieve 500 mA cm-2 , significantly better than the OER activity over commercial RuO2 /NF under the same current density (1.57 V vs RHE).

Enhancement of Catalytic Activity via Inevitable Reconstruction of the Ni-Mo Interface for Alkaline Hydrogen Oxidation.

The inevitable oxidation of nickel-metal-based catalysts exposed to the air will lead to instability and poor reproducibility of a catalytic interface, which is usually ignored and greatly hinders their application for the catalysis of alkaline hydrogen oxidation. The details on the formation of a world-class nickel-based HOR catalyst Ni3-MoOx/C-500 are reported via an interfacial reconstruction triggered by passive oxidation upon air exposure. Interfacial reconstruction, initiated with various Ni-Mo metal ratios and annealing temperature, can fine-tune the Ni-Mo interface with an increased work function and a reduced d-band center. The optimized Ni3-MoOx/C exhibits a record high mass activity of 102.8 mA mgNi -1, a top-level exchange current density of 76.5 µA cmNi -2, and exceptional resistance to CO poisoning at 1000 ppm CO for hours. The catalyzed alkaline exchange membrane fuel cell exhibits a maximum power output of 600 mW cm-2 and excellent stability, ranking it as one of the most active non-precious metals HOR catalysts to date.

In Situ Constructing Metal-Organic Complex Interface Layer Using Biomolecule Enabling Stabilize Zn Anode.

Aqueous zinc-ion batteries (ZIBs) are considered as a promising candidate for next-generation large-scale energy storage due to their high safety, low cost, and eco-friendliness. Unfortunately, commercialization of ZIBs is severely hindered owing to rampant dendrite growth and detrimental side reactions on the Zn anode. Herein, inspired by the metal-organic complex interphase strategy, the authors apply adenosine triphosphate (ATP) to in situ construct a multifunctional film on the metal Zn surface (marked as ATP@Zn) by a facile etching method. The ATP-induced interfacial layer enhances lipophilicity, promoting uniform Zn2+ flux and further homogenizing Zn deposition. Meanwhile, the functional interlayer improves the anticorrosion ability of the Zn anode, effectively suppressing corrosion and hydrogen evolution. Consequently, the as-prepared ATP@Zn anode in the symmetric cell exhibits eminent plating/stripping reversibility for over 2800 h at 5.0 mA cm-2 and 1 mAh cm-2. Furthermore, the assembled ATP@Zn||MnO2 full cells are investigated to evaluate practical feasibilities. This work provides an efficient and simple strategy to prepare stabilized Zn anode toward high-performance ZIBs.

Benzoic Acid: Electrode-Regenerated Molecular Catalyst to Boost Cycloolefin Epoxidation.

Stoichiometric oxidants are always consumed in organic oxidation reactions. For example, olefins react with peroxy acids to be converted to epoxy, while the oxidant, peroxy acid, is downgraded to carboxylic acid. In this paper, we aim to regenerate carboxylic acid into peroxy acid through electric water splitting at the anode, in order to construct an electrochemical catalytic cycle to accomplish the cycloolefin epoxidation reaction. Benzoic acid, which can be strongly adsorbed onto the anode and rapidly converted to peroxy acid, was selected to catalyze the cycloolefin epoxidation. Furthermore, the peroxybenzoic acid will be further activated on the electrode to fulfill the epoxidation and release the benzoic acid to complete the catalytic cycle. In this designed reaction cycle, benzoic acid acts as a molecular catalyst with the assistance of the electrode-generated reactive oxygen species (ROS). This method can successfully reform the consumable oxidants to molecular catalysts, which can be generalized to other green organic syntheses.

How Size and Strain Effect Synergistically Improve Electrocatalytic Activity: A Systematic Investigation Based on PtCoCu Alloy Nanocrystals.

To reveal how the size effect and strain effect synergistically regulate the mass activity (MA) and specific activity (SA) of Pt alloy nanocrystal catalysts in oxygen reduction reaction (ORR), remains to be difficult due to the highly entangled factors. In this work, six ternary PtCoCu catalysts with sequentially changed composition, size, and compression strain are prepared. It is found that the smaller the alloy particles, the higher the electrochemical active surface area (ECSA) and MA values, that is, the particle size plays a decisive role in the size of the ECSA and MA. While, along alloy size decrease, the intrinsic activity SA first increases, then remains unchanged, and finally rapidly increases again. This detailed analysis shows that for the alloys above 4 nm, it is the surface coordination number that decides the SA, while for those below 4 nm, it is the well-regulated compression strain that determines the SA. Particularly, Pt47 Co26 Cu27 demonstrates the MA of 1.19 A mgPt -1 and SA of 1.48 mA cm-2 , being 7.9 and 6.4 times those of commercial Pt/C respectively, representing an especially superior ORR catalyst.

Stable Lithium-Sulfur Batteries Ensured by GeS2 and α-S8 Lattice Matching During the Charge Process.

The charge process of lithium-sulfur batteries (LSBs) is a process in which molecular polarity decreases and the volume shrinks gradually, which is the process most likely to cause lithium polysulfides (LiPSs) loss and interfacial collapse. In this work, GeS2 is utilized, whose (111) lattice plane exactly matches with the (113) lattice of α-S8 , to solve these problems. GeS2 can regulate the interconversion-deposition behavior of S-species during the charge process. Soluble LiPSs can be spontaneously adsorbed on the GeS2 surface, then obtain electrons and eventually convert to α-S8 molecules. More importantly, the α-S8 molecules will crystallize uniformly along the (111) lattice plane of GeS2 to maintain a stable cathode-electrolyte interface. Therefore, outstanding charge/discharge LSBs are successfully accomplished.

Nanoarray Architecture of Ultra-Lithiophilic Metal Nitrides for Stable Lithium Metal Anodes.

Lithium metal anode (LMA) is puzzled by the serious issues corresponding to infinite volume change and notorious lithium dendrite during long-term stripping/plating process. Herein, the transition metal nitrides array with outstanding lithiophilicity, including CoN, VN, and Ni3 N, are decorated onto carbon framework as "nests" to uniform Li nucleation and guide Li metal deposition. These transition metal nitrides with excellent conductivity can guarantee the fast electron transport, therefore maintain a stable interface for Li reduction. In addition, the designed multi-dimensional structure of metal nitride array decorated carbon framework can effectively regulate the growth of Li metal during the stripping/plating process. Of note, attributing to the lattice-matching between CoN and Li metal, the composite Li/CoN@CF anode exhibits ultra-stable cycling performance in symmetrical cells (over 4000 h@1 mA cm-2 with 1 mAh cm-2 and 1000h@20 mA cm-2 with 20 mAh cm-2 ). The assembled full cells based on Li/CoN@CF composite anode, LiFePO4 or S as cathodes, deliver excellent cycling stability and rate capability. This strategy provides an effective approach to develop a stable lithium metal anode for lithium metal batteries.

Establishing Transition Metal Phosphides as Effective Sulfur Hosts in Lithium-Sulfur Batteries through the Triple Effect of "Confinement-Adsorption-Catalysis".

Structurally optimized transition metal phosphides are identified as a promising avenue for the commercialization of lithium-sulfur (Li-S) batteries. In this study, a CoP nanoparticle-doped hollow ordered mesoporous carbon sphere (CoP-OMCS) is developed as a S host with a "Confinement-Adsorption-Catalysis" triple effect for Li-S batteries. The Li-S batteries with CoP-OMCS/S cathode demonstrate excellent performance, delivering a discharge capacity of 1148 mAh g-1 at 0.5 C and good cycling stability with a low long-cycle capacity decay rate of 0.059% per cycle. Even at a high current density of 2 C after 200 cycles, a high specific discharge capacity of 524 mAh g-1 is maintained. Moreover, a reversible areal capacity of 6.56 mAh cm-2 is achieved after 100 cycles at 0.2 C, despite a high S loading of 6.8 mg cm-2 . Density functional theory (DFT) calculations show that CoP exhibits enhanced adsorption capacity for sulfur-containing substances. Additionally, the optimized electronic structure of CoP significantly reduces the energy barrier during the conversion of Li2 S4 (L) to Li2 S2 (S). In summary, this work provides a promising approach to optimize transition metal phosphide materials structurally and design cathodes for Li-S batteries.

Mesoporous Carbon-Based Materials for Enhancing the Performance of Lithium-Sulfur Batteries.

The most promising energy storage devices are lithium-sulfur batteries (LSBs), which offer a high theoretical energy density that is five times greater than that of lithium-ion batteries. However, there are still significant barriers to the commercialization of LSBs, and mesoporous carbon-based materials (MCBMs) have attracted much attention in solving LSBs' problems, due to their large specific surface area (SSA), high electrical conductivity, and other unique advantages. The synthesis of MCBMs and their applications in the anodes, cathodes, separators, and "two-in-one" hosts of LSBs are reviewed in this study. Most interestingly, we establish a systematic correlation between the structural characteristics of MCBMs and their electrochemical properties, offering recommendations for improving performance by altering the characteristics. Finally, the challenges and opportunities of LSBs under current policies are also clarified. This review provides ideas for the design of cathodes, anodes, and separators for LSBs, which could have a positive impact on the performance enhancement and commercialization of LSBs. The commercialization of high energy density secondary batteries is of great importance for the achievement of carbon neutrality and to meet the world's expanding energy demand.

The increased anterior talofibular ligament-posterior talofibular ligament angle on MRI may help evaluate chronic ankle instability.

PURPOSE: This study intended to compare the difference between the anterior talofibular ligament (ATFL) and posterior talofibular ligament (PTFL) angle with chronic ankle instability (CAI) patients and healthy volunteers, and to confirm whether using the ATFL-PTFL angle could be a reliable assessment method for CAI, so as to improve the accuracy and specificity of clinical diagnosis. METHODS: This retrospective study included 240 participants: 120 CAI patients and 120 healthy volunteers between 2015 and 2021. The ATFL-PTFL angle of the ankle region was gaged in the cross-sectional supine position on MRI between two groups. After participants undergoing a comprehensive MRI scanning, ATFL-PTFL angles were regarded as the main indicator of patients with the injured ATFLs and healthy volunteers to compare, and were measured by an experienced musculoskeletal radiologist. Moreover, other qualitative and quantitative indicators referring to anatomical and morphological characteristics of the AFTL were included in this study with MRI, such as the length, width, thickness, shape, continuity, and signal intensity of the ATFL, which can be used as secondary indicators. RESULTS: In the CAI group, the ATFL-PTFL angle was 90.8° ± 5.7°, which was significantly different from the non-CAI group where the ATFL-PTFL angle for 80.0° ± 3.7° (p < 0.001). As for the ATFL-MRI characteristics, the length (p = 0.003), width (p < 0.001), and thickness (p < 0.001) in the CAI group were also significantly different from the non-CAI group. Over 90% of the cases, patients of the CAI group had injured ATFL with an irregular shape, non-continuous, and high or mixed signal intensity. CONCLUSION: Compared with healthy people, the ATFL-PTFL angle of most CAI patients is larger, which can be used as a secondary index to diagnose CAI. However, the MRI characteristic changes of ATFL may not relate to the increased ATFL-PTFL angle.

Fe-N-C Boosts the Stability of Supported Platinum Nanoparticles for Fuel Cells.

The poor durability of Pt-based nanoparticles dispersed on carbon black is the challenge for the application of long-life polymer electrolyte fuel cells. Recent work suggests that Fe- and N-codoped carbon (Fe-N-C) might be a better support than conventional high-surface-area carbon. In this work, we find that the electrochemical surface area retention of Pt/Fe-N-C is much better than that of commercial Pt/C during potential cycling in both acidic and basic media. In situ inductively coupled plasma mass spectrometry studies indicate that the Pt dissolution rate of Pt/Fe-N-C is 3 times smaller than that of Pt/C during cycling. Density functional theory calculations further illustrate that the Fe-N-C substrate can provide strong and stable support to the Pt nanoparticles and alleviate the oxide formation by adjusting the electronic structure. The strong metal-substrate interaction, together with a lower metal dissolution rate and highly stable support, may be the reason for the significantly enhanced stability of Pt/Fe-N-C. This finding highlights the importance of carbon support selection to achieve a more durable Pt-based electrocatalyst for fuel cells.

Ultrathin and Super Strong UHMWPE Supported Composite Anion Exchange Membranes with Outstanding Fuel Cells Performance.

For high-performance anion exchange membrane fuel cells (AEMFCs), the anion exchange membrane (AEMs) should be as thin as possible to reduce the ohmic resistance. However, the mechanical stability of ultrathin AEMs cannot be guaranteed, as well as a huge risk of gas (H2 &O2 ) permeation. In this work, composite AEMs based on ultrahigh molecular weight polyethylene (UHMWPE) are prepared by in situ bulk polymerization. The as-prepared composite membranes can be as thin as 4 µm, and possess super high strength beyond 150 MPa. It also shows extremely low hydrogen permeation, low water uptake, low dimensional swelling, high conductivity, and good alkaline stability. In addition, the fuel cell performance based on the ultrathin composite AEMs exhibits outstanding peak power density of 1014 and 534 mW cm-2 for H2 -O2 and H2 -Air (CO2 -free) at 65 °C, respectively, as well as good short-term durability.

Solid-State Synthesis of Highly Dispersed Nitrogen-Coordinated Single Iron Atom Electrocatalysts for Proton Exchange Membrane Fuel Cells.

Fe-N-C with atomically dispersed Fe single atoms is the most promising candidate to replace platinum for the oxygen reduction reaction (ORR) in fuel cells. However, the conventional synthesis procedures require quantities solvents and metal precursors, sluggish adsorption process, and tedious washing, resulting in limited metal doping and uneconomical for large-scale production. For the first time, Fe2O3 is adopted as the Fe precursor to derive abundant single Fe atoms dispersed on carbon surfaces. The Fe-N-C catalyst synthesized by this simple method shows an excellent ORR activity with half-wave potentials of 0.82 and 0.90 V in acidic and alkaline solutions, respectively. A single fuel cell with an optimized Fe-N-C cathode shows a high peak power density of 0.84 W cm-2. The solid-state transformation synthesis method developed in this study may shed light on mass production of single-atom-based catalysts.

Recent Progress in Precious Metal-Free Carbon-Based Materials towards the Oxygen Reduction Reaction: Activity, Stability, and Anti-Poisoning.

The large-scale application of polymer electrolyte membrane fuel cells (PEMFCs) depends heavily on the development of high-performance and cost-effective oxygen reduction reaction (ORR) electrocatalysts to replace the traditional Pt-based materials. Among the numerous candidates of ORR electrocatalysts, precious metal-free carbon-based materials have received ever-increasing attention for their unique electronic features, tunable nanostructures, and robustness. Although tremendous efforts have been devoted to raising the intrinsic properties of precious metal-free carbon-based materials, there exists a lot of room for them to be improved in activity, stability, and poison-tolerance. In this Minireview, the latest strategies for enhancing activity by increasing the accessible active sites and promoting the intrinsic activity have been summarized. In addition, with special emphasis on devastating catalyst poisoning, up-to-data tactics for elevating the stability and poison-tolerance are introduced. Finally, conclusions and perspectives are also presented.

Mo2N-Ni/NF Heterostructure Boosts Electrocatalytic Hydrogen Evolution with Pt-Like Activity.

The sustainable development of a hydrogen economy requires hydrogen production from water electrolysis at a low cost, but the limited production of active and robust electrocatalysts using materials that are abundant on earth has restrained development. This article reports a heterostructure of a Mo2N phase and metal Ni nanocrystals and its activities in the hydrogen evolution reaction (HER) in alkaline electrolytes. Hydrogen is produced by the catalyst in alkaline electrolytes at a density of 10 mA cm-2 at an overpotential of only 20 mV with a small Tafel slope of 39.9 mV dec-1, in which the catalyst exhibits a synergetic effect of compact Mo2N and Ni interfacial connections, producing localized hotspots that accelerate water dissociation and hydrogen desorption. This makes the catalyst one of the most effective Pt-free species. Experimental and DFT theoretical results show that the exceptional HER electrocatalytic activity produced by the Mo2N-Ni/NF heterogeneous structure is related to the unique highly unshielded structure and high intrinsic activity accompanied by a nearly thermoneutral H-adsorption energy.

Tuning Interfacial Structures for Better Catalysis of Water Electrolysis.

Interface modulation, as an old concept of heterogeneous catalysis, represents an emerging, fast-growing and exciting direction in the field of water electrolysis. Over the past five years, diverse hetero-nanostructures have been synthesised as water electrolysis catalysts by taking advantage of interface modulation. However, it seems that the performance (i.e., efficiency and durability) of these materials needs to be further improved. Therefore, a comprehensive summary of recent achievements and the challenging issues concerning the regulation of material functionalities through interface modulation is necessary and helpful. Herein, firstly, the fundamentals of water electrolysis are outlined, and then the delicate design and fine control of well-defined interfaces, as well as related mechanisms for performance improvement are discussed. Finally, future opportunities and challenges in the everlasting pursuit of highly efficient and robust water electrolysis catalysts are highlighted.

Theoretical research on the oxidation mechanism of doped carbon based catalysts for oxygen reduction reaction.

To understand the essential reasons of poor durability and rapid initial performance loss of heteroatom doped graphene catalysts during the electrochemical oxygen reduction reaction (ORR) process, it is necessary to explore the detailed mechanism of carbon active site oxidation reaction (COR) at different electrode potentials, as it may greatly influence the ORR activity. Herein, density functional theory (DFT) calculation is used to investigate all possible COR mechanisms, including Direct-COR and Indirect-COR, on four typical doped-graphene, and understand the competing relation between COR and ORR from a thermodynamic point of view. Our systematic calculations found that the Direct-COR is affected directly by the structural stability of doped-graphene relative to pure graphite, and the Indirect-COR can be accelerated largely by the ORR process due to the ORR intermediate, such as O and OOH. The competition relation between COR and ORR is mainly influenced by the interaction between the doped-graphene and reaction species, stability of doped-structure, ORR mechanism, and electrode potential. For COR, the partial oxidation of doped-graphene is the dominant oxidation reaction compared to complete oxidation in the ORR potential range. More importantly, both partial and complete oxidation of doped-graphene can remarkably depress the ORR activity. Hence, COR should be one of the major contributors to the rapid initial performance loss of carbon based catalysts in stability testing. Our results provide a comprehensive and deep understanding of the oxidation of carbon active sites on doped-graphene surfaces and can guide the design of more robust doped-carbon based catalysts.

Modifying the sensibility of nonmetal-doped phosphorene by local or global properties.

Doping heteroatoms into phosphorene has attracted considerable attention due to its effectiveness in enhancing the stability and tailoring the electronic properties as well as sensing capability. In this work, we performed a density functional theory (DFT) calculation to study the effect of nonmetallic heteroatom dopants (X, X = Be, B, C, N, O, S, Se, Te, F, Cl, Br and I) on the stability and sensibility of X-doped phosphorene. We found that phosphorene structures doped with the 2nd period and VIA group atoms possess relatively high internal stability due to the effective X-P bonding. More interestingly, the interaction between P sites and small species can be modified effectively by a local property-the charge (Q) of P sites-and/or a global property-the Fermi level (EFermi) of X-doped phosphorene-depending on the charge transfer degree between the species and the P sites. For the species with dramatic charge transfer, the local Q of the P site plays the most important role. For the species with moderate charge transfer, the major determinant of sensibility is the local Q and global EFermi. This work reveals the relation between the properties of X-doped phosphorene and the physico-chemical parameters of X, including the electronegativity, atomic number, and X-P bonding strength, and provides a useful guideline for choosing the appropriate nonmetallic dopants to enhance the stability and sensibility of X-doped phosphorene towards special species.

Intrinsic effects of strain on low-index surfaces of platinum: roles of the five 5d orbitals.

Surface strain has been widely applied in catalyst design. It has been reported that tensile strain can weaken the adsorption of species on certain metal surfaces similar to the effects of compressive strain. This result contradicts the widely accepted rule predicated on the d-band center. Here, by using DFT calculations, we confirmed the abnormal adsorption behaviour of certain species on strained Pt low-index surfaces and found that the behaviour is dependent on the surfaces and species. Tensile strain on the close-packed Pt(111) and Pt(100) surfaces enhances species adsorption, while tensile strain on the open Pt(110) surface weakens species adsorption. This result is attributed to the asynchronous change in the five 5d orbitals due to the inconsistency between interlayer contraction and biaxial stretching. The dramatic contraction of interlayer spacing on the tensile strained Pt(110) surface sharply downshifts the dz2 center, then weakens species adsorption. Thus, due to the different roles of the five d orbitals in binding species, the inconsistent change in the five d orbitals is the intrinsic mechanism of the effects of strain on metal catalysts. Selectively tuning the five d orbitals might provide a new strategy to modify the adsorption behaviour of species on Pt-based catalysts and may result in extraordinarily high catalytic activities.

Systematic exploration of N,C coordination effects on the ORR performance of Mn-Nx doped graphene catalysts based on DFT calculations.

A single-atom TM-Nx (TM = Fe, Co, Mn, etc.) embedded graphene matrix is known for its excellent activity and durability in oxygen reduction reaction (ORR) catalysis. Among them, Mn-N4 sites have been theoretically proved to undergo a complete 4-electron pathway with low ORR overpotentials and low activation barriers in O2 dissociation. However, in reality there still remain significant activity gaps between such Mn-N4 based catalysts (such as MnPc and MnP) and Fe-N4 or Pt-group metal catalysts. The inferior ORR performance of MnPc and MnP could be attributed to the strong binding ability of Mn that causes great difficulties in removing the ORR products from the surface sites. On this basis, 17 types of Mn-Nx models containing various three-, four- and five-coordination groups were established. Systematic density functional theory (DFT) calculations were performed to investigate the N,C coordination effects on their corresponding ORR activities. Scaling relations were found among the binding strengths of key ORR intermediates, which could be modulated by the N doping level among different coordination groups. A volcano plot for ORR overpotentials (ηSHE) as a function of *OH adsorption free energy (ΔG*OH) was further established. The 3D five-coordination sites exhibit much higher ORR activity due to the great decrease in strong binding abilities compared with 2D three- or four-coordination sites. Particularly, (Cyan)Mn-N4/D is positioned near the apex of the volcano plot with an ηSHE of 0.33 V even lower than that of Pt(111) (0.34 V). Furthermore, the electron withdrawing/donating mechanisms among Mn, N, C, and O were investigated and related to the binding abilities of different coordination groups. Electronic structure calculations indicate that the binding abilities of Mn-Nx well correlate with the σ-type anti-bonding components between Mn-3d and O-2p states near the Fermi energy level.