Facet Engineering and Pore Design Boost Dynamic Fe Exchange in Oxygen Evolution Catalysis to Break the Activity-Stability Trade-Off.

The oxygen evolution reaction (OER) plays a vital role in renewable energy technologies, including in fuel cells, metal-air batteries, and water splitting; however, the currently available catalysts still suffer from unsatisfactory performance due to the sluggish OER kinetics. Herein, we developed a new catalyst with high efficiency in which the dynamic exchange mechanism of active Fe sites in the OER was regulated by crystal plane engineering and pore structure design. High-density nanoholes were created on cobalt hydroxide as the catalyst host, and then Fe species were filled inside the nanoholes. During the OER, the dynamic Fe was selectively and strongly adsorbed by the (101̅0) sites on the nanohole walls rather than the (0001) basal plane, and at the same time the space-confining effect of the nanohole slowed down the Fe diffusion from catalyst to electrolyte. As a result, a local high-flux Fe dynamic equilibrium inside the nanoholes for OER was achieved, as demonstrated by the Fe57 isotope labeled mass spectrometry, thereby delivering a high OER activity. The catalyst showed a remarkably low overpotential of 228 mV at a current density of 10 mA cm-2, which is among the best cobalt-based catalysts reported so far. This special protection strategy for Fe also greatly improved the catalytic stability, reducing the Fe leaching amount by 2 orders of magnitude compared with the pure Fe hydroxide catalyst and thus delivering a long-term stability of 130 h. An assembled Zn-air battery was stably cycled for 170 h with a low discharge/charge voltage difference of 0.72 V.

S and O Co-Coordinated Mo Single Sites in Hierarchically Porous Tubes from Sulfur-Enamine Copolymerization for Oxygen Reduction and Evolution.

The highly efficient bifunctional catalyst for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) is the key to achieving high-performance rechargeable Zn-air batteries. Non-precious-metal single-atom catalysts (SACs) have attracted intense interest due to their low cost and very high metal atomic utilization; however, high-activity bifunctional non-precious-metal SACs are still rare. Herein, we develop a new nanospace-confined sulfur-enamine copolymerization strategy to prepare a new type of bifunctional Mo SACs with O/S co-coordination (Mo-O2S2-C) supported on the multilayered, hierarchically porous hollow tubes. The as-prepared catalyst can not only expose more active sites and facilitate mass transfer due to their combined micropores, mesopores, and macropores but also have the S/O co-coordination structure for optimizing the adsorption energies of the ORR intermediates. Its ORR activity is among the highest, and it shows a low overpotential of 324 mV for the OER at 10 mA cm-2 in all of the reported Mo-based catalysts. When assembled in a Zn-air battery, it exhibits a high maximal power density of 197.3 mW cm-2 and a long service life of 50 hours, superior to those of Zn-air batteries using commercial Pt/C+IrO2.

Guided Design of Efficient Oxygen Evolution Catalysts Using Patent Analysis.

The facile and rapid design of efficient oxygen evolution reaction (OER) catalysts holds paramount significance for energy conversion devices, such as water electrolyzers and fuel cells. Despite substantial progress in catalyst synthesis and performance exploration, the design and selection processes remain inefficient. In this context, we integrate patent analysis with catalyst design, leveraging the scholarly research functionalities within patent analyses to aid in the design and synthesis of a NiFeRu-carbon catalyst as a high-performance OER catalyst. The results demonstrate that the NiFeRu-Carbon catalyst with low Ru loading (0.3 wt %) exhibits an overpotential of only 219 mV at 10 mA cm-2 under alkaline conditions, and after continuous operation for 200 h, the overpotential only attenuates by 15 mV. The incorporation of high-valence Ru dopants elevated the intrinsic activity of individual catalytic sites within NiFe-layered double hydroxides (LDHs). During the catalytic process, the partial dissolution of Ru might lead to the generation of numerous oxygen vacancies within NiFe- LDH, thereby enhancing the catalyst's activity and stability.

Powder Metallurgy Route to Ultrafine-Grained Refractory Metals.

Ultrafine-grained (UFG) refractory metals are promising materials for applications in aerospace, microelectronics, nuclear energy, and many others under extreme environments. Powder metallurgy (PM) allows to produce such materials with well-controlled chemistry and microstructure at multiple length scales and near-net shape manufacturing. However, sintering refractory metals to full density while maintaining a fine microstructure is still challenging due to the high sintering temperature and the difficulty to separate the kinetics of densification versus grain growth. Here an overview of the sintering issues, microstructural design rules, and PM practices towards UFG and nanocrystalline refractory metals are sought to be provided. The previous efforts shall be reviewed to address the processing challenges, including the use of fine/nanopowders, second-phase grain growth inhibitors, and field-assisted sintering techniques. Recently, pressureless two-step sintering has been successfully demonstrated in producing dense UFG refractory metals down to ≈300 nm average grain size with a uniform microstructure and this technological breakthrough shall be reviewed. PM progresses in specific materials systems shall be next reviewed, including elementary metals (W and Mo), refractory alloys (W-Re), refractory high-entropy alloys, and their composites. Last, future developments and the endeavor towards UFG and nanocrystalline refractory metals with exceptionally uniform microstructure and improved properties are outlined.

Prediction of Oxygen Evolution Activity for NiCoFe Oxide Catalysts via Machine Learning.

Transition metal (such as Fe, Co, and Ni) oxides are excellent systems in the oxygen evolution reaction (OER) for the development of non-noble-metal-based catalysts. However, direct experimental evidence and the physical mechanism of a quantitative relationship between physical factors and oxygen evolution activity are still lacking, which makes it difficult to theoretically and accurately predict the oxygen evolution activity. In this work, a data-driven method for the prediction of overpotential (OP) for (Ni-Fe-Co)O x catalysts is proposed via machine learning. The physical features that are more related to the OP for the OER have been constructed and analyzed. The random forest regression model works exceedingly well on OP prediction with a mean relative error of 1.20%. The features based on first ionization energies (FIEs) and outermost d-orbital electron numbers (DEs) are the principal factors and their variances (δFIE and δDE) exhibit a linearly decreasing correlation with OP, which gives direct guidance for an OP-oriented component design. This method provides novel and promising insights for the prediction of oxygen evolution activity and physical factor analysis in (Ni-Fe-Co)O x catalysts.

Using Machine Learning to Predict Oxygen Evolution Activity for Transition Metal Hydroxide Electrocatalysts.

Electrocatalytic water splitting is an attractive way to generate hydrogen and oxygen for obtaining clean energy. Oxygen evolution reaction (OER), as one of the half reactions of oxygen evolution, is kinetically unfavorable involving the transfer of four electrons. Hydroxides are promising candidates for efficient OER electrocatalysts toward water splitting because of their high intrinsic activity and active surface area. However, quantitative prediction of hydroxide electrocatalytic performances from high-dimensional component spaces remains a challenge, severely hindering the performance-oriented precise composition and process design. Herein, we introduce a machine learning-based OER activity prediction method for hydroxide catalysts under extensive doping space for the first time. The relationship among composition, morphology, phase, pH value of the electrolyte, type of the working electrode, and overpotential was successfully fitted by the random forest algorithm. The model shows a good precision on the forecast of new experiments with a mean relative error of 4.74%. Furthermore, a new high-activity hydroxide catalyst Ni0.77Fe0.13La0.1 was rationally designed and experimentally prepared, showing an ultra-low OP of 226 mV for a current density of 10 mA cm-2. This work provides an effective and novel way for hydroxide electrocatalyst prediction, which can further enhance the electrocatalyst design toward high catalytic performance.

Large-scale synthesis of ultrafine Fe3C nanoparticles embedded in mesoporous carbon nanosheets for high-rate lithium storage.

Fe3C modified by the incorporation of carbon materials offers excellent electrical conductivity and interfacial lithium storage, making it attractive as an anode material in lithium-ion batteries. In this work, we describe a time- and energy-saving approach for the large-scale preparation of Fe3C nanoparticles embedded in mesoporous carbon nanosheets (Fe3C-NPs@MCNSs) by solution combustion synthesis and subsequent carbothermal reduction. Fe3C nanoparticles with a diameter of ∼5 nm were highly crystallized and compactly dispersed in mesoporous carbon nanosheets with a pore-size distribution of 3-5 nm. Fe3C-NPs@MCNSs exhibited remarkable high-rate lithium storage performance with discharge specific capacities of 731, 647, 481, 402 and 363 mA h g-1 at current densities of 0.1, 1, 2, 5 and 10 A g-1, respectively, and when the current density reduced back to 0.1 A g-1 after 45 cycles, the discharge specific capacity could perfectly recover to 737 mA h g-1 without any loss. The unique structure could promote electron and Li-ion transfer, create highly accessible multi-channel reaction sites and buffer volume variation for enhanced cycling and good high-rate lithium storage performance.

Correction: Large-scale synthesis of ultrafine Fe3C nanoparticles embedded in mesoporous carbon nanosheets for high-rate lithium storage.

[This corrects the article DOI: 10.1039/D1RA08516F.].

Mesoporous Single Crystals with Fe-Rich Skin for Ultralow Overpotential in Oxygen Evolution Catalysis.

The oxygen evolution reaction (OER) is a key reaction in water splitting and metal-air batteries, and transition metal hydroxides have demonstrated the most electrocatalytic efficiency. Making the hydroxides thinner for more surface commonly fails to increase the active site number, because the real active sites are the edges. Up to now, the overpotentials of most state-of-the-art OER electrocatalysts at a current density of 10 mA cm-2 (η10 ) are still larger than 200 mV. Herein, a novel design of mesoporous single crystal (MSC) with an Fe-rich skin to boost the OER is shown. The edges around the mesopores provide lots of real active sites and the Fe modification on these sites further improves the intrinsic activity. As a result, an ultralow η10 of 185 mV is achieved, and the turnover frequency based on Fe atoms is as high as 16.9 s-1 at an overpotential of 350 mV. Moreover, the catalyst has an excellent catalytic stability, indicated by a negligible current drop after 10 000 cyclic voltammetry cycles. The catalyst enables Zn-air batteries to run stably over 270 h with a low charge voltage of 1.89 V. This work shows that MSC materials can provide new opportunities for the design of electrocatalysts.

Single-Atom Co Doped in Ultrathin WO3 Arrays for the Enhanced Hydrogen Evolution Reaction in a Wide pH Range.

Owing to the scarcity of Pt, low-cost, stable, and efficient nonprecious metal-based electrocatalysts that can be applied in a wide pH range for the hydrogen evolution reaction (HER) are urgently required. Herein, a highly efficient and robust HER catalyst that is applicable at all pH values is fabricated, containing isolated Co-single atomic sites anchored in the self-supported WO3 arrays grown on Cu foam. At a current density of 10 mA cm-2, the HER overpotentials are 117, 105, and 149 mV at pH values of 0, 7, and 14, respectively, which are significantly lower than those of the undoped WO3, suggesting superior electrocatalytic H2-evolution activity at all pH values. The catalyst also exhibits long-term stability over a wide pH range, particularly in an acidic medium over 24 h, owing to the excellent anticorrosion properties of WO3. Density functional theory calculations prove that the enhanced HER activity is attributed to the isolated Co sites because these optimize the adsorption energy of H* species on WO3. Moreover, the high electrical conductivity of Co-doped WO3 and the three-dimensional array structure supported on the porous metal support afford a catalyst with suitable HER kinetics to enhance the catalytic performance.

[Mechanical properties of 3D-printed titanium mesh and its biocompatibility in vitro].

PURPOSE: To compare the mechanical properties of 3D-printed titanium meshes and pre-shaped titanium meshes, and to evaluate the effects of 3D-printed titanium meshes on cell proliferation and differentiation. METHODS: 3D- printed titanium meshes were produced and prepared with laser printing machine. The mechanical properties were analyzed by static tension and compression load test. Bone marrow mesenchymal stem cells (BMSCs) were extracted from 4-week-old male SD rats. BMSCs were co-cultured with 3D-printed titanium meshes of different apertures. Cell counting kit-8 (CCK-8) assay was used to detect cell proliferation. Alkaline phosphatase (ALP) activity assay was used to test ALP activity. The expression of related osteogenic genes was tested by real-time PCR. The adhesion and growth of BMSCs were investigated by scanning electron microscopy (SEM) and living / dead cell staining. SPSS 22.0 software package was used for statistical analysis of the results. RESULTS: The results of 3D-printing Ti-meshes tension and compression loading experiment were excellent. The 3D-printing Ti-meshes showed no inhibitory effects on cell proliferation, survival and adhesion, but had a positive effect on osteogenesis of BMSCs. CONCLUSIONS: The mechanical properties of 3D-printed Ti-meshes are excellent. The 3D-printed Ti-meshes have good biocompatibility.

Solution Synthesis of Co-Ni-W-Based ODS Alloy Powder.

Low-temperature combustion synthesis was utilized to prepare Co-Ni-W-based oxide dispersion strengthened (ODS) alloy powder. The influence of the U/Co and C/Co ratios on the morphology and specific surface area of the combusted powder was investigated. Particle size, phase constituents, and element distribution of the resulting Co-Ni-W-based ODS alloy powder were characterized. The results indicate that insufficient urea induced no autocombustion reaction, while excess urea and glucose inhibited the combustion reaction. The optimized contents of urea and glucose were around U/Co = 1.2 and C/Co = 1.5, and the specific surface area of the powder reached 43.5 m²/g. The lamellar Co-Ni-W-based ODS alloy powder with particle sizes of 1-21 µm was the soft agglomeration of a high population of nanosized (65 nm) particles. These nanoparticles grew from 65 to 260 nm in the reduction temperature range of 700-900 °C. Homogeneous distribution of Co, Ni, W, and Y in the Co-Ni-W-based ODS alloy powder was achieved.

Tuning Metallic Co0.85Se Quantum Dots/Carbon Hollow Polyhedrons with Tertiary Hierarchical Structure for High-Performance Potassium Ion Batteries.

Potassium-ion batteries (KIBs) are a potential candidate to lithium-ion batteries (LIBs) but possess unsatisfactory capacity and rate properties. Herein, the metallic cobalt selenide quantum dots (Co0.85Se-QDs) encapsulated in mesoporous carbon matrix were designed via a direct hydrothermal method. Specifically, the cobalt selenide/carbon composite (Co0.85Se-QDs/C) possesses tertiary hierarchical structure, which is the primary quantum dots, the secondary petals flake, and the tertiary hollow micropolyhedron framework. Co0.85Se-QDs are homogenously embedded into the carbon petals flake, which constitute the hollow polyhedral framework. This unique structure can take the advantages of both nanoscale and microscale features: Co0.85Se-QDs can expand in a multidimensional and ductile carbon matrix and reduce the K-intercalation stress in particle dimensions; the micropetals can restrain the agglomeration of active materials and promote the transportation of potassium ion and electron. In addition, the hollow carbon framework buffers volume expansion, maintains the structural integrity, and increases the electronic conductivity. Benefiting from this tertiary hierarchical structure, outstanding K-storage performance (402 mAh g-1 after 100 cycles at 50 mA g-1) is obtained when Co0.85Se-QDs/C is used as KIBs anode. More importantly, the selenization process in this work is newly reported and can be generally extended to prepare other quantum dots encapsulated in edge-limited frameworks for excellent energy storage.

A self-standing silver/crosslinked-poly(vinyl alcohol) network with microfibers, nanowires and nanoparticles and its linear aggregation.

Silver/polymer nanocomposites have made inroads into the fields of electronic devices, thermally conductive materials, antimicrobial agents and sensors. Here, we present the hydrothermal synthesis of a novel three-dimensional self-standing silver/crosslinked-poly(vinyl alcohol) (Ag/crosslinked-PVA) hybrid network constructed by linking three different subunits, namely, microfibers, nanowires and nanoparticles. One-dimensional crosslinked-PVA-based microfibers act as the skeleton of the sponge. Ag nanoparticles are uniformly embedded in the interior of the microfibers, and Ag nanowires grow outward from the interior of the microfibers. This Ag/crosslinked-PVA multi-architecture has not be observed or reported in current state-of-the-art studies. We simultaneously carry out two types of reactions, chemical reduction of Ag+ ions and intermolecular crosslinking of PVA chains, in the synthesis under hydrothermal conditions. Ag nanoparticles are formed and dispersed in the crosslinked-PVA microspheres. Then, these Ag/crosslinked-PVA microspheres bridge each other, forming microchains and microfibers. Ultimately, linear aggregation, which has rarely been mentioned in the literature, occurs in some adjacent Ag nanoparticles in the microfibers, and the Ag nanoparticles reorganize into nanowires. The Ag/crosslinked-PVA network is shown to be converted into a Ag/C composite through annealing, which exhibits electrocatalytic activity for glucose oxidation and can be used as a self-supporting electrode in an antibacterial nonenzymatic glucose sensor.

Hollow Multihole Carbon Bowls: A Stress-Release Structure Design for High-Stability and High-Volumetric-Capacity Potassium-Ion Batteries.

Potassium-ion batteries are potential alternatives to lithium-ion batteries for large-scale energy storage considering the low cost and high abundance of potassium. However, it is challenging to obtain stable electrode materials capable of undergoing long-term potassiation/depotassiation due to the high accumulated stress associated with the huge volume variation of the electrode. Here, we simulate the von Mises stress distributions of four different carbon three-dimensional models under an isotropic initial stress by the finite element method and reveal the critical role of the structure of a hollow multihole bowl on the strain-relaxation behavior. In this regard, nitrogen/oxygen codoped carbon hollow multihole bowls (CHMBs) are synthesized via hydrothermal carbonization coupled with an emulsion-templating strategy using biomass as the carbon source. Consistent with our simulation results, the CHMB anode remains stable for over 1000 cycles and delivers a high reversible capacity of 304 mAh g-1 at 0.1 A g-1. In addition to the reduced stress accumulation, the good electrochemical performances are also attributed to the surface capacitive mechanism and the shortened electron/ion transport distance in CHMBs. In particular, the CHMB composite electrode has a volumetric specific capacity 56% higher than that of hollow spheres due to the high tapped density of the bowl-shaped particles.

Fabrication of La2O3 Uniformly Doped Mo Nanopowders by Solution Combustion Synthesis Followed by Reduction under Hydrogen.

This work reports the preparation of La2O3 uniformly doped Mo nanopowders with the particle sizes of 40⁻70 nm by solution combustion synthesis and subsequent hydrogen reduction (SCSHR). To reach this aim, the foam-like MoO2 precursors (20⁻40 nm in size) with different amounts of La2O3 were first synthesized by a solution combustion synthesis method. Next, these precursors were used to prepare La2O3 doped Mo nanopowders through hydrogen reduction. Thus, the content of La2O3 used for doping can be accurately controlled via the SCSHR route to obtain the desired loading degree. The successful doping of La2O3 into Mo nanopowders with uniform distribution were proved by X-ray photon spectroscopy and transmission electron microscopy. The preservation of the original morphology and size of the MoO2 precursor by the La2O3 doped Mo nanopowders was attributed to the pseudomorphic transport mechanism occurring at 600 °C. As shown by X-ray diffraction, the formation of Mo2C impurity, which usually occurs in the direct H2 reduction process, can be avoided by using the Ar calcination-H2 reduction process, when residual carbon is removed by the carbothermal reaction during Ar calcination at 500 °C.

Facile synthesis of novel bowl-like hollow carbon spheres by the combination of hydrothermal carbonization and soft templating.

For the first time, bowl-like hollow carbon spheres (BHCSs) have been designed and fabricated by the combination of hydrothermal carbonization and soft templating. The obtained BHCSs exhibit well-defined shapes with the size ranging from 1 to 2 µm. As electrodes of electrochemical double layer capacitors they showed good performance.

Facile route for synthesis of mesoporous graphite encapsulated iron carbide/iron nanosheet composites and their electrocatalytic activity.

Mesoporous graphite encapsulated Fe3C/Fe nanosheet composites have been synthesized by a facile template free method using ferric nitrate, glycine and glucose as raw materials. X-ray diffraction, transmission electron microscopy, high-resolution transmission electron microscopy and Raman spectrometer have been used to characterize the composites. The formation process and morphology of the products have been discussed in detail. Interestingly, this facile route can synthesize graphite encapsulated Fe3C, Fe3C/Fe and Fe composites with two dimensional nanosheet structure by tuning the reaction temperature and the Fe3C and Fe nanoparticles with size less than 30nm are well dispersed on the carbon sheet. The mesoporous graphite encapsulated Fe3C/Fe nanosheet composites with a high specific surface area have application in non-noble metal electrocatalysis for hydrogen evolution reaction.

Hollow Porous VOx/C Nanoscrolls as High-Performance Anodes for Lithium-Ion Batteries.

Novel hollow porous VOx/C nanoscrolls are synthesized by an annealing process with the VOx/octadecylamine (ODA) nanoscrolls as both vanadium and carbon sources. In the preparation, the VOx/ODA nanoscrolls are first achieved by a two-phase solvothermal method using ammonium metavanadat as the precursor. Upon subsequent heating, the intercalated amines between the vanadate layers in the VOx/ODA nanoscrolls decompose into gases, which escape from inside the nanoscrolls and leave sufficient pores in the walls. As the anodes of lithium-ion batteries (LIBs), such hollow porous VOx/C nanoscrolls possess exceedingly high capacity and rate capability (904 mAh g-1 at 1 A g-1) and long cyclic stability (872 mAh g-1 after 210 cycles at 1 A g-1). The good performance is derived from the unique structural features of the hollow hierarchical porous nanoscrolls with low crystallinity, which could significantly suppress irreversible Li+ trapping as well as improve Li+ diffusion kinetics. This universal method of annealing amine-intercalated oxide could be widely applied to the fabrication of a variety of porous electrode materials for high-performance LIBs and supercapacitors.

Synthesis of Mesoporous Single Crystal Co(OH)2 Nanoplate and Its Topotactic Conversion to Dual-Pore Mesoporous Single Crystal Co3O4.

A new class of mesoporous single crystalline (MSC) material, Co(OH)2 nanoplates, is synthesized by a soft template method, and it is topotactically converted to dual-pore MSC Co3O4. Most mesoporous materials derived from the soft template method are reported to be amorphous or polycrystallined; however, in our synthesis, Co(OH)2 seeds grow to form single crystals, with amphiphilic block copolymer F127 colloids as the pore producer. The single-crystalline nature of material can be kept during the conversion from Co(OH)2 to Co3O4, and special dual-pore MSC Co3O4 nanoplates can be obtained. As the anode of lithium-ion batteries, such dual-pore MSC Co3O4 nanoplates possess exceedingly high capacity as well as long cyclic performance (730 mAh g(-1) at 1 A g(-1) after the 350th cycle). The superior performance is because of the unique hierarchical mesoporous structure, which could significantly improve Li(+) diffusion kinetics, and the exposed highly active (111) crystal planes are in favor of the conversion reaction in the charge/discharge cycles.