Crack Formation and Control in an AlCoCrFeNi High Entropy Alloy Fabricated by Selective Laser Melting.

The equiatomic AlCoCrFeNi high entropy alloy (HEA) is prone to cracking during the additive manufacturing process due to the high cooling rates observed, which limits its application to a large extent. In this study, the selective laser melting (SLM) technique was adopted to fabricate the alloy and the mechanism of crack formation was revealed. Most importantly, a new design strategy was proposed to suppress the generation of cracks, and the optimization of the preparation process was also studied in detail. It is found that the interlaminar crack is related to the heat input at the edge of the specimen, and the internal cracks are formed by solidification cracks. Alloys without interlaminar crack can be prepared by means of combination of the side inclination angle and the process parameters. Side inclination angle optimization provides a possibility for the preparation of crack-free AlCoCrFeNi HEA by SLM.

Carbon-Based Composites for Oxygen Evolution Reaction Electrocatalysts: Design, Fabrication, and Application.

The four-electron oxidation process of the oxygen evolution reaction (OER) highly influences the performance of many green energy storage and conversion devices due to its sluggish kinetics. The fabrication of cost-effective OER electrocatalysts via a facile and green method is, hence, highly desirable. This review summarizes and discusses the recent progress in creating carbon-based materials for alkaline OER. The contents mainly focus on the design, fabrication, and application of carbon-based materials for alkaline OER, including metal-free carbon materials, carbon-based supported composites, and carbon-based material core-shell hybrids. The work presents references and suggestions for the rational design of highly efficient carbon-based OER materials.

Decreased structural pathways mediating functional connectivity in obstructive sleep apnea.

BACKGROUND: Obstructive sleep apnea (OSA) is a common sleep breathing disorder that is often accompanied by changes in structural connectivity (SC) and functional connectivity (FC). However, the current understanding of the interaction between SC and FC in OSA is still limited. METHODS: The aim of this study is to integrate complementary neuroimaging modalities into a unified framework using multi-layer network analysis methods and to reveal their complex interrelationships. We introduce a new graph metric called SC-FC bandwidth, which measures the throughput of SC mediating FC in a multi-layer network. The bandwidth differences between two groups are evaluated using the network-based statistics (NBS) method. Additionally, we traced and analyzed the SC pathways corresponding to the abnormal bandwidth. RESULTS: In both the healthy control and patients with OSA, the majority offunctionally synchronized nodes were connected via SC paths of length 2. With the NBS method, we observed significantly lower bandwidth between the right Posterior cingulate gyrus and right Cuneus, bilateral Middle frontal gyrus, bilateral Gyrus rectus in OSA patients. By tracing the high-proportion SC pathways, it was found that OSA patients typically exhibit a decrease in direct SC-FC, SC-FC triangles, and SC-FC quads intra- and inter-networks. CONCLUSION: Complex interrelationship changes have been observed between the SC and FC in patients with OSA, which might leads to abnormal information transmission and communication in the brain network.

Polyaniline-graphene based composites electrode materials in supercapacitor: synthesis, performance and prospects.

Supercapacitors (SCs) have become one of the most popular energy-storage devices for high power density and fast charging/discharging capability. Polyaniline is a class of conductive polymer materials with ultra-high specific capacitance, and the excellent mechanical properties will play a key role in the research of flexible SCs. The synergistic effect between polyaniline and graphene is often used to overcome their respective inherent shortcomings, thus the high-performance polyaniline-graphene based nanocomposite electrode materials can be prepared. The development of graphene-polyaniline nanocomposites as electrode materials for SCs depends on their excellent microstructure design. However, it is still difficult to seek a balance between graphene performance and functionalization to improve the weak interfacial interaction between graphene and polyaniline. In this manuscript, the latest preparation methods, research progress and research results of graphene-polyaniline nanocomposites on SCs are reviewed, and the optimization of electrode structures and performances is discussed. Finally, the prospect of graphene-polyaniline composites is expected.

Recent progress in hierarchical nanostructures for Ni-based industrial-level OER catalysts.

Exploring efficient and low-cost oxygen evolution reaction (OER) electrocatalysts reaching the industrial level current density is crucial for hydrogen production via water electrolysis. In this feature article, we summarize the recent progress in hierarchical nanostructures for the industrial-level OER. The contents mainly concern (i) the design of a hierarchical structure; (ii) a Ni-based hierarchical structure for the industrial current density OER; and (iii) the surface reconstruction of the hierarchical structure during the OER process. The work provides valuable guidance and insights for the manufacture of hierarchical nanomaterials and devices for industrial applications.

Bio-inspired design of NiFeP nanoparticles embedded in (N,P) co-doped carbon for boosting overall water splitting.

The design and synthesis of cost-effective and stable bifunctional electrocatalysts for water splitting via a green and sustainable fabrication way remain a challenging problem. Herein, a bio-inspired method was used to synthesize NiFeP nanoparticles embedded in (N,P) co-doped carbon with the added carbon nanotubes. The obtained Ni0.8Fe0.2P-C catalyst displayed excellent hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) performances in both alkaline and alkaline simulated seawater solutions. The optimal Ni0.8Fe0.2P-C/NF only needs overpotentials of 45 and 242 mV to reach the current density of 10 mA cm-2 under HER and OER working conditions in 1.0 M KOH solution, respectively. First-principles calculations revealed the presence of a strong interaction between the carbon layer and metal phosphide nanoparticles. Benefiting from this and carbon nanotubes modification, the fabricated Ni0.8Fe0.2P-C presents impressive stability, working continuously for 100 h without collapse. A low alkaline cell voltage of 1.56 V for the assembled Ni0.8Fe0.2P-C/NF//Ni0.8Fe0.2P-C/NF electrocatalyzer could afford a current density of 10 mA cm-2. Moreover, when integrated with a photovoltaic device, the bifunctional Ni0.8Fe0.2P-C electrocatalyst demonstrates application potential for sustainable solar-driven water electrolysis.

S-Species-Evoked High-Valence Ni2+ δ of the Evolved ß-Ni(OH)2 Electrode for Selective Oxidation of 5-Hydroxymethylfurfural.

An efficient NiSx -modified ß-Ni(OH)2 electrode is reported for the selective oxidation reaction of 5-hydroxymethylfurfural (HMFOR) with excellent electrocatalytic 5-hydroxymethylfurfural (HMF) selectivity (99.4%), conversion (97.7%), and Faradaic efficiency (98.3%). The decoration of NiSx will evoke high-valence Ni2+ δ species in the reconstructed ß-Ni(OH)2 electrode, which are the real active species for HMFOR. The generated NiSx /Ni(OH)O modulates the proton-coupled electron-transfer (PCET) process of HMFOR, where the electrocatalytically generated Ni(OH)O can effectively trap the protons from the CHO end in HMF to realize electron transfer. The oxygen evolution reaction (OER) competes with the HMFOR when NiSx /Ni(OH)O continues to accumulate, to generate the NiSx /NiOx (OH)y intermediate. Density functional theory (DFT) calculations and experimental results verify that the adsorption energy of HMF can be optimized through the increased NiSx composition for more efficient capture of protons and electrons in the HMFOR.

The adsorption of single Au atom and nucleation on γ-Al2O3 surfaces.

Single-atom catalysts (SACs) in heterogeneous catalysts have attracted increasing attention and the adsorption and nucleation of single atom on the surface are closely related to the performance of the catalyst. The present work employed density functional theory calculations to examine the adsorption of single Au atom and nucleation on γ-Al2O3 surfaces at the atomic level. The effect of surface hydroxyls group on the adsorption and nucleation of single Au atom on γ-Al2O3 surfaces is explored. It was found that the spillover reactions of surface hydroxyls H atoms with the deposited Au- are not available on the hydroxylated surface. The interaction of Au to the clean surface is the stronger than to the hydroxylated surface. The even-odd alternations of Aux and weak binding of single Au atoms to γ-Al2O3 leads to large even-numbered Au cluster on the surface. Density of states and electron density difference analysis show that the electronic structure of Au/γ-Al2O3 is quite different from the reported Cu and Pd on Al2O3.

Differential sensitization toward lanthanide metal-organic framework for detection of an anthrax biomarker.

A novel Tb-doped Eu-based metal-organic framework (Eu-MOF@Tb) has been developed by incorporating hexanuclear europium cluster and 2,2'-bipyridine-5,5'-dicarboxylic acid as well as coordination with Tb(III). Owing to the diverse coordination status of Tb(III) and Eu(III) in MOF, antenna effect emission from Tb(III) can be invoked by dipicolinic acid (DPA), but the luminescence originating from Eu(III) remains unchanged. Taking advantage of this phenomenon, a ratiometric luminescent method for detection of DPA, a biomarker for Bacillus subtilis spores, was developed through differential sensitization toward lanthanide ions. This analysis method allowed for the detection of DPA in the 0.2-10 µM concentration range, with a detection limit of 60 nM. It was further validated by spiked recoveries (89.3-110%) of real-world samples with RSD values in the range 3.9-11%. Alongside this, a paper indicator test was prepared for naked-eye detection of DPA via a dose-sensitive color evolution from red to green under UV light. The effectiveness of the proposed approach was explored in the detection of bacterial spores in real biological and environmental samples and indicated great potential for applications as a real-time monitoring system against the anthrax threat.

Rational design of 3D N-doped graphene with a holey structure as a bifunctional electrode for sensitive methyl parathion detection and supercapacitors.

N-doped graphene with nano-sized holes possesses abundant electrochemically active sites at the exposed edge and an open porous structure, leading to a better electrochemical performance and faster electron and ion transport than the basal planes in graphene. In this study, three-dimensional graphene with a porous structure and abundant doped N (3d-NHG) were synthesized as bifunctional electrodes for methyl parathion (MP) detection and supercapacitors. The roles of N-doping and the holey construction in the electrochemical performance of the 3d-NHG were systematically investigated through a combined theory-experiment strategy. The 3d-NHG-based electrochemical sensor successfully detected methyl parathion in the range of 38 nm-380 µM with a low detection limit (2.27 nM) and superior sensitivity. Furthermore, the 3d-NHG also demonstrated potential for use in supercapacitors with a specific capacitance of 207 F g-1 at 1 A g-1 and excellent rate capability (76% capacitance retention at 10 A g-1). Density functional theory calculations revealed that the exposed carbon sites at the edge are the reactive sites for species adsorption. Moreover, the holey structure in 3d-NHG plays a dominating role in electrochemical processes and in the enhanced electrocatalysis. This work provides guidance for the rational design of high-performance bifunctional electrodes for MP detection and supercapacitors by defect engineering.

Carbon-incorporated bimetallic phosphide nanospheres derived from MOFs as superior electrocatalysts for hydrogen evolution.

Preparing low-cost and highly efficient electrocatalysts for the hydrogen evolution reaction using a simple strategy still faces challenges. In this work, we proposed a facile phosphating process to successfully transform CoFe-BTC (BTC = 1,3,5-benzenetricarboxylate) precursors into carbon-incorporated bimetallic phosphide (CoFe-P/C) nanospheres. Due to the synergistic effect between bimetals and uniformly covered carbon shells outside, the as-synthesized porous bimetallic phosphide nanospheres exhibit superior HER activity, enhanced kinetics, and excellent cycle durability in both acidic and alkaline solutions. The optimized material could afford a current density of 10 mA cm-2 with overpotentials of 138 and 193 mV for the HER in acidic and alkaline solutions, respectively. Meanwhile, it delivered small Tafel slopes of 84 and 78 mV dec-1 for the HER in 0.5 M H2SO4 and 1.0 M KOH, respectively. Moreover, an assembled alkaline electrolyzer enabled a low voltage of 1.62 V to drive a current density of 10 mA cm-2 for overall water splitting. DFT calculations indicate that the CoP-Fe2P composite is supposed to exhibit better HER performance than each component, revealing the vital role of the interfacial site in catalyzing the HER.

Pilot-Scale Vinification of Cabernet Sauvignon Using Combined Lactiplantibacillus plantarum and Saccharomyces cerevisiae to Achieve Wine Acidification.

Insufficient acidity in grape berries from warm climate regions has been exacerbated due to global warming, thereby becoming a major concern for winemaking. The wine lactic acid bacterium Lactiplantibacillus plantarum has potential to ameliorate wine acidity by producing lactic acid from hexose metabolism, but its impact on wine compositions and sensory outcomes is not well studied. Here, we evaluated acidification and fermentation performance of indigenous L. plantarum in two inoculation regimes (i.e., reverse inoculation and co-inoculation) by conducting pilot-scale vinification using Cabernet Sauvignon with low acidity. Important parameters of the bio-acidified wines, including fermentation kinetics, basic oenological parameters, volatile and sensory profile were compared to those in wines produced by single Saccharomyces cerevisiae with/without chemical acidification. Total titratable acidity in L. plantarum wines were either comparable or significantly higher compared to the chemical acidification control. Chemical profiling reviewed remarkable differences in certain organic acids and major volatile compounds, especially an up to a five-fold, six-fold, and nine-fold increase in lactic acid, ethyl lactate and isoamyl lactate, respectively. Changes in chemical compositions of the bio-acidified wines resulted in differentiated sensory perception compared to the control wines. Except having higher scores for "wine acidity", the flavour profile of the bio-acidified wines was shifted towards "jammy fruit" and "butter" aromas. Together, these findings highlighted the applicability of using L. plantarum to induce biological acidification along with modulation of wine flavour.

The surface structure, stability, and catalytic performances toward O2 reduction of CoP and FeCoP2.

The systematic atomistic level investigation of low-index surface structures, stabilities, and catalytic performances of CoP and FeCoP2 towards the O2 reduction reaction (ORR) is vital for their applications. Employing first-principles calculations, it is revealed that CoP and FeCoP2 present the same surface stability in the order of (101) ≈ (011) > (111) > (001) > (110) > (010) > (100). They also possess a similar Wulff equilibrium crystal shape with (101) and (011) exposing the largest surface area. From the electronic view, FeCoP2 presents improved electronic conductivity compared with CoP. From the energy view, whether FeCoP2 delivers improved electrocatalytic activity toward the ORR with respect to CoP depends on the reactive surfaces and sites. Among the 4 surfaces considered, only CoP(101), FeCoP2(101) and FeCoP2(011) delivered ORR performances theoretically when the bridge metal-metal site acts as the reactive center, which makes CoP(011) the only exception. CoP(101)-bCo-Co and FeCoP2(011)-bFe-Co exhibit a larger thermodynamic limiting potential than FeCoP2(101)-bCo-Co, suggesting their higher performances toward the ORR. The last step of HO* desorption as the rate-limiting step accounts for 3/4. The third step of transformation from O* to HO* as the most sluggish step accounts for 1/4. The work function, d-band center, Bader charge, and electronic localization function calculations are performed to reveal the HO adsorption nature. The present work provides fundamental insight into the effect of Fe doping into CoP, the determination of the catalyst surface and the key species adsorption nature to guide the rational design of high-performance materials.

Oxidative Coupling of Methane: Examining the Inactivity of the MnOx -Na2 WO4 /SiO2 Catalyst at Low Temperature.

Oxidative coupling of methane (OCM) catalyzed by MnOx -Na2 WO4 /SiO2 has great industrial promise to convert methane directly to C2-3 products, but its high light-off temperature is the most challenging obstacle to commercialization and its working mechanism is still a mystery. We report the discovery of a low-temperature active and selective MnOx -Na2 WO4 /SiO2 catalyst enriched with Q2 units in the SiO2 carrier, being capable of converting 23 % CH4 with 72 % C2-3 selectivity at 660 °C. From experiments and theoretical calculations, a large number of Q2 units in the MnOx -Na2 WO4 /SiO2 catalyst is a trigger for markedly lowering the light-off temperature of the Mn3+ ↔Mn2+ redox cycle involved in the OCM reaction because of the easy formation of MnSiO3 . Notably, the MnSiO3 formation proceeds merely through the SiO2 -involved reaction in the presence of Na2 WO4 : Mn7 SiO12 +6 SiO2 ↔7 MnSiO3 +1.5 O2 . The Na2 WO4 not only drives the light-off of this cycle but also gets it working with substantial selectivity toward C2-3 products. Our findings shine a light on the rational design of more advanced MnOx -Na2 WO4 based OCM catalysts through establishing new Mn3+ ↔Mn2+ redox cycles with lowered light-off temperature.

Chemically Activating Tungsten Disulfide via Structural and Electronic Engineering Strategy for Upgrading the Hydrogen Evolution Reaction.

Both improving the intrinsic activity and activating basal plane sites of the layered metal dichalcogenides are desirable to enhance their electrocatalytic performance for energy storage and conversion. Herein, we present palladium (Pd)-doped tungsten disulfide (WS2) epitaxially sheathed around linear tungsten oxide for the hydrogen evolution reaction (HER). The Pd doping is evidenced to tune the electronic structure of WS2 for activating basal sites of WS2, while the unique core-shell structure facilitates charge transfer. The as-prepared Pd-WS2/W3O with 5.65 wt % Pd content exhibits a small overpotential of only 54 mV at -10 mA cm-2 and superior stability in the acidic electrolyte, which are superior to that of the 5 wt % Pt/C benchmark and are unprecedented in the reported WS2-based electrocatalysts. Theoretical results have revealed that Pd substituting for W in coordination with four S atoms is thermodynamically stable, and the in-plane S atoms adjacent to the doped Pd represent new catalytic active centers for promoting hydrogen adsorption. This work provides a new multiscale structural and electronic engineering strategy for improving the catalytic performance of transition-metal dichalcogenides.

Defect-Engineered NiCo-S Composite as a Bifunctional Electrode for High-Performance Supercapacitor and Electrocatalysis.

Defect engineering is a reasonable solution to improve the surface properties and electronic structure of nanomaterials. However, how to introduce dual defects into nanomaterials by a simple way is still facing challenge. Herein, we propose a facile two-step solvothermal method to introduce Fe dopants and S vacancies into metal-organic framework-derived bimetallic nickel cobalt sulfide composites (NiCo-S). The as-prepared Fe-doped NiCo-S (Fe-NiCo-S) possesses improved charge storage kinetics and activities as electrode material for supercapacitors and the oxygen evolution reaction (OER). The obtained Fe-NiCo-S nanosheet has a high specific capacitance (2779.6 F g-1 at 1 A g-1) and excellent rate performance (1627.2 F g-1 at 10 A g-1). A hybrid supercapacitor device made of Fe-NiCo-S as the positive electrode and reduced graphene oxide (rGO) as the negative electrode presents a high energy density of 56.0 Wh kg-1 at a power density of 847.1 W kg-1 and excellent cycling stability (capacity retention of 96.5% after 10,000 cycles at 10 A g-1). Additionally, the Fe-NiCo-S composite modified by Fe doping and S vacancy has an ultralow oxygen evolution overpotential of 247 mV at 10 mA cm-2. Based on the density functional theory (DFT) calculation, defects cause more electrons to appear near the Fermi level, which is conducive to electron transfer in electrochemical processes. Our work provides a rational strategy for facilely introducing dual defects into metal sulfides and may provide a novel idea to prepare electrode materials for energy storage and energy conversion application.

Oxygen-deficient metal oxides supported nano-intermetallic InNi3C0.5 toward efficient CO2 hydrogenation to methanol.

Direct CO2 hydrogenation to methanol using renewable energy-generated hydrogen is attracting intensive attention, but qualifying catalysts represents a grand challenge. Pure-/multi-metallic systems used for this task usually have low catalytic activity. Here, we tailored a highly active and selective InNi3C0.5/ZrO2 catalyst by tuning the performance-relevant electronic metal-support interaction (EMSI), which is tightly linked with the ZrO2 type-dependent oxygen deficiency. Highly oxygen-deficient monoclinic-ZrO2 support imparts high electron density to InNi3C0.5 because of the considerably enhanced EMSI, thereby enabling InNi3C0.5/monoclinic-ZrO2 with an intrinsic activity three or two times as high as that of InNi3C0.5/amorphous-ZrO2 or InNi3C0.5/tetragonal-ZrO2 The EMSI-governed catalysis observed in the InNi3C0.5/ZrO2 system is extendable to other oxygen-deficient metal oxides, in particular InNi3C0.5/Fe3O4, achieving 25.7% CO2 conversion with 90.2% methanol selectivity at 325°C, 6.0 MPa, 36,000 ml gcat -1 hour-1, and H2/CO2 = 10:1. This affordable catalyst is stable for at least 500 hours and is also highly resistant to sulfur poisoning.

Carbon coating on metal oxide materials for electrochemical energy storage.

During the past decades, nano-structured metal oxide electrode materials have received growing attention due to their low development cost and high theoretical specific capacity, accordingly, quite a lot of metal oxide electrode materials are being used in electrochemical energy storage devices. However, the further development was limited by the relatively low electrical conductivity and the volume expansion during electrochemical reactions. Thus, many approaches have been proposed to obtain high-efficiency metal oxide electrode materials, such as designing nanomaterials with ideal morphology and high specific surface area, optimizing with carbon-based materials (such as graphene and glucose) to prepare nanocomposites, combining with conductive substrates to enhance the conductivity of electrodes, etc. Owning to the advantages of low cost and high chemical stability of carbon materials, core-shell structure formed by carbon-coated metal oxides is considered to be a promising solution to solve these problems. Therefore, this review mainly focuses on recent research advances in the field of carbon-coated metal oxides for energy storage, summarizing the advantages and disadvantages of common metal oxides and different types of carbon sources, and proposing methods to optimize the material properties in terms of structure and morphology, carbon layer thickness, coating method, specific surface area and pore size distribution, as well as improving electrical conductivity. In addition, the double or multi-layer coating strategy is also a reflection of the continuous development of carbon coating method. Hopefully, this rereview may provide a new direction for the renewal and development of future energy storage electrode materials.

Single-metal-atom catalysts supported on graphdiyne catalyze CO oxidation.

Single-metal-atom catalysts supported on graphdiyne (GDY) exhibit great potential for catalyzing low temperature CO oxidation in solving the increasingly serious environmental problems caused by CO emissions due to the high catalytic activity, clear structure, uniform metal distribution and low cost. First principle calculations were employed to study CO oxidation activities of four M@GDY single-atom catalysts (M = Pt, Rh, Cu, and Ni). For each catalyst, five possible reaction mechanisms including bi-molecular and tri-molecular reactions were discussed. According to the calculated reaction barriers, the preferred reaction pathway is via the bi-molecular Langmuir-Hinshelwood (BLH) ((CO + O2)* → OCOO* → CO2 + O*) route to yield the first CO2 molecule with 0.55, 0.51, and 0.53 eV as the energy barriers of the rate-limiting steps of Pt@GDY, Rh@GDY, and Cu@GDY, respectively, whereas for Ni@GDY, it switches to the tri-molecular Eley-Rideal (TER1) ((2CO)* + O2→ OCOOCO* → 2CO2) mechanism with the reaction barrier of the rate-limiting step being 1.27 eV. Based on the energy difference in the initial states of the five reaction mechanisms, TER1 is generally viable. No matter it is based on the calculated reaction barrier or the energy of the initial state of each mechanism, the non-noble Cu@GDY is supposed to be an efficient catalyst as the noble ones. The electronic properties are calculated to explain the bonding strength and origin of the catalytic performance. The GDY support plays an important role in the electron transfer process.

A Zeolitic-Imidazole Framework-Derived Trifunctional Electrocatalyst for Hydrazine Fuel Cells.

Hydrazine fuel cells are promising sustainable power sources. However, the high price and limited reserves of noble metal catalysts that promote the sluggish cathodic and anodic electrochemical reactions hinder their practical applications. Reflecting the enhanced diffusion and improved kinetics of nanostructured non-noble metal electrocatalysts, we report an efficient zeolitic-imidazole framework-derived trifunctional electrocatalyst for hydrazine oxidation, oxygen, and hydrogen peroxide reduction. Experimental results and theoretical calculations corroborate that the nanocarbon architecture with abundant Co-N species enhances the electronic interaction and optimizes the energy barriers of anodic hydrazine oxidation and cathodic oxygen reduction. The resulting assembled hydrazine-oxygen fuel cell yields a cell voltage and power density of 0.74 V and 20.5 mW cm-2, respectively. Moreover, benefiting from the liquid-liquid diffusion, the hydrazine-hydrogen peroxide cell shows a boosted cell voltage and power density, corresponding to 1.68 V and 41.0 mW cm-2. This work offers a highly active non-noble metal multifunctional electrocatalyst with a pioneering diffusion philosophy in the liquid electrochemical cells.