Role of amorphous engineering and cerium doping in NiFe oxyhydroxide for electrocatalytic water oxidation.

Amorphous engineering and atomistic doping provide an effective way to improve the catalytic activity in the oxygen evolution reaction (OER) of transition metal layered double hydroxides. Herein, Cerium (Ce) was introduced into NiFe-based oxyhydroxide using a modified aqueous sol-gel procedure. Ce as an electron acceptor promoted the coupling oxidation of Ni2+/3+ in NiFe oxyhydroxide, and the activated oxyhydroxide showed excellent catalytic activity in OER. The amorphous NiFeCe oxyhydroxide electrocatalyst demonstrated great modified OER catalytic activity under alkaline conditions and excellent cyclic stability, with an overpotential of only 284 mV at 50 mA cm-2, which was significantly better than amorphous NiFe oxyhydroxide and crystalline NiFeCe oxyhydroxide. Theoretical investigations further indicated that the overpotential of the rate-determining step (*OOH deprotonation) decreased from 0.66 to 0.41 V after Ce doping and strong electron interaction, effectively reducing the dependence of proton activity in the solution of OER, and optimizing the adsorption/desorption process of related oxygen-containing species in the reaction. This work also provides a good reference for optimizing OER activity by using rare-earth-metal induced electronic regulation strategies.

WCx-Supported RuNi Single Atoms for Electrocatalytic Oxygen Evolution.

Single-atom catalysts anchored to oxide or carbonaceous substances are typically tightly coordinated by oxygen or heteroatoms, which certainly impact their electronic structure and coordination environment, thereby affecting their catalytic activity. In this study, we prepared a stable oxygen evolution reaction (OER) catalyst on tungsten carbide using a simple pyrolysis method. The unique structure of tungsten carbide allows the atomic RuNi catalytic site to weakly bond to the surface W and C atoms. XRD patterns and HRTEM images of the WCx-RuNi showed the characteristics of phase-pure WC and W2C, and the absence of nanoparticles. Combined with XPS, the atomic dispersion of Ru/Ni in the catalyst was confirmed. The catalyst exhibits excellent catalytic ability, with a low overpotential of 330 mV at 50 mA/cm2 in 1 m KOH solutions, and demonstrates high long-term stability. This high OER activity is ascribed to the synergistic action of metal Ru/Ni atoms with double monomers. The addition of Ni increases the state density of WCx-RuNi near the Fermi level, promoting the adsorption of oxygen-containing intermediates and enhancing electron exchange. The larger proximity of the d band center to the Fermi level suggests a strong interaction between the d electrons and the valence or conduction band, facilitating charge transfer. Our research offers a promising avenue for reasonable utilization of inexpensive and durable WCx carrier-supported metal single-atom catalysts for electrochemical catalysis.

Iron clusters regulate local charge distribution in Fe-N4 sites to boost oxygen electroreduction.

The atomically-dispersed and nitrogen-coordinated iron (FeNC) on a carbon catalyst is a potential non-noble metal catalyst that can replace precious metal electrocatalysts. However, its activity is often unsatisfactory owing to the symmetric charge distribution around the iron matrix. In this study, atomically- dispersed Fe-N4 and Fe nanoclusters loaded with N-doped porous carbon (FeNCs/FeSAs-NC-Z8@34) were rationally fabricated by introducing homologous metal clusters and increasing the N content of the support. FeNCs/FeSAs-NC-Z8@34 exhibited a half-wave potential of 0.918 V, which exceeded that of the commercial benchmark Pt/C catalyst. Theoretical calculations verified that introducing Fe nanoclusters can break the symmetric electronic structure of Fe-N4, thus inducing charge redistribution. Furthermore, it can optimize a part of Fe 3d occupancy orbitals and accelerate OO fracture in OOH* (rate-determining step), thus significantly improving oxygen reduction reaction activity. This work provides a reasonably advanced pathway to modulate the electronic structure of the single-atom center and optimize the catalytic activity of single-atom catalysts.

Constructing atomically-dispersed Mn on ZIF-derived nitrogen-doped carbon for boosting oxygen reduction.

Exploring durable and highly-active non-noble-metal nanomaterials to supersede Pt-based nanomaterials is an effective way, which can reduce the cost and boost the catalytic efficiency of oxygen reduction reaction (ORR). Herein, we constructed atomically-dispersed Mn atoms on the ZIF-derived nitrogen-doped carbon frameworks (Mn-Nx/NC) by stepwise pyrolysis. The Mn-Nx/NC relative to pure nitrogen-doped carbon (NC) exhibited superior electrocatalytic activity with a higher half-wave potential (E 1/2 = 0.88 V) and a modest Tafel slope (90 mV dec-1) toward ORR. The enhanced ORR performance of Mn-Nx/NC may be attributed to the existence of Mn-Nx active sites, which can more easily adsorb intermediates, promoting the efficiency of ORR. This work provides a facile route to synthesize single-atom catalysts for ORR.

Designing hierarchical iron doped nickel-vanadium hydroxide microsphere as an efficient electrocatalyst for oxygen evolution reaction.

Exploring highly active and inexpensive electrocatalysts for oxygen evolution reaction (OER) is considered to be one of the preconditions for the development of energy and environment-related technologies. Nickel-based layered double hydroxides (LDHs) are extensively-studied OER electrocatalysts, but they still require relatively high overpotentials to achieve threshold current densities. In this work, iron-doped nickel-vanadium hydroxide microspheres (Fe-doped NiV HMS) were synthesized by doping iron ions into the NiV HMS through a facile cation-exchange method. The Fe-doped NiV HMS are hollow hierarchical structure stacked by high-density perpendicularly-lying nanosheets, which provide enough space for electrolyte penetration and diffusion. Owing to optimized composition and hollow hierarchical structure, the Fe-doped NiV HMS exhibits excellent electrocatalytic performance, which possessed a very low running overpotential (255 mV at 10 mA cm-2) and a smallest Tafel slope (56 mV dec-1) compared with hierarchical NiV HMS toward OER. Electrochemical results and density functional theory (DFT) manifest that Fe doping could regulate the electronic structure of NiV HMS, thus improving its electrical conductivity and electron transfer rate, and thus enhancing its catalytic activity. This research provides a convenient way to prepare Ni-based hydroxides as promising OER catalysts.

Synergies of Atomically Dispersed Mn/Fe Single Atoms and Fe Nanoparticles on N-Doped Carbon toward High-Activity Eletrocatalysis for Oxygen Reduction.

PGM-free (platinum group metal) electrocatalysts are intensively investigated and used as low-cost catalysts for the oxygen reduction reaction (ORR) in the field of fuel cells, but further studying their performance improvement methods and actual reaction mechanism is still a big a challenge. In this work, a novel eletrocatalyst containing atomically dispersed Mn/Fe single atoms (SAs) and Fe nanoparticles (NPs) on N-doped carbonaceous (nanosheet/nanotube hybrids) is fabricated via a simple pyrolysis method. This high-activity ORR electrocatalyst has higher half-wave potential (E1/2 = 0.91 V) and superior long-term durability in alkaline solutions and outperforms Pt/C catalysts, which can be ascribed to the synergetic interaction between Mn/Fe SAs and Fe-NPs. FeNPs/MnFeSAs-NC-25 has stronger reactant adsorption ability and a lower dissociation energy barrier than FeNPs/FeSAs-NC, which is conducive to breaking the O-O bond and accelerating ORR kinetics. This work presents a method to synthesize carbon-based electrocatalysts with high ORR activity and stability and shows that a variety of active sites encapsulated in N-doped carbonaceous materials can be a class of competitive candidates for PGM-free electrocatalysts.

Precise constructed atomically dispersed Fe/Ni sites on porous nitrogen-doped carbon for oxygen reduction.

Exploring highly-efficient noble-metal-free electrocatalysts for oxygen reduction reaction (ORR) is crucial for preparation of rechargeable metal-air batteries. Herein, FeNi-mIm (guest) was loaded on the surface of ZIF-8 (host) via a novel host-guest strategy, and the resulting ZIF-8@FeNi(mIm)X precursors can be converted to FeNi SAs/NC catalysts with controllable structures. Robust metal-organic framework (MOF)-derived atomically dispersed Fe/Ni dual single atom electrocatalysts for ORR were developed, followed by pyrolysis of the precursors. Characterizations showed that the atomically-dispersed Fe/Ni active sites were uniformly embedded in the N-doped carbon framework. As a result, the ORR performance was obviously improved with lower half-wave potential (E1/2 = 0.91 V) in alkaline media. Such improvement is mainly attributed to the synergy of fully-exposed bimetallic single atom active sites caused by the interaction of Fe/Ni 3d orbitals. The lower adsorption energy of intermediate hydroxyl groups on the active sites and the smaller ORR energy barrier were calculated by the density functional theory. The novelty FeNi SAs/NC catalysts showed faster ORR dynamics in the rate-determining step of four-electron transfer. The synthesis strategy reported here provides an efficient approach to construct high performance dual single-atom catalysts with fully-exposed active sites on the surface.

Highly Dispersed CoO Embedded on Graphitized Ordered Mesoporous Carbon as an Effective Catalyst for Selective Fischer-Tropsch Synthesis of C5+ Hydrocarbons.

Herein, we report the high Fischer-Tropsch synthesis performance of the Co-based catalysts supported on graphitized ordered mesoporous carbon (GMC-900) by using a facile strategy. Compared with CMK-3 and active carbon (AC), the obtained GMC-900 by using pollution-free soybean oil as a carbon source exhibited enhanced catalytic performance after loading Co species due to its highly crystallized graphitic structure and uniform dispersion of CoO. As a result, Co/GMC-900 was an effective catalyst with the maximum C5+ selectivity of 52.6%, which much outperformed Co/CMK-3 and Co/AC. This research provides an approach to produce advanced Co-based catalysts with satisfactory performance for efficient Fischer-Tropsch synthesis.

An Efficient Catalyst Derived from Carboxylated Lignin-Anchored Iron Nanoparticle Compounds for Carbon Monoxide Hydrogenation Application.

Catalytic activity and target product selectivity are strongly correlated to the size, crystallographic phase, and morphology of nanoparticles. In this study, waste lignin from paper pulp industry is employed as the carbon source, which is modified with carboxyl groups at the molecular level to facilitate anchoring of metals, and a new type of carbon-based catalyst was obtained after carbonization. As a result, the size of the metal particles is effectively controlled by the chelation between -COO- and Fe3+. Furthermore, Fe/CM-CL with a particle size of 1.5-2.5 nm shows excellent catalytic performance, the conversion of carbon monoxide reaches 82.3%, and the selectivity of methane reaches 73.2%.

Short-term Efficacy of the Percutaneous Vertebroplasty Using a Curved Versus Straight Vertebroplasty Needle in Osteoporotic Vertebral Compression Fractures.

The purpose of this study was to compare the efficacy of the curved puncture approach with 2 conventional approaches in percutaneous vertebroplasty (PVP) for the treatment of single-level osteoporotic vertebral compression fractures. Ninety-six patients with a single-level thoracolumbar vertebral fracture were surgically treated in the authors' department from February 2016 to February 2018. Patients were randomly divided into 3 groups, including 25 patients who had PVP punctured with a curved vertebroplasty needle (group C), 40 patients with unipedicular PVP with a straight vertebroplasty needle (group U), and 31 patients with bipedicular PVP with a straight vertebroplasty needle (group B). The short-term efficacies of PVP using different vertebroplasty needles were compared. Significant differences were tested preoperatively and postoperatively in vertebral body height variation, visual analog scale score, and Oswestry Disability Index in each of the 3 groups (P<.05). There was no significant difference among the groups in terms of Cobb angle correction and bone cement leakage. Group C and group U were superior to group B in terms of operative time and injected cement volume (P<.05). Twenty-four (96.0%) patients in group C and 29 (93.5%) patients in group B had centered cement distribution without significant differences (P>.05), which was superior to group U (P<.05). Curved puncture PVP achieved a satisfactory clinical outcome for osteoporotic vertebral compression fractures, with the advantages of less operative time, less injected cement volume, and more reasonable cement distribution for stabilization of the affected vertebrae. [Orthopedics. 2021;44(1):e131-e138.].

One-dimensional nitrogen-doped carbon frameworks embedded with zinc-cobalt nanoparticles for efficient overall water splitting.

Metal-organic frameworks (MOFs)-derived catalysts exhibit highly-efficient hydrogen or oxygen evolution performance on water splitting. However, it is an urgent problem to construct bifunctional electrocatalysts for both hydrogen and oxygen evolution performance. Herein, we adopted Ag nanowires as templates to prepare one-dimensional Ag nanowire@ZIF-8@ZIF-67 precursors (1D AgNW@ZIF-8@ZIF-67). Through pyrolysis, AgNW@ZIF-8@ZIF-67 precursors transformed into nitrogen-doped carbon frameworks (NCF) embedded with zinc-cobalt (ZnCo) nanoparticles on the surface of Ag NWs (denoted as Ag@ZnCo/NCF nanohybrids). The nanohybrids were consisted of Ag NWs with good conductivity and ZnCo/NCF nanohybrids with rich accessible active sites. Benefiting from their large specific surface area, accessible active sites and synergistic effect among components, Ag@ZnCo/NCF nanohybrids exhibit lower overpotentials of 139 mV and 279 mV at the current density of 10 mA cm-2 for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in alkaline solution, severally. Compared with other catalysts, Ag@ZnCo/NCF nanohybrids possess smaller Tafel slope, indicating their higher catalytic activity. This work provides a new perspective for designing low-cost and highly efficient bifunctional electrocatalysts for overall water splitting.

Exosomes in osteoarthritis and cartilage injury: advanced development and potential therapeutic strategies.

Articular cartilage injury is a common clinical problem, which can lead to joint dysfunction, significant pain, and secondary osteoarthritis (OA) in which major surgical procedures are mandatory for treatment. Exosomes, as endosome-derived membrane-bound vesicles, participating in intercellular communications in both physiological and pathophysiological conditions, have been attached great importance in many fields. Recently, the significance of exosomes in the development of OA has been gradually concerned, while the therapeutic value of exosomes in cartilage repair and OA treatment has also been gradually revealed. The functional difference of different types and derivations of exosomes are determined by their specific contents. Herein, we provide comprehensive understanding on exosome and OA, including how exosomes participating in OA, the therapeutic value of exosomes for cartilage injury/OA, and related bioengineering strategies for future therapeutic design.

The dual character of exosomes in osteoarthritis: Antagonists and therapeutic agents.

Exosomes have gained increasing attention as they participate in cell cross-talk in pathological environments and are functional paracrine factors of therapeutic stem cells. Osteoarthritis (OA) is a common age-related degenerative joint disease, leading to a debilitating lifestyle for sufferers. However, currently no drugs on the market promote cartilage repair, and the patients usually have to undergo arthroplasty in the late stage of OA. Although significant progress has been made in the development of stem cells for the treatment of OA and cartilage injury, problems like immune rejection remain. Recently, increasing evidence has demonstrated that exosomes from the joint microenvironment ("negative" exosomes) could play vital and complicated roles in the progression of OA. Moreover, exosomes from therapeutic cells ("therapeutic" exosomes) have also shown enormous potential for OA therapy/cartilage repair. Here, we first discuss the definition and biological background of exosomes. Then, we critically examine the roles of the "negative" exosomes in OA-affected joint. Then, we will cover the potential of the "therapeutic" exosomes for OA therapy/cartilage repair. Next, the recent progress of tissue engineering with exosomes, especially for OA therapy/cartilage repair, will also be discussed. Finally, the limitations and opportunities of exosome-based OA therapy will be outlined. STATEMENT OF SIGNIFICANCE: As natural extracellular vesicles, exosomes participate in the intercellular communication. On the basis of biological characteristics of exosomes, exosomes have their two sides for osteoarthritis (OA). On the one hand, exosomes in the OA microenvironment are involved in pathology of OA. On the other hand, exosomes from therapeutic cells have the potential as advanced strategies for OA therapy. In addition, the development of tissue engineering technology is beneficial to the exosome-based OA therapy. According to the latest research status, exosomes are of great significance and interest for the personalized and precision treatment of OA in the future, despite the limitations and challenges.

Characteristics, sources and health risks of toxic species (PCDD/Fs, PAHs and heavy metals) in PM2.5 during fall and winter in an industrial area.

Particulate toxic species, such as polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs), polycyclic aromatic hydrocarbons (PAHs) and heavy metals may have significant health risks. This study investigated characteristics, sources and health risks of all three classes of toxic species in PM2.5 (particles with aerodynamic diameter ≤2.5 µm) samples collected at an industrial area in Changzhou, a big city in the Yangtze Delta region of China. Fourteen heavy metals altogether constituted 2.87% of PM2.5 mass, with Fe, Al and Zn as the major elements. Principal component analysis (PCA) suggested that heavy metals came from four sources: vehicles, industry, crustal dust, mixed coal combustion and industrial process. The daily average concentration of 18 PAHs was 235.29 ng/m3, accounting for 0.21% of PM2.5 mass. The dominant PAHs were high molecular weight ones, contributing 73.5% to the total PAHs. Diagnostic analyses indicated that sources of PAHs included vehicle/coal combustion and petroleum emissions, wherein diesel emission played a more important role than gasoline emission. PCA showed that the largest contributor of PAHs was vehicle exhaust mixed with coal combustion, followed by three industry-related sources. Total concentration of 17 PCDD/Fs varied between 3.14 and 37.07 pg/m3, with an average of 14.58 pg/m3. The 10 PCDFs accounted for 70.5% of total concentration of 17 PCDD/Fs. Health risk assessments showed that the carcinogenic risk of heavy metals was acceptable, while risks from PAHs and PCDD/Fs cannot be ignored. Back trajectory analysis indicated that local/regional transported air masses from northern China was the major source areas of the toxic species.

Data on the convenient fabrication of carbon doped WO3-x ultrathin nanosheets for photocatalytic aerobic oxidation of amines at room temperature.

The oxidation of amines to imines is an important chemical transformation. In this article, we report original data on the synthesis of carbon doped WO3-x ultrathin nanosheets via an acid-assisted one-pot process, which exhibit excellent photocatalytic activity in the aerobic oxidation of amines to corresponding imines under visible light irradiation at room temperature. The composition, microstructure, morphology, photocatalytic activity of the corresponding samples and possible mechanism are included here. The data are related to "Oxide Defect Engineering Enables to Couple Solar Energy into Oxygen Activation" (Zhang et al., 2016).

Influence of Molecular Weight on Structure and Catalytic Characteristics of Ordered Mesoporous Carbon Derived from Lignin.

Bio-renewable lignin has been used as a carbon source for the preparation of porous carbon materials. Nevertheless, up to now, there are few studies about the influence of molecular weight of lignin on the structure and morphology of the ordered mesoporous carbon. Here, we synthesized the ordered mesoporous carbon derived from different molecular weights of lignin and Pluronic F127. Fortunately, we found that molecular weight is an important factor for obtaining highly ordered channels, high specific surface area, and ordered mesoporous carbon. More importantly, the narrow well-defined mesoporous channel could exert a spatial restriction effect to some extent, which can serve as nanoreactors for efficient reactions and enhance catalytic performance. The highly ordered mesoporous carbon from lignin is a good candidate for Fischer-Tropsch synthesis catalyst supports.

Investigation of submicron aerosol characteristics in Changzhou, China: Composition, source, and comparison with co-collected PM2.5.

Mass concentrations and chemical compositions of submicron particles (PM1) collected during July 2015 to April 2016 in Changzhou, a city in the Yangtze River Delta region, were systematically investigated for the first time. Specifically, an Aerodyne soot particle aerosol mass spectrometer (SP-AMS) was employed to characterize the water-soluble organic matter (WSOM). The average concentration of PM1 was 63.6 µg m-3, occupying ∼60% of co-collected PM2.5 mass. Water soluble inorganic ions (WSIIs) was the most abundant component with secondary ions (SO42-, NO3- and NH4+) as the dominant species. Organic matter (OM) accounted for 21.6% of PM1, with approximately 80% was water-soluble. Trace metals could constitute up to 3.0% of PM1 mass, and Fe, Al and Zn were the three most abundant ones. PAHs were predominated by ones with 5-6 rings, occupying over half of the PAHs mass; further analyses showed that fuel and coal combustion had significant contributions to PAHs. Positive matrix factorization of the WSOM data separated four factors: a traffic-related hydrocarbon-like OA (HOA), a local OA (LOA) likely associated with cooking and coal combustion emissions, etc., a secondary nitrogen-enriched OA (NOA) and an oxygenated OA (OOA). PCA analyses showed that crustal source was likely important for PM1 too. Back trajectory results implied that both PM1 and PM2.5 were mainly derived from local/regional emissions. Our findings present results regarding the PM1 chemistry and its relationship with the PM2.5 in Changzhou, which are valuable for the government to make effective policies to reduce the aerosol pollution in and near the city.

Synthesis of silicon carbide nanocrystals from waste polytetrafluoroethylene.

Resource utilization of waste plastic could solve the problem of environmental pollution and simultaneously relieve energy shortages, achieving sustainable development. In this study, the conversion of waste polytetrafluoroethylene (PTFE) to cubic silicon carbide (SiC) nanoparticles has been described. The structures and morphologies of the obtained SiC were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Furthermore, the FTIR spectrum of the obtained SiC sample suggests that the waste PTFE was completely converted into SiC in our approach.

Chemical synthesis of germanium nanoparticles with uniform size as anode materials for lithium ion batteries.

A simple Mg-thermal reduction reaction is reported to synthesize germanium (Ge) nanoparticles with a uniform size at a low temperature of 400 °C in an autoclave. The as-prepared Ge nanoparticles exhibit promising anode applications in lithium ion batteries with high capacity and excellent cycling stability.

Optimizing mixed culture of two acidophiles to improve copper recovery from printed circuit boards (PCBs).

In the previous research, the effects of different addition time and amount of printed circuit boards (PCBs) on cells growth and metals recovery in separated and mixed culture of Acidithiobacillus thiooxidans and Acidithiobacillus ferrooxidans were investigated. This paper aimed to optimize mixed culture of both acidophiles for maximizing PCBs addition amounts and copper leaching percentage simultaneously. Initially, influences of inoculums ratio between two acidophiles on their cells growth were studied. Then, initial medium pH and concentrations of FeSO4 · 7H2O and elemental sulfur (S(0)) were optimized by response surface methodology (RSM) to improve copper recovery. Finally, multiple-point PCBs addition was tested to determine maximal amounts. Results showed that with initial inoculums ratio (Af:At) 1:2, pH 1.56, FeSO4 · 7H2O and S(0) at 16.88 and 5.44 g/L, and PCBs addition 28.8 g/L, copper recovery reached 92.6% after 240 h cultivation. It was indicated that copper could be efficiently leached out from increased PCBs addition amount and FeSO4 · 7H2O was remarkably reduced from 22.1 to 16.88 g/L.