Chelation-mediated in-situ formation of ultrathin cobalt(oxy)hydroxides on hematite photoanode towards enhanced photoelectrochemical water oxidation

In this work,a facile chelation-mediated route was developed to fabricate ultrathin cobalt(oxy)hydroxides(CoOOH)nanosheets on hematite photoanode(Fe_(2)O_(3)).The route contains two steps of the adsorption of[Co-EDTA]^(2-)species on Fe_(2)O_(3) nanorod array followed by the hydrolysis in alkaline solution.The resulting CoOOH/Fe_(2)O_(3) exhibits a remarkably improved photocurrent density of 2.10 mA cm^(-2) at 1.23 V vs.RHE,which is ca.2.8 times that of bare Fe_(2)O_(3).In addition,a negative shift of onset potential ca.200 mV is achieved.The structural characterizations reveal the chelate EDTA plays important roles that enhance the adsorption of Co species and the formation of contact between CoOOH and Fe_(2)O_(3).(Photo)electrochemical analysis suggests,besides providing active sites for water oxidation,CoOOH at large extent promotes the charge separation and the charge transfer via passivating surface states and suppressing charge recombination.It also found CoOOH possesses some oxygen vacancies,which could act as trapping centers for photogenerated holes and facilitate the charge separation.Intensity modulated photocurrent spectroscopy(IMPS)shows that,under low applied potential the water oxidation mainly occurs on CoOOH,while under high applied potential the water oxidation could occur on both CoOOH and Fe_(2)O_(3).The findings not only provide an efficient strategy for designing ultrathin(oxy)hydroxides on semiconductors for PEC applications but also put forward a new insight on the role of CoOOH during water oxidation.

Structural control of magnetic nanoparticles for positive nuclear magnetic resonance imaging

In addition to the tens of millions of medical doses consumed annually around the world,a vast number of nuclear magnetic resonance imaging(MRI)contrast agents are being deployed in MRI research and development,offering precise diagnostic information,targeting capabilities,and analyte sensing.Superparamagnetic iron oxide nanoparticles(SPIONs)are notable among these agents,providing effective and versatile MRI applications while also being heavy-metal-free,bioconjugatable,and theranostic.We designed and implemented a novel two-pronged computational and experimental strategy to meet the demand for the efficient and rigorous development of SPION-based MRI agents.Our MATLAB-based modeling simulation and magnetic characterization revealed that extremely small maghemite SPIONs in the 1-3 nm range possess significantly reduced transversal relaxation rates(R_(2))and are therefore preferred for positive(T_(1)-weighted)MRI.Moreover,X-ray diffraction and X-ray absorption fine structure analyses demonstrated that the diffraction pattern and radial distribution function of our SPIONs matched those of the targeted maghemite crystals.In addition,simulations of the X-ray near-edge structure spectra indicated that our synthesized SPIONs,even at 1 nm,maintained a spherical structure.Furthermore,in vitro and in vivo MRI investigations showed that our 1-nm SPIONs effectively highlighted whole-body blood vessels and major organs in mice and could be cleared through the kidney route to minimize potential post-imaging side effects.Overall,our innovative approach enabled a swift discovery of the desired SPION structure,followed by targeted synthesis,synchrotron radiation spectroscopic studies,and MRI evaluations.The efficient and rigorous development of our high-performance SPIONs can set the stage for a computational and experimental platform for the development of future MRI agents.

Lithiophilic CoF_(2)@C hollow spheres towards spatial lithium deposition for stable lithium metal batteries

Lithium metal(LM)is a promising anode for next-generation batteries due to its high theoretical capacity and low electrode potential.Nonetheless,side reactions,volume change,and unwanted lithium dendrite growth seriously limit the practical application of LM.Herein,with the aid of a hard template approach,a novel lithiophilic CoF_(2)-carbon hollow sphere(CoF_(2)@C-HS)composite material is successfully prepared via a facile in-situ fluorination and etching strategy.The lithiophilic CoF_(2) acts as nucleation sites to reduce nucleation overpotential as well as induces the spatial Li deposition and the formation of LiFrich solid electrolyte interphase(SEI),and the hollow carbon matrix can enhance the electrical conductivity and offer free space for LM deposition.Theoretical simulations reveal that the synergistic effect of lithiophilic CoF_(2) and hollow carbon matrix homogenizes the electric field distribution and Li~+flux.Benefiting from these advantages,the CoF_(2)@C-HS-modified copper substrate electrode delivers an enhanced Coulombic efficiency(CE)of 93.7%for 280 cycles at 1 mA cm^(-2)and 1 mA h cm^(-2).The symmetrical cell using CoF_(2)@C-HS can stably cycle more than 1800 h with a low voltage hysteresis of 11 mV at a current density of 0.5 MA cm^(-2)and an areal capacity of 0.5 mA h cm^(-2).Moreover,the Li@CoF_(2)@C-HS composite anode enables more than 300 stable cycles at 1 C with a capacity retention of 95%in LiFePO_(4)-based full cell and 110 stable cycles at 1 C in LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)-based highvoltage full cell.This work might shed a new light on designing lithiophilic hosts to spatially confine LM deposition,realizing dendrite-free LM anodes and the practical applications of LM batteries.

Raman和TPR法研究丙烷氧化脱氢VOx/MoOx/Al2O3催化剂

采用原位激光拉曼和程序升温还原法研究了VOx分散于载有单层MoOx(4.8 Mo/nm2)的Al2O3上丙烷氧化脱氢.比较了这些催化剂和VOx/Al2O3的脱氢速率和选择性.在一定VOx表面密度下,每克VOx/MoOx/Al2O3催化剂的脱氢反应速率比VOx/Al2O3催化剂的高1.5～2倍.中间层MoOx通过抑制丙烷和丙烯燃烧反应速率增加了丙烯选择性.偏钒酸铵作钒源,使用钒的醇盐制备催化剂可使VOx形成高分散的单钒酸根和多聚钒酸根配位结构、减少V2O5晶粒的生成及促使V-O-Mo键的形成.催化剂的C3H6形成速率与其H2消耗速率成线性关系.

Paper-derived cobalt and nitrogen co-doped carbon nanotube@porous carbon as a nonprecious metal electrocatalyst for the oxygen reduction reaction

The oxygen reduction reaction(ORR)is a vitally important process in fuel cells.The development of high‐performance and low‐cost ORR electrocatalysts with outstanding stability is essential for the commercialization of the electrochemical energy technology.Herein,we report a facile synthesis of cobalt(Co)and nitrogen(N)co‐doped carbon nanotube@porous carbon(Co/N/CNT@PC‐800)electrocatalyst through a one‐step pyrolysis of waste paper,dicyandiamide,and cobalt(II)acetylacetonate.The surface of the hierarchical porous carbon supported a large number of carbon nanotubes(CNTs),which were derived from dicyandiamide through the catalysis of Co.The addition of Co resulted in the formation of a hierarchical micro/mesoporous structure,which was beneficial for the exposure of active sites and rapid transportation of ORR‐relevant species(O2,H+,OH?,and H2O).The doped N and Co formed more active sites to enhance the ORR activity of the electrocatalyst.The Co/N/CNT@PC‐800 material exhibited optimal ORR performance with an onset potential of 0.005 V vs.Ag/AgCl and a half‐wave potential of?0.173 V vs.Ag/AgCl.Meanwhile,the electrocatalyst showed an excellent methanol tolerance and a long‐term operational durability than that of Pt/C,as well as a quasi‐four‐electron reaction pathway.The low‐cost and simple synthesis approach makes the Co/N/CNT@PC‐800 a prospective electrocatalyst for the ORR.Furthermore,this work provides an alternative approach for exploring the use of biomass‐derived electrocatalysts for renewable energy applications.

High–Speed electron beam curing of thick electrode for high energy density Li-ion batteries

Electron beam curing is demonstrated as a promising method for high speed,low cost and environmentally friendly battery electrode manufacturing.This work reports transfer of this process to pilot scale equipment and evaluation of electrochemical performance in prototype 1.5 Ah pouch cells.Thick LiNi0.5Mn0.3Co0.2O2(NMC532)composite electrodes with an areal loading of 25 mg cm^-2(~4 mAh cm^-2)are successfully cured at a line speed of 500 feet per minute at 275 keV.Compared to the NMC532 cathode processed via a conventional coating method,the electron beam cured electrodes show higher capacity fade in the first 100 cycles,but similar fade rate afterwards.Further improvement strategies are proposed and discussed.This work demonstrates that electron beam curing is a promising method for manufacturing thick battery electrodes at high speeds and low capital/operation cost.

In situ spectroscopic insights into the redox and acid-base properties of ceria catalysts

Cerium oxide(ceria)plays an important and fascinating role in heterogeneous catalysis as illustrated by its versatile use as a catalyst,a catalyst support,or a promotor in various oxidation and reduction reactions.Central to these reactions is the rich defect chemistry,facile redox capability,and unusual acid-base properties of ceria.Understanding the unique redox and acid-base properties of ceria is essential to build the structure-catalysis relationship so that improved catalytic functions can be achieved for ceria-based materials.Among the characterization toolbox,spectroscopic approach indisputably stands out for its unparalleled power in offering chemical insights into the surface properties of ceria at atomic and molecular level.In this review,we summarize advances in revealing the redox and acid-base properties of ceria via a variety of spectroscopic methods including optical,X-ray,neutron,electronic and nuclear spectroscopy.Both direct spectroscopy characterization and its coupling with probe molecules are analyzed to illustrate how the nature,strength and density of different surface sites are influenced by the pretreatment,the morphology and size of ceria nanoparticles.Further directions in taking advantage of in situ/operando spectroscopy for better understanding the catalysis of ceria-based materials are proposed in the summary and outlook section.

A review of the interactions between ceria and H2 and the applications to selective hydrogenation of alkynes

Cerium oxide(ceria) has found a wide variety of applications in catalysis including as a catalyst, a modifier, or a support, largely thanks to its robust redox properties and versatile acid-base function. While it is often utilized for oxidation reactions, ceria has recently attracted intense research interest for its unusual ability to selectively hydrogenate alkynes to alkenes. The intriguing hydrogenation ability of ceria has sparked renewed research efforts to understand how pure ceria works as a hydrogenation catalyst. In this review, recent advances in both experimental and computational studies of ceria are summarized, focusing on the interaction of ceria with H2 and in hydrogenation reactions. Significant insights from various studies including in situ spectroscopy/microscopy and theoretic modeling of ceria in hydrogen-involved reactions are discussed, which shed light on the origin of the hydrogenation ability of ceria and the reaction mechanisms involved in ceria-catalyzed alkyne hydrogenation. Ways to further improve both the mechanistic understanding and catalytic performance of ceria-based materials for hydrogenation reactions are proposed at the end in the summary and outlook section.

Phosphorylated mesoporous carbon as effective catalyst for the selective fructose dehydration to HMF

Phosphorylated mesoporous carbons （PMCs） were investigated as catalysts in the dehydration of fructose to hydroxymethylfurfural （HMF）. The acidic PMCs show better selectivity to HMF compared to sulfonated carbon catalyst （SC） despite lower activity. The concentration of P-O groups on the PMC was correlated with the activity/selectivity of the catalysts; the higher the P-O concentration, the higher the activity. However, the higher the P-O content, the lower the selectivity to HME Indeed, a lower concentration of the P-O groups minimized the degradation of HMF to levulinic acid and the formation of by-products, such as humines. Stability tests showed that these systems deactivate due to the formation of humines and water insoluble by-products derived from the dehydration of fructose which blocked the catalytically active sites.

Global characterization of modifications to the charge isomers of IgG antibody

Posttranslational modifications of antibody products affect their stability,charge distribution,and drug activity and are thus a critical quality attribute.The comprehensive mapping of antibody modifications and different charge isomers(CIs)is of utmost importance,but is challenging.We intended to quantitatively characterize the posttranslational modification status of CIs of antibody drugs and explore the impact of posttranslational modifications on charge heterogeneity.The CIs of antibodies were fractionated by strong cation exchange chromatography and verified by capillary isoelectric focusing-whole column imaging detection,followed by stepwise structural characterization at three levels.First,the differences between CIs were explored at the intact protein level using a top-down mass spectrometry approach;this showed differences in glycoforms and deamidation status.Second,at the peptide level,common modifications of oxidation,deamidation,and glycosylation were identified.Peptide mapping showed nonuniform deamidation and glycoform distribution among CIs.In total,10 N-glycoforms were detected by peptide mapping.Finally,an in-depth analysis of glycan variants of CIs was performed through the detection of enriched glycopeptides.Qualitative and quantitative analyses demonstrated the dynamics of 24 N-glycoforms.The results revealed that sialic acid modification is a critical factor accounting for charge heterogeneity,which is otherwise missed in peptide mapping and intact molecular weight analyses.This study demonstrated the importance of the comprehensive analyses of antibody CIs and provides a reference method for the quality control of biopharmaceutical analysis.

Boosting High-Rate Zinc-Storage Performance by the Rational Design of Mn_(2)O_(3) Nanoporous Architecture Cathode

Manganese oxides are regarded as one of the most promising cathode materials in rechargeable aqueous Zn-ion batteries(ZIBs)because of the low price and high security.However,the practical application of Mn2O3 in ZIBs is still plagued by the low specific capacity and poor rate capability.Herein,highly crystalline Mn2O3 materials with interconnected mesostructures and controllable pore sizes are obtained via a ligand-assisted self-assembly process and used as high-performance electrode materials for reversible aqueous ZIBs.The coordination degree between Mn2+and citric acid ligand plays a crucial role in the formation of the mesostructure,and the pore sizes can be easily tuned from 3.2 to 7.3 nm.Ascribed to the unique feature of nanoporous architectures,excellent zinc-storage performance can be achieved in ZIBs during charge/discharge processes.The Mn2O3 electrode exhibits high reversible capacity(233 mAh g−1 at 0.3 A g−1),superior rate capability(162 mAh g−1 retains at 3.08 A g−1)and remarkable cycling durability over 3000 cycles at a high current rate of 3.08 A g−1.Moreover,the corresponding electrode reaction mechanism is studied in depth according to a series of analytical methods.These results suggest that rational design of the nanoporous architecture for electrode materials can effectively improve the battery performance.

Preface to Special Issue on Advances in Ceria Catalysis

Ceria,which acts as a“star”among the metal-oxides,has established to be one of the most promising materials for chemical transformations and energy applications owing to its redox and acid–base properties.Ceria has become a key component in three-way catalytic converters,water-gas shift reaction,CO oxidation,methane combustion,and complex organic reactions.More importantly,introducing of other metals to ceria,tailoring the shape of the ceria,and reducing structure size of ceria,usually decrease the formation energy of oxygen vacancy(V?)and lead to unique catalytic performances.

作为炭材料前驱体的离子液聚合物的简易合成(英文)

采用一步法合成新型离子液聚合物,并以聚合物作为炭材料的前驱体。这种新型离子液聚合物的特征包括:聚合无需添加引发剂,聚合引入的阴离子能够控制材料的微孔大小。以含Cl-的离子液聚合物为前驱体合成的炭材料具有较小的比表面积(47m2/g),而以含较大(三氟甲基磺酰基)亚胺基阴离子的离子液聚合物为前驱体合成的炭材料具有较大的比表面积(595m2/g)。含二氰胺阴离子的离子液聚合物为前驱体合成的炭材料的比表面积为30m2/g。

Few-layered graphene via gas-driven exfoliation for enhanced supercapacitive performance

High-quality graphene flakes have long been desirable for numerous applications including energy stor- age, printable electronics, and catalysis. In this contribution, we report a green, efficient, facile gas-driven exfoliation process for the preparation of high-quality graphene in large scale. The gas exfoliation process was realized by the interplay between the expansion of interlayer at high temperature and the gasifi- cation of liquid nitrogen within the interlayer. Detailed experiments demonstrated that the higher tem- perature was critical to the formation of fewer layers. The exfoliated graphene was proved to be of high quality. We further investigated the electrochemical behavior of this exfoliated graphene. As a result, this few-layered graphene demonstrated an enhanced capability as a supercapacitor, much higher than its counterpart parent material.

Ni_xWO_(2.72) nanorods as an efficient electrocatalyst for oxygen evolution reaction

Ni_xWO_(2.72) nanorods(NRs) are synthesized by a one-pot reaction of Ni(acac)_2 and WCl_4. In the rod structure, Ni(Ⅱ) intercalates in the defective perovskite-type WO_(2.72) and is stabilized. The Ni_xWO_(2.72) NRs show the x-dependent electrocatalysis for the oxygen evolution reaction(OER) in 0.1 M KOH with Ni_(0.78)WO_(2.72) being the most efficient, even outperforming the commercial Ir-catalyst. The synthesis is not limited to Ni_xWO_(2.72) but can be extended to M_xWO_(2.72)(M = Co, Fe) as well,providing a new class of oxide-based catalysts for efficient OER and other energy conversion reactions.

Activation and surface reactions of CO and H2 on ZnO powders and nanoplates under CO hydrogenation reaction conditions

Activation and surface reactions of CO and H2 on ZnO powders and nanoplates under CO hydrogenation reaction conditions were(quasi) in situ studied using temperature programmed surface reaction spectra, diffuse reflectance Fourier transform infrared spectroscopy, inelastic neutron scattering spectroscopy and electron paramagnetic resonance. CO undergoes disproportion reaction to produce gaseous CO2 and surface carbon adatoms, and adsorbs to form surface formate species. H2 adsorption forms dominant irreversibly-adsorbed surface hydroxyl groups and interstitial H species and very minor surface Zn-H species. Surface formate species and hydroxyl groups react to produce CO2 and H2, while surface carbon adatoms are hydrogenated by surface Zn-H species sequentially to produce CH(a), CH2(a), CH3(a)and eventually gaseous CH4. The ZnO nanoplates, exposing a higher fraction of Zn-ZnO(0001) and OZnO(000–1) polar facets, are more active than the ZnO powders to catalyze CO hydrogenation to CH4.These results provide fundamental understanding of the reaction mechanisms and structural effects of CO hydrogenation reaction catalyzed by ZnO-based catalysts.

Defects in Statically Unstable Solids: The Case for Cubic Perovskite α-CsPbI3

High-temperature phases of solids are often dynamically stable only.First-principles study of point defects in such solids at 0 K is prohibited by their static instability,which results in random structures of the defect-containing supercell so that the total energy of the supercell is randomly affected by structural distortions far away from the defect.Taking cubic perovskiteα-Cs Pb I_(3) as an example,we first present the problem incurred by the static instability and then propose an approach based on molecular dynamics to carry out ensemble average for tackling the problem.Within affordable simulation time,we obtain converged defect ionization energies,which are unattainable by a standard approach and allow us to evaluate its defect tolerance property.Our work paves the way for studying defects in statically unstable solids.

Formation of carbon and oxygen rich surface layer on high purity magnesium by atmospheric carbon dioxide plasma

Carbon and oxygen-rich corrosion barrier layer formed on Mg by a simple and scalable CO_(2) atmospheric plasma(CO_(2)-AP)process.The reactive CO_(2)-AP interacts with the Mg surface and forms a unique layered structure with the top MgCO_(3)/MgO-intermixed particulates pillars and the bottom dense layer.The surface features were simultaneously formed on the nano-/micro-structured MgO layer by carbonate molecules,plasma-active CO_(2) molecules,and/or other volatile organic compounds on the nano-/micro-structured MgO particle layer.The resulting surfaces after CO_(2)-AP were either hydrophobic or hydrophilic and exhibited lower anodic current or high resistance for Mg corrosion.For the hydrophobic surfaces of CO_(2)-AP treated Mg,molecular dynamic simulations were performed to understand the origin of hydrophobicity and identified that the amorphous carbon layers formed on the Mg surface are the source.The environmentally benign abundant-gas-based process enables the cost reduction associated with waste treatment,generation of by-product,and supply of raw material.

Computational Design of Azo-anthraquinone Schiff Base Mn Complexes as Mediators for Biofuel Cell Cathode

The cathode of biofuel cell reduces molecular oxygen to water using four electrons, an enzyme of multicopper oxidase family, laccase, is contained, though its electron transfer efficiency from the electrode resulted in rate determining process. To improve this electron, transfer via mediators, we have investigated several mediator metal complexes between the electrode and laccase, in particular hydrophobic pocket on the surface. We have discussed DFT computational results and selected experimental data of new Mn(III/II) Schiff base complexes having redox active (anthraquinone) ligands and photochromic (azobenzene) ligands about azobenzene moiety at the sole molecular level. Moreover, we carried out computational docking simulation of laccase and complexes considering trans-cis photoisomerization (electronic states) and Weigert effect (molecular orientation to fit better) of azobenzene moiety. Additionally, actual experimental data also presented to indicate the expected merits for mediators.