Highly selective electrosynthesis of imines via electroreduction coupling of nitroarenes with aryl aldehydes on Co_(9)S_(8)with positively charged sulfur vacancies

The electrocatalytic synthesis of imines through the reductive imination of nitroarenes with aldehydes is a facile,environmentally friendly,and valuable process.In this study,high selectivity electrosynthesis of imines was realized through the electrocatalytic C-N coupling reaction between nitroarenes and aryl aldehydes on Co_(9)S_(8)nanoflowers with rich sulfur vacancies(Co_(9)S_(8)-Vs).Comparative experiments revealed that positively charged sulfur vacancies play a pivotal role in boosting catalytic selectivity towards imines.Electron-deficient sulfur vacancies intensified the adsorption of negatively charged Ph-NO_(2),thereby enhancing the conversion rate of the electrochemical nitrobenzene-reduction reaction(eNB-RR).Simultaneously,sulfur vacancies augmented the adsorption capability of negatively charged Ph-CHO,enriching Ph-CHO species at the electrode interface and expediting the Schiff base condensation reaction rate.The experimental results show that the reaction conditions can satisfy the different nitroarenes and aryl aldehydes in the electrocatalytic aqueous-phase system under mild conditions to obtain the corresponding imine products in high selectivity.This study provides a facile and environmentally friendly pathway for future electrocatalytic synthesis of imine.

正常赖默—悌曼反应研究:超声波辐射与相转移催化合成方法

系统研究了正常及反常赖政－悌曼反应（NormalorAbnormalReliner－TiemannReavction，NRYorART）；研究了相转移住化方法和超声波辐射技术及其在正常Reliner—Tiemann（NRT）反应中的应用，从而使反应条件温和，效率增加，对邻比大，时间缩短，取得较好收效。

Electrochemical lithium storage performance of three-dimensional foam-like biocarbon/MoS2 composites

Molybdenum disulfide(MoS2)was loaded on biocarbon using waste camellia dregs(CDs)as the carbon source,which was further coated with dopamine hydrochloride to construct biocarbon/MoS2 electrode composites.The electrochemical lithium storage performance of the composites with different MoS2 contents was investigated.SEM results demonstrated that the composite had a three-dimensional foam-like structure with MoS2 as the interlayer.XRD and HRTEM tests revealed that MoS2 interlayer spacing in the composite was expanded.XPS analysis showed that new Mo—N bonds were formed in the active material.The electrochemical tests showed that the composite with a MoS2 content of 63%had a high initial specific capacity of 1434 mA·h/g at a current density of 100 mA/g.After a long cycle at a high current,it also showed good cycling stability and the capacity retention was nearly 100%.In addition,it had good lithium ion deintercalation ability in the electrochemical kinetics test.

Nucleation and growth mechanism of electrodeposited Ni−W alloy

The nucleation and growth mechanism of electrodeposited Ni−W alloy were investigated.Cyclic voltammetry(CV)and chronoamperometry(CA)were used to examine the electrochemical behavior and nucleation mechanism of the electrodeposited Ni−W alloy.The nucleation type and kinetic parameters of the electrodeposited Ni−W alloy were obtained from the CA analysis results.SEM,AFM,and TEM were also used to investigate the nucleation and growth process of the electrodeposition of Ni−W alloy.The results demonstrate that the nucleation and initial stages of the growth phase of the Ni−W alloy undergo the formation,movement,and aggregation of atoms,single crystals,and nanoclusters.When the size of single crystal increases up to approximately 10 nm and the average size of the crystal granules is approximately 68 nm,they no longer grow.Increasing the applied potential increases the number of nuclei but does not affect the size of the final crystal granules.Therefore,the electrodeposited Ni−W alloy shows a nanocrystalline structure.

Pulse electroplating of Ni-W-P coating and its anti-corrosion performance

Ni-W-P coatings were electrodeposited on copper substrates by pulse electroplating.Effects of electrolyte pH(1-3),temperature(40-80°C),average current density(1-7A/dm2)and pulse frequency(200-1000Hz)on deposition rate,structure and corrosion resistance performance of Ni-W-P coatings were studied by single factor method.Surface morphology,crystallographic structure and composition of Ni-W-P coatings were investigated by means of scanning electron microscopy,X-ray diffractometry and energy dispersive X-ray spectroscopy,respectively.Corrosion resistance performances of Ni-W-P coatings were studied by potentiodynamic polarization and electrochemical impedance spectroscopy in3.5%NaCl solution(mass fraction)and soil-containing solution.It was found that the pulse electroplated Ni-W-P coatings have superior corrosion resistance performance and the electroplating parameters significantly affect the structure and corrosion resistance performance of Ni-W-P coatings.The optimized parameters of pulse electroplating Ni-W-P coatings were as follows:pH2.0,temperature60°C,average current density4A/dm2,and pulse frequency600Hz.The Ni-W-P coating prepared under the optimized parameters has superior corrosion resistance(276.8kΩ)and compact surface without any noticeable defect.

Electronic structure regulation on layered double hydroxides for oxygen evolution reaction

Oxygen evolution reactions(OERs)as core components of energy conversion and storage technology systems,such as water splitting and rechargeable metal–air batteries,have attracted considerable attention in recent years.Transition metal compounds,particularly layered double hydroxides(LDHs),are considered as the most promising electrocatalysts owing to their unique two-dimensional layer structures and tunable components.However,heir poor intrinsic electrical conductivities and the limited number of active sites hinder their performances.The regulation of the electronic structure is an effective approach to improve the OER activity of LDHs,including cationic and anionic regulation,defect engineering,regulation of intercalated anions,and surface modifications.In this review,we summarize recent advances in the regulation of the electronic structures of LDHs used as electrocatalysts in OERs.In addition,we discuss the effects of each regulation type on OER activities.This review is expected to shed light on the development and design of effective OER electrocatalysts by summarizing various electronic structure regulation pathways and the effects on their catalytic performances.

pH-Induced selective electrocatalytic hydrogenation of furfural on Cu electrodes

The efficient and selective electrocatalytic hydrogenation(ECH)of furfural is considered a green strategy for achieving biomass-derived high-value chemicals.Regulating an aqueous electrolytic environment,a green hydrogen energy source of water,is significant for improving the selectivity of products and reducing energy consumption.In this study,we systematically investigated the mechanism of pH dependence of product selectivity in the ECH of furfural on Cu electrodes.Under acidic conditions,the oxygen atom dissociated directly from hydrogenated furfural-derived alkoxyl intermediates,followed by stepwise hydrogenation until H_(2)O formation via a thermodynamically favorable proton-coupled electron transfer process,thereby inducing a high proportion of the hydrogenolysis product(2-methylfuran).However,under partial alkaline conditions,furfural could be directly hydrogenated to furfuryl alcohol(selectivity~98%)due to the high-energy barrier of the deoxidation process via a surface hydride(Had)transfer.Our results highlight the vital role of the electrolytic environment in furfural selective conversion and broaden our fundamental understanding of hydrodeoxygenation reactions in ECH.

Electrochemically formed PtFeNi alloy nanoparticles on defective NiFe LDHs with charge transfer for efficient water splitting

Efficient and stable bifunctional electrocatalysts for water splitting is essential for producing hydrogen and alleviating huge energy consumption.Meanwhile,charge transfer engineering is an efficient approach to modulate the localized electronic properties of catalysts and tune the electrocatalytic performance.Herein,we tactfully fabricate PtFeNi alloys/NiFe layered double hydroxides(LDHs)heterostructure by an easily electrochemical way with a small amount of Pt.The experimental and theoretical results unravel that the charge transfer on the alloy clusters modulated by the defective substrates(NiFe LDHs),which synergistically optimizes the adsorption energy of the reaction intermediates.The electrocatalyst exhibits an ultra‐low overpotential of 81 and 243 mV at the current density of 100 mA cm^(–2) for hydrogen evolution and oxygen evolution,respectively.Furthermore,the overall water splitting indicates that PtFeNi alloys/NiFe LDHs presents an ultra‐low overpotential of 265 and 406 mV to reach the current density of 10 and 300 mA cm^(–2),respectively.It proves that the PtFeNi alloys/NiFe LDHs catalyst is an excellent dual‐function electrocatalyst for water splitting and promising for industrialization.This work provides a new electrochemical approach to construct the alloy heterostructure.The prepared heterostructures act as an ideal platform to investigate the charge re‐distribution behavior and to improve the electrocatalytic activity.

Cobalt‐regulation‐induced dual active sites in Ni_(2)P for hydrazine electrooxidation

Better understanding of electrochemical reaction behaviors of hydrazine electrooxidation at metal phosphides has long been desired and the optimization of reaction kinetics has been proved to be operable.Herein,the dehydrogenation kinetics of hydrazine electrooxidation at Ni_(2)P is adjusted by Co as the(Ni_(0.6)Co_(0.4))_(2)P catalyzes HzOR effectively with onset potential of–45 mV and only 113 mV is needed to drive the current density of 50 mA cm^(‒2),showing over 60 mV lower than Ni_(2)P and Co_(2)P.It also delivers the maximum power density of 263.0 mW cm^(-2) for direct hydrazine fuel cell.Detailed experimental results revealed that Co doping not only decreases the adsorption energy of N_(2)H_(4) on Ni sites,lowering the energy barrier for dehydrogenation,but also acts as the active sites in the optimal reaction coordination to boost the reaction kinetics.This work represents a breakthrough in improving the catalytic performance of non‐precious metal electrocatalysts for hydrazine electrooxidation and highlights an energy‐saving electrochemical hydrogen production method.

Regulating carbon work function to boost electrocatalytic activity for the oxygen reduction reaction

Electronic regulation of carbon is essential for developing non-platinum electrocatalysts for oxygen reduction reactions(ORRs).In this work,we used Cs to further regulate the electronic structure of nitrogen-doped(N-doped)carbon.The Cs atoms coordinated with the nitrogen atom in the N-doped carbon for injecting electrons into the carbon conjugate structure and reducing the work function of the carbon network.The low-work-function surface improved electron donation,facilitated O_(2) dissociation,and enhanced the adsorption of an OOH^(*) intermediate.Thus,electrocatalytic performance for the ORR was improved.The material shows potential as an ORR electrocatalyst comparable with Pt/C.

Sulfuryl Group-Involved Drugs Approved by the Food and Drug Administration(FDA)from 2021 to 2023

Organic sulfone compounds,exhibiting interesting bioactivities,were widely applied in the field of pharmaceutical and medicine.And numerous of sulfuryl group-involved drugs were approved by the Food and Drug Administration(FDA).Odevixibat,maralixibat chloride and belzutifan approved in 2021 could be applied in the treatment of progressive familial intrahepatic cholestasis(PFIC),cholestatic pruritus and clear cell renal cell carcinoma(ccRCC),respectively.In 2022,abrocitinib,pyrukynd and voquezna were approved for the treatment of atopic dermatitis,pyruvate kinase deficiency(PKD)and acid-related disorders,respectively.Defencath for preventing bloodstream infections,sparsentan for treatment of proteinuria related to IgA nephropathy,and xacduro for treatment of hospital-acquired bacterial pneumonia(HABP)were approved in 2023.In this review,the synthesis and therapies of these sulfuryl group-involved drugs approved from 2021 to 2023 are discussed in details.