Influence of O-O formation pathways and charge transfer mediator on lipid bilayer membrane-like photoanodes for water oxidation

Inspired by the function of crucial components in photosystemⅡ(PSⅡ),electrochemical and dyesensitized photoelectrochemical(DSPEC)water oxidation devices were constructed by the selfassembly of well-designed amphipathic Ru(bda)-based catalysts(bda=2,2'-bipyrdine-6,6'-dicarbonoxyl acid)and aliphatic chain decorated electrode surfaces,forming lipid bilayer membrane(LBM)-like structures.The Ru(bda)catalysts on electrode-supported LBM films demonstrated remarkable water oxidation performance with different O-O formation mechanisms.However,compared to the slow charge transfer process,the O-O formation pathways did not determine the PEC water oxidation efficiency of the dyesensitized photoanodes,and the different reaction rates for similar catalysts with different catalytic paths did not determine the PEC performance of the DSPECs.Instead,charge transfer plays a decisive role in the PEC water oxidation rate.When an indolo[3,2-b]carbazole derivative was introduced between the Ru(bda)catalysts and aliphatic chain-modified photosensitizer in LBM films,serving as a charge transfer mediator for the tyrosine-histidine pair in PSⅡ,the PEC water oxidation performance of the corresponding photoanodes was dramatically enhanced.

Polymeric viologen-based electron transfer mediator for improving the photoelectrochemical water splitting on Sb_(2)Se_(3) photocathode

The photogenerated charge carrier separation and transportation of inside photocathodes can greatly influence the performance of photoelectrochemical(PEC)H2 production devices.Coupling TiO_(2) with p-type semiconductors to construct heterojunction structures is one of the most widely used strategies to facilitate charge separation and transportation.However,the band position of TiO_(2) could not perfectly match with all p-type semiconductors.Here,taking antimony selenide(Sb_(2)Se_(3))as an example,a rational strategy was developed by introducing a viologen electron transfer mediator(ETM)containing polymeric film(poly-1,1′-dially-[4,4′-bipyridine]-1,1′-diium,denoted as PV^(2+))at the interface between Sb_(2)Se_(3) and TiO_(2) to regulate the energy band alignment,which could inhibit the recombination of photogenerated charge carriers of interfaces.With Pt as a catalyst,the constructed Sb_(2)Se_(3)/PV^(2+)/TiO_(2)/Pt photocathode showed a superior PEC hydrogen generation activity with a photocurrent density of−18.6 mA cm^(-2) vs.a reversible hydrogen electrode(RHE)and a half-cell solar-to-hydrogen efficiency(HC-STH)of 1.54%at 0.17 V vs.RHE,which was much better than that of the related Sb_(2)Se_(3)/TiO_(2)/Pt photocathode without PV^(2+)(−9.8 mA cm^(-2),0.51%at 0.10 V vs.RHE).

一种基于动态可寻址会话的服务器无感知计算

服务器无感知计算作为云原生范式中快速发展的新兴技术,因其按需付费、自动资源伸缩和底层环境屏蔽等特点而受到越来越多的开发人员欢迎.FaaS(函数即服务)作为Serverless架构的主要实现方式,以函数粒度对应用进行解耦和执行.大多数云服务提供商也为应用开发人员提供了基于Serverless架构的应用搭建服务,这些服务允许开发人员以函数的形式部署代码,并根据实际的请求量进行自动扩缩容.然而,在部署有状态函数时,由于Serverless架构的无状态特性,管理其中的有状态数据变得复杂,往往无法满足Serverless中函数对有状态数据的访问性能要求.因此,本文提出了一种基于有状态和动态可寻址会话机制的服务器无感知计算系统XFaaS,实现了低开销的有状态数据访问和更高的应用吞吐.实验结果表明,通过采用XFaaS系统部署有状态函数的方式,可以降低有状态数据访问时延3个数量级,并提高2倍以上的函数最大吞吐量.

Artificial intelligence-assisted automatic and index-based microbial single-cell sorting system for One-Cell-One-Tube

Identification,sorting,and sequencing of individual cells directly from in situ samples have great potential for in-depth analysis of the structure and function of microbiomes.In this work,based on an artificial intelligence(AI)-assisted object detection model for cell phenotype screening and a cross-interface contact method for single-cell exporting,we developed an automatic and index-based system called EasySort AUTO,where individual microbial cells are sorted and then packaged in a microdroplet and automatically exported in a precisely indexed,“One-Cell-One-Tube”manner.The target cell is automatically identified based on an AI-assisted object detection model and then mobilized via an optical tweezer for sorting.Then,a crossinterface contact microfluidic printing method that we developed enables the automated transfer of cells from the chip to the tube,which leads to coupling with subsequent single-cell culture or sequencing.The efficiency of the system for single-cell printing is>93%.The throughput of the system for single-cell printing is~120 cells/h.Moreover,>80%of single cells of both yeast and Escherichia coli are culturable,suggesting the superior preservation of cell viability during sorting.Finally,AI-assisted object detection supports automated sorting of target cells with high accuracy from mixed yeast samples,which was validated by downstream single-cell proliferation assays.The automation,index maintenance,and vitality preservation of EasySort AUTO suggest its excellent application potential for single-cell sorting.

Promotion of the oxygen evolution performance of Ni–Fe layered hydroxides via the introduction of a proton-transfer mediator anion

Developing efficient catalysts with high durability and activity for the oxygen evolution reaction(OER)is imperative for sustainable energy conversion technologies,including hydrogen generation and CO_(2) reduction,as well as other electrochemical energy storage systems.To this end,a comprehensive understanding of the mechanism for the water oxidation reaction is vital.Herein,a surfactant,nonafluoro-1-butanesulfonate(FBS),was introduced into Ni-Fe layered double hydroxide(Ni Fe-FBS/CFP)via electrochemical deposition on the surface of a carbon fiber paper(CFP)substrate.The as-prepared Ni Fe-FBS/CFP electrode exhibited excellent catalytic activities for OER compared to the Ni-Fe layered double hydroxide based electrode(Ni Fe-LDH/CFP),an excellent stability of 15 h,and an ultralow Tafel slope of 25.8 m V dec-1.Furthermore,by combining the results of p H-dependent kinetics investigations,chemical probing,proton inventory studies,and isotopic and atom-protontransfer measurements,it was observed that a proton-transfer process controls the reaction rates of both the Ni Fe-LDH and Ni Fe-FBS catalysts,and the residual sulfonate groups serve as proton transfer mediator to accelerate the proton transfer rate.

Switching the O-O Bond Formation Pathways of Ru-pda Water Oxidation Catalyst by Third Coordination Sphere Engineering

Water oxidation is a vital anodic reaction for renewable fuel generation via electrochemical-and photoelectrochemical-driven water splitting or CO_(2)reduction.Ruthenium complexes,such as Ru-bda family,have been shown as highly efficient wateroxidation catalysts(WOCs),particularly when they undergo a bimolecular O-O bond formation pathway.In this study,a novel Ru(pda)-type(pda^(2–)=1,10-phenanthroline-2,9-dicarboxylate)molecular WOC with 4-vinylpyridine axial ligands was immobilized on the glassy carbon electrode surface by electrochemical polymerization.Electrochemical kinetic studies revealed that this homocoupling polymer catalyzes water oxidation through a bimolecular radical coupling pathway,where interaction between two Ru(pda)–oxyl moieties(I2M)forms the O-O bond.The calculated barrier of the I2M pathway by densityfunctional theory(DFT)is significantly lower than the barrier of a water nucleophilic attack(WNA)pathway.By using this polymerization strategy,the Ru centers are brought closer in the distance,and the O-O bond formation pathway by the Ru(pda)catalyst is switched from WNA in a homogeneous molecular catalytic system to I2M in the polymerized film,providing some deep insights into the importance of third coordination sphere engineering of the water oxidation catalyst.