基于微生物作为智能模板的电催化剂制备与应用研究进展

通过电催化实现可再生能源的存储与转化对于改善能源结构、保护生态环境、实现碳达峰和碳中和的国家战略具有重大意义。而开发低成本、高效的电催化剂成为全世界科学家共同面对的挑战。微生物在自然界中广泛存在,具有结构、组成和代谢丰富的特点,可以成为电催化剂的模板以及碳、磷、硫等非金属元素以及金属元素的来源,而且具有无毒、生产可重复性好、易于规模化等优点,已成为电催化剂制备的新趋势。对此,本文综述了微生物“智能”引导制备电催化剂的发展及在电催化析氢(HER)、电催化析氧(OER)、氧还原反应(ORR)、二氧化碳还原(CO_(2)RR)、锂电池(LBs)等领域的应用现状。希望有助于推动微生物代谢与催化剂微纳结构关系以及与催化反应的构效关系的深入理解,最后针对这类材料的问题挑战及其未来发展方向进行了探讨与展望。

Water Splitting:From Electrode to Green Energy System

Hydrogen(H2)production is a latent feasibility of renewable clean energy.The industrial H2 production is obtained from reforming of natural gas,which consumes a large amount of nonrenewable energy and simultaneously produces greenhouse gas carbon dioxide.Electrochemical water splitting is a promising approach for the H2 production,which is sustainable and pollution-free.Therefore,developing efficient and economic technologies for electrochemical water splitting has been an important goal for researchers around the world.The utilization of green energy systems to reduce overall energy consumption is more important for H2 production.Harvesting and converting energy from the environment by different green energy systems for water splitting can efficiently decrease the external power consumption.A variety of green energy systems for efficient producing H2,such as two-electrode electrolysis of water,water splitting driven by photoelectrode devices,solar cells,thermoelectric devices,triboelectric nanogenerator,pyroelectric device or electrochemical water-gas shift device,have been developed recently.In this review,some notable progress made in the different green energy cells for water splitting is discussed in detail.We hoped this review can guide people to pay more attention to the development of green energy system to generate pollution-free H2 energy,which will realize the whole process of H2 production with low cost,pollution-free and energy sustainability conversion.

Laser Synthesis and Microfabrication of Micro/ Nanostructured Materials Toward Energy Conversion and Storage

Nanomaterials are known to exhibit a number of interesting physical and chemical properties for various applications,including energy conversion and storage,nanoscale electronics,sensors and actuators,photonics devices and even for biomedical purposes.In the past decade,laser as a synthetic technique and laser as a microfabrication technique facilitated nanomaterial preparation and nanostructure construction,including the laser processing-induced carbon and non-carbon nanomaterials,hierarchical structure construction,patterning,heteroatom doping,sputtering etching,and so on.The laser-induced nanomaterials and nanostructures have extended broad applications in electronic devices,such as light–thermal conversion,batteries,supercapacitors,sensor devices,actuators and electrocatalytic electrodes.Here,the recent developments in the laser synthesis of carbon-based and non-carbon-based nanomaterials are comprehensively summarized.An extensive overview on laser-enabled electronic devices for various applications is depicted.With the rapid progress made in the research on nanomaterial preparation through laser synthesis and laser microfabrication technologies,laser synthesis and microfabrication toward energy conversion and storage will undergo fast development.

Applications of 2D-Layered Palladium Diselenide and Its van der Waals Heterostructures in Electronics and Optoelectronics

The rapid development of two-dimensional(2D)transition-metal dichalcogenides has been possible owing to their special structures and remarkable properties.In particular,palladium diselenide(PdSe_(2))with a novel pentagonal structure and unique physical characteristics have recently attracted extensive research inter-est.Consequently,tremendous research progress has been achieved regarding the physics,chemistry,and electronics of PdSe_(2).Accordingly,in this review,we recapitulate and summarize the most recent research on PdSe_(2),including its structure,properties,synthesis,and appli-cations.First,a mechanical exfoliation method to obtain PdSe_(2) nanosheets is introduced,and large-area synthesis strate-gies are explained with respect to chemical vapor deposition and metal selenization.Next,the electronic and optoelectronic properties of PdSe_(2) and related hetero-structures,such as field-effect transistors,photodetectors,sensors,and thermoelec-tric devices,are discussed.Subsequently,the integration of systems into infrared image sensors on the basis of PdSe_(2) van der Waals heterostructures is explored.Finally,future opportunities are highlighted to serve as a general guide for physicists,chemists,materials scientists,and engineers.Therefore,this com-prehensive review may shed light on the research conducted by the 2D material community.

Chromium phosphide nanoparticles embedded in porous nitrogen-/phosphorus-doped carbon as efficient electrocatalysts for a nitrogen reduction reaction

The resource recovery of heavy metals from effluent has significant environmental implications and potential commercial value.Chromium phosphide nanoparticles embedded in a nitrogen-/phosphorus-doped porous carbon matrix(CrP/NPC)are synthesized via a consecutive Cr^(6+)leachate treatment and resource recovery process.Electrochemical testing shows that CrP/NPC shows excellent nitrogen reduction reaction(NRR)performance,which yields the highest NH_(3) production rate of 22.56μg h^(−1) mg^(−1)_(cat).and Faradaic efficiency(16.37%)at−0.5 V versus the reversible hydrogen electrode in a 0.05M Na_(2)SO_(4) aqueous solution,as well as robust catalytic stability.The isotopic experiments using ^(15)N^(2) as a nitrogen source confirm that the detected NH_(3) is derived from the NRR process.Finally,density functional theory(DFT)calculations show that the electron deficiency environment of the Cr site can significantly reduce the barrier of the NRR process and promote the formation of intermediate species.

MoC nanoclusters anchored Ni@N‐doped carbon nanotubes coated on carbon fiber as three‐dimensional and multifunctional electrodes for flexible supercapacitor and self‐heating device

With the rapid development of different kinds of wearable electronic devices,flexible and high‐capacity power sources have attracted increasing attention.In this study,a facile strategy to fabricate Ni nanoparticles embedded in N‐doped carbon nanotubes(CNTs)(Ni@NCNTs)homogeneously coated on the surface of carbon fiber with a multistructural component of molybdenum carbide(MoC/Ni@NCNTs/CC)was synthesized.There are two forms of MoC in MoC/Ni@NCNTs/CC,including the MoC nanoclusters in a size of 2 to 4 nm anchored on Ni@N‐doped CNTs and the MoC nanoparticles as an interface between MoC/Ni@NCNTs and carbon cloth(CC).Multifunctional MoC/Ni@NCNTs/CC served as both positive and negative electrode and a heater in flexible supercapacitors and in wearable devices,which exhibited excellent electrochemical and heating performance.Besides,an all‐solid‐state supercapacitor consists of two pieces of MoC/Ni@NCNTs/CC that exhibited extraordinary energy storage performance with high‐energy density(78.7μWh/cm2 at the power density of 2.4 mW/cm2)and excellent cycling stability(≈91%capacity retention after 8000 cycles).Furthermore,all‐solid‐state flexible supercapacitors were incorporated with an MoC/Ni@NCNTs/CC electrode into self‐heating flexible devices for keeping the human body warm.Thus,MoC/Ni@NCNTs/CC is a promising electrode material for flexible and wearable storage systems and heating electronic application.

Applications of Carbon Nanotubes in the Internet of Things Era

The post-Moore's era has boosted the progress in carbon nanotube-based transistors.Indeed,the 5 G communication and cloud computing stimulate the research in applications of carbon nanotubes in electronic devices.In this perspective,we deliver the readers with the latest trends in carbon nanotube research,including high-frequency transistors,biomedical sensors and actuators,brain–machine interfaces,and flexible logic devices and energy storages.Future opportunities are given for calling on scientists and engineers into the emerging topics.

A Wire-Shaped Supercapacitor in Micrometer Size Based on Fe_3O_4 Nanosheet Arrays on Fe Wire

One-dimensional(1D, wire-and fiber-shaped)supercapacitors have recently attracted interest due to their roll-up, micrometer size and potential applications in portable or wearable electronics. Herein, a 1D wireshaped electrode was developed based on Fe_3O_4 nanosheet arrays connected on the Fe wire, which was prepared via oxidation of Fe wire in 0.1 M KCl solution(pH 3) with O2-rich environment under 70 °C. The obtained Fe_3O_4 nanosheet arrays displayed a high specific capacitance(20.8 m F cm^(-1) at 10 mV s^(-1)) and long cycling lifespan(91.7% retention after 2500 cycles). Theexcellent performance may attribute to the connected nanosheet structure with abundant open spaces and the intimate contact between the Fe_3O_4 and iron substrate. In addition, a wire-shaped asymmetric supercapacitor was fabricated and had excellent capacitive properties with a high energy density(9 l Wh cm^(-2)) at power density of 532.7 l W cm^(-2) and remarkable long-term cycling performance(99% capacitance retention after 2000 cycles).Considering low cost and earth-abundant electrode material, as well as outstanding electrochemical properties, the assembled supercapacitor will possess enormous potential for practical applications in portable electronic device.

Carbon-based Electrocatalysts for Hydrogen Evolution Reaction Modulated by Embedded Metals

Development of effective technologies for clean and sustainable hydrogen energy has been attracting great attention lately,as hydrogen is hailed as a promising energy source to reduce our dependence on fossil fuels and benefit the environment by reducing the emissions of greenhouse and other toxic gases.Toward this end,an effective and promising approach is based on the electrolysis of water

Modulating p-type doping of two-dimensional material palladium diselenide

The van der Waals heterostructures have evolved as novel materials for complementing the Si-based semiconductor technologies.Group-10 noble metal dichalcogenides(e.g.,PtS_(2),PtSe_(2),PdS_(2),and PdSe_(2))have been listed into two-dimensional(2D)materials toolkit to assemble van der Waals heterostructures.Among them,PdSe_(2) demonstrates advantages of high stability in air,high mobility,and wide tunable bandgap.However,the regulation of p-type doping of PdSe_(2) remains unsolved problem prior to fabricating p–n junction as a fundamental platform of semiconductor physics.Besides,a quantitative method for the controllable doping of PdSe_(2) is yet to be reported.In this study,the doping level of PdSe_(2) was correlated with the concentration of Lewis acids,for example,SnCl_(4),used for soaking.Considering the transfer characteristics,the threshold voltage(the gate voltage corresponding to the minimum drain current)increased after SnCl_(4) soaking treatment.PdSe_(2) transistors were soaked in SnCl_(4) solutions with five different concentrations.The threshold voltages from the as-obtained transfer curves were extracted for linear fitting to the threshold voltage versus doping concentration correlation equation.This study provides in-depth insights into the controllable p-type doping of PdSe_(2).It may also push forward the research of the regulation of conductivity behaviors of 2D materials.

Laser constructed vacancy-rich TiO_(2-x)/Ti microfiber via enhanced interfacial charge transfer for operando extraction-SERS sensing

Semiconductor-molecule surface-enhanced Raman scattering(SERS),especially the stronger interfacial charge transfer process(ICTP),represents a frontier in the field of SERS with spectral reproducibility and unparalleled selectivity.Herein,through a laser microfabrication method in situ,the free-standing,super hydrophilic and vacancy-rich TiO_(2-x)/Ti is successfully synthesized.Using blue TiO_(x)/Ti(B-TiO_(x)/Ti)as preconcentrated substrate,a nanomolar-level limit of detection of 12 nmol/L at 1385 cm–1,is confirmed using crystal violet(CV)bacteriostat as a model under 532 nm excitation.Furthermore,the results demonstrate that the SERS enhancement mechanism is via the moderate adulteration of oxygen vacancy,which leads to a narrow value of band gap and increases the ICTP of substrate to molecules.Using a hand-held extractor assembled with B-TiO_(x)/Ti microfiber,the operando analysis of mixtures distributed information excited in different parts of Asian carp is facilely achieved.This work guides the controlled synthesis of vacancy-rich TiO_(2-x)/Ti nanostructure and its application in ultrasensitive extraction-SERS detection.It also provides the direction for the rapid and operando transmission of biological information with temporal and spatial concentration distribution in human tissues by highly sensitized materials.

Fabrication of patterned transparent conductive glass via laser metal transfer for efficient electrical heating and antibacteria

Vapor deposition and three-dimensional(3D)printing technology are considered to be conventional methods to achieve patterned metal film preparation through the assistance of masks and high temperature.Therefore,there are still some challenges in fabricating metal films in template-free and normal temperature environment.In this work,we report a flexible and rapid laser metal transfer(LMT)technique for fabricating the various metal films(Cu,Ni,Sn,Al,Fe,and Ag)with different patterns without templates on arbitrary substrates(glass,polyimide(PI)films,and aluminum nitride(AlN)ceramic).Especially,the obtained transparent conductive glass displays high transmittance(more than 90%)and adjustable resistances(≈5Ω).According to the Joule effect,the interface resistance between Cu particles and copper oxide coating produces the high temperature approximately 280℃ at 2 V in a short time(≈60 s)and remains stable at 120℃ over 12 h.At last,the multifunctional glass with Cu patterns also shows excellent bactericidal activity(≈95%).This work demonstrates that laser metal transfer is an exceeding effective means of fabricating the micro/nano structures with potential applications in functional devices.

Boosting flexible electronics with integration of two-dimensional materials

Flexible electronics has emerged as a continuously growing field of study.Two-dimensional(2D)materials often act as conductors and electrodes in elec-tronic devices,holding significant promise in the design of high-performance,flexible electronics.Numerous studies have focused on harnessing the potential of these materials for the development of such devices.However,to date,the incorporation of 2D materials in flexible electronics has rarely been summa-rized or reviewed.Consequently,there is an urgent need to develop compre-hensive reviews for rapid updates on this evolving landscape.This review covers progress in complex material architectures based on 2D materials,including interfaces,heterostructures,and 2D/polymer composites.Addition-ally,it explores flexible and wearable energy storage and conversion,display and touch technologies,and biomedical applications,together with integrated design solutions.Although the pursuit of high-performance and high-sensitivity instruments remains a primary objective,the integrated design of flexible electronics with 2D materials also warrants consideration.By combin-ing multiple functionalities into a singular device,augmented by machine learning and algorithms,we can potentially surpass the performance of existing wearable technologies.Finally,we briefly discuss the future trajectory of this burgeoning field.This review discusses the recent advancements in flex-ible sensors made from 2D materials and their applications in integrated archi-tecture and device design.

Metal-encapsulated nitrogen-doped carbon nanotube arrays electrode for enhancing sulfion oxidation reaction and hydrogen evolution reaction by regulating of intermediate adsorption

For treatment of sulfion-containing wastewater,coupling the electrochemical sulfion oxidation reaction(SOR)with hydrogen evolution reaction(HER)can be an ideal way for sulfur and H_(2)resources recovery.Herein,we synthesize a metal-modified carbon nanotube arrays electrode(Co@N-CNTs/CC)for SOR and HER.This electrode has excellent performance for SOR and HER attributed to the unique array structure.It can achieve 99.36 mA/cm^(2)at 0.6 V for SOR,and 10 mA/cm^(2)at 0.067 V for HER.Density functional theory calculations verify that metal modification is able to regulate the electronic structure of carbon nanotube,which is able to optimize the adsorption of intermediates.Employed Co@N-CNTs/CC as bifunctional elec-trodes to establish a hybrid electrolytic cell can reduce about 67%of energy consumption compared with the traditional water splitting electrolytic cell.Finally,the hybrid electrolytic cell is used to treat actual sulfion-containing wastewater,achieving the sulfur yield of 30 mg h^(−1)cm^(−2)and the hydrogen production of 0.64 mL/min.

Laser-processed lithium niobate wafer for pyroelectric sensor

During the past few decades, pyroelectric sensors have attracted extensiveattention due to their prominent features. However, their effectiveness is hinderedby low electric output. In this study, the laser processed lithium niobate(LPLN) wafers are fabricated to improve the temperature–voltage response.These processed wafers are utilized to construct pyroelectric sensors as well ashuman–machine interfaces. The laser induces escape of oxygen and the formationof oxygen vacancies, which enhance the charge transport capability on thesurface of lithium niobate (LN). Therefore, the electrodes gather an increasedquantity of charges, increasing the pyroelectric voltage on the LPLN wafers toa 1.3 times higher voltage than that of LN wafers. For the human–machineinterfaces, tactile information in various modes can be recognized by a sensorarray and the temperature warning system operates well. Therefore, the lasermodification approach is promising to enhance the performance of pyroelectricdevices for applications in human–machine interfaces.

Coordination-based synthesis of Fe single-atom anchored nitrogen-doped carbon nanofibrous membrane for CO_(2)electroreduction with nearly 100%CO selectivity

Carbon-based materials with single-atom(SA)transition metals coordinated with nitrogen(M-N_(x))have attracted extensive attention due to their superior electrochemical CO_(2)reduction reaction(CO_(2)RR)performance.However,the uncontrolled recombination of metal atoms during the typical high-temperature synthesis process in M-N_(x)causes deterioration of CO_(2)RR activity.Herein,by using electrospinning,we propose a novel strategy for constructing a highly active and selective SA Fe-modified N-doped porous carbon fiber membrane catalyst(Fe-N-CF).This carbon membrane has an interconnected threedimensional structure and a hierarchical porous structure,which can not only confine Fe to be single atom as active centers,but also provide a diffusion channel for CO_(2)molecules.Relying on its special structure and stable mechanical properties,Fe-N-CF is directly used for CO_(2)RR,which presents an excellent selectivity(CO Faradaic efficiency of 97%)and stability.DFT calculations reveals that the synthesized Fe-N_(4)-C can significantly reduce the energy barrier for intermediate COOH^(*)formation and CO desorption.This work highlights the specific advantages of using electrospinning method to prepare the optimal SA catalysts.

Modulating pollutant adsorption and peroxymonosulfate activation sites on Co_(3)O_(4)@N,O doped-carbon shell for boosting catalytic degradation activity

The construction of double active sites for pollutant adsorption and peroxymonosulfate(PMS)activation on the surface of catalyst is conducive to further enhancing the pollutant-removing effect.Herein,a N,O co-doped carbon-encapsulated tricobalt tetraoxide(Co_(3)O_(4)@N,O-C)with double active sites is prepared by a one-step laser carbonization method.The optimized Co_(3)O_(4)@N,O-C shows excellent tetracycline(TC)removal ability,in which the k value reaches 0.608 min^(-1).On the surface of Co_(3)O_(4)@N,O-C,TC is adsorbed to the N site,and PMS is activated at the O site.Building double active sites on the catalyst surface not only avoids competition for the active site,but also confines the pollutant molecules to the surface of the catalyst,thus shortening the migration distance between reactive oxygen species(ROS)and the pollutant and boosting the removal efficiency of pol-lutants.In addition,the Co_(3)O_(4)@N,O-C/PMS system exhibits both good resistance to environmental interference and cyclic stability.Finally,a practical continuous flow reactor based on Co_(3)O_(4)@N,O-C catalyst is built,which shows a stable and efficient TC degradation performance.

Ferrocene-induced switchable preparation of metal-nonmetal codoped tungsten nitride and carbide nanoarrays for electrocatalytic HER in alkaline and acid media

Transition metal nitride/carbide(TMN/C)have been actively explored as low-cost hydrogen evolution reaction(HER)electrocatalysts owing to their Pt-like physical and chemical properties.Unfortunately,pure TMN/C suffers from strong hydrogen adsorption and lacks active centers for water dissociation.Herein,we developed a switchable WO_(3)-based in situ gas–solid reaction for preparing sophisticated Fe-N doped WC and Fe-C doped WN nanoarrays.Interestingly,the switch of codoping and phase can be effectively manipulated by regulating the amount of ferrocene.Resultant Fe-C-WN and Fe-N-WC exhibit robust electrocatalytic performance for HER in alkaline and acid electrolytes,respectively.The collective collaboration of morphological,phase and electronic effects are suggested to be responsible for the superior HER activity.The smallest|ΔGH*|value of Fe-NWC indicates preferable hydrogen-evolving kinetics on the Fe-N-WC surface for HER under acid condition,while Fe-C-WN is suggested to be beneficial to the adsorption and dissociation of H_(2)O for HER in alkaline electrolyte.

Multi-interface collaboration of graphene cross-linked NiS-NiS_(2)-Ni_(3)S_(4) polymorph foam towards robust hydrogen evolution in alkaline electrolyte

Electrocatalytic hydrogen production in alkaline media is extensively adopted in industry. Unfortunately, further performance improvement is severely impeded by the retarded kinetics, which requires the fine regulation of water dissociation, hydrogen recombination, and hydroxyl desorption. Herein, we develop a multi-interface engineering strategy to make an elaborate balance for the alkaline hydrogen evolution reaction (HER) kinetics. The graphene cross-linked three-phase nickel sulfide (NiS-NiS_(2)-Ni_(3)S_(4)) polymorph foam (G-NNNF) was constructed through hydrothermal sulfidation of graphene wrapped nickel foam as a three-dimensional (3D) scaffold template. The G-NNNF exhibits superior catalytic activity toward HER in alkaline electrolyte, which only requires an overpotential of 68 mV to drive 10 mA·cm^(−2) and is better than most of the recently reported metal sulfides catalysts. Density functional theory (DFT) calculations verify the interfaces between nickel sulfides (NiS/NiS_(2)-Ni_(3)S_(4)) and cross-linked graphene can endow the electrocatalyst with preferable hydrogen adsorption as well as metallic nature. In addition, the electron transfer from Ni_(3)S_(4)/NiS_(2) to NiS results in the electron accumulation on NiS and the hole accumulation on Ni_(3)S_(4)/NiS_(2), respectively. The electron accumulation on NiS favors the optimization of the H* adsorption, whereas the hole accumulation on Ni_(3)S_(4) is beneficial for the adsorption of H_(2)O. The work about multi-interface collaboration pushes forward the frontier of excellent polymorph catalysts design.

Enhanced electrocatalytic activity of Co@N-doped carbon nanotubes by ultrasmall defect-rich TiO2 nanoparticles for hydrogen evolution reaction

Despite being technically possible, splitting water to generate hydrogen is practically unfeasible, mainly because of the lack of sustainable and efficient earth-abundant catalysts for the hydrogen-evolution reaction （HER）. Herein, we report a durable and highly active electrochemical HER catalyst based on defect-rich TiO2 nanoparticles loaded on Co nanoparticles@N-doped carbon nanotubes （D-TiOdCo@NCT） synthesized by electrostatic spinning and a subsequent calcining process. The ultrasmall TiO2 nanoparticles are 1.5-2 nm in size and have a defect-rich structure of oxygen vacancies. D-TiO2/Co@NCT exhibits excellent HER catalytic activity in an acidic electrolyte （0.5 M H2SO4）, with a low onset potential of -57.5 mV （1 mA·cm^-2）, a small Tafel slope of 73.5 mV·dec^-1, and extraordinary long-term durability. X-ray photoelectron spectroscopy, electron paramagnetic resonance spectroscopy, and theoretical calculations confirm that the Ti3. defect-rich structure can effectively regulate the catalytic activity for electrochemical water splitting.