CO_(2) conversion to solar fuels and chemicals:Opening the new paths

This future article discusses the new prospects and directions of CO_(2)conversion via the photo-electrocatalytic(PEC)route.The second(2nd)generation solar fuels and chemicals(SFs)are generated directly in PEC systems via electrons/protons reactions without forming molecular H_(2)as an intermediate,overcoming the thermodynamics limitations and practical issues encountered for electro-fuels produced by multistep thermocatalytic processes(i.e.CO_(2)conversion with H_(2)coming from water electrolysis).A distributed and decentralized production of SFs requires very compact,highly integrated,and intensified technologies.Among the existing reactors of advanced design(based on artificial leaves or photosynthesis),the integrated photovoltaic plus electrocatalytic(PV-EC)device is the only system(demonstrated at large scale)to produce SFs with high solar-to-fuel(STF)efficiency.However,while the literature indicates STF efficiency as the main(and only)measure of process performance,we remark here the need to refer to productivity(in terms of current density)and make tests with reliable flow PEC systems(with electrodes of at least 5–10 cm^(2))to accelerate the scaling-up process.Using approaches that minimize downstream separation costs is also mandatory.Many limitations exist in PEC systems,but most can be overcome by proper electrode and cell engineering,thus going beyond the properties of the electrocatalysts.As examples of current developments,we present the progress of(i)artificial leaf/tree devices for green H_(2)distributed production and(ii)a PEC device producing the same chemicals at both cathode and anode parts without downstream operations for green solvent distributed production.Based on these developments,future directions,such as producing fertilizers and food components from the air,are outlined.The aim is to provide new ideas and research directions from a personal perspective.

Early Cambrian Mollusc Watsonella crosbyi:A Potential GSSP Index Fossil for the Base of the Cambrian Stage 2

The mollusc Watsonella crosbyi was studied on the basis of material from the lower Cambrian Dahai Member of the Zhujiaqing Formation in eastern Yunnan, China and the Pestrotsvet Formation of the Aldan River region in the Siberian Platform. This fossil had been excessively described under different names in the literature, such as Heraultia varensalensis Cobboid, 1935, H. sibirica Missarzhevsky, 1974, Heraultipegma yunnanensis He and Yang, 1982, H. yannanese He and Yang,1982, Watsonella yunnanensis, W. crosbyi Grabau, 1900, etc. Taxonomic revision shows that other species are junior synonyms of W. crosbyi. Analysis of functional morphology implies that W. crosbyi may be rather a heicionelloid than a rostroconch since its univalved conch is untorted endogastric and lacks a rostrum and a true internal pegma. Replicas of the original microstrnctures preserved on the surfaces of phosphatic internal moulds confirm that the shell consists of two layers. The inner layer is lamello-fibrillar, and the outer layer is spherulitic prismatic. The widespread geographical occurrences in both siliciclastic and carbonate rocks of the late Terreneuvian indicate that W. crosbyi is an important index fossil for global correlations and subdivision of the Cambrian Series I （Terreneuvian）.The first appearance datum （FAD） of W. crosbyi is suggested to be a potential GSSP （Global Boundary Stratotype Section and Point） candidate marker for defining the base of the Cambrian Stage 2.

A perspective on carbon materials for future energy application

Nanocarbon materials play a critical role in the development of new or improved technologies and devices for sustainable production and use of renewable energy. This perspective paper defines some of the trends and outlooks in this exciting area, with the effort of evidencing some of the possibilities offered from the growing level of knowledge, as testified from the exponentially rising number of publications, and putting bases for a more rational design of these nanomaterials. The basic members of the new carbon family are fullerene, graphene, and carbon nanotube. Derived from them are carbon quantum dots, nanohorn, nanofiber, nano ribbon, nanocapsulate, nanocage and other nanomorphologies. Second generation nanocarbons are those which have been modified by surface functionalization or doping with heteroatoms to create specific tailored properties. The third generation of nanocarbons is the nanoarchitectured supramolecular hybrids or composites of the first and second genera- tion nanocarbons, or with organic or inorganic species. The advantages of the new carbon materials, relating to the field of sustainable energy, are discussed, evidencing the unique properties that they offer for developing next generation solar devices and energy storage solutions.

碳基催化剂:为开发下一代纳米工程催化材料开辟新方法(英文)

This essay analyses some of the recent development in nanocarbons (carbon materials having a defined and controlled nano-scale dimension and functional properties which strongly depend on their nano-scale features and architecture), with reference to their use as advanced catalytic materials. It is remarked how their features open new possibilities for catalysis and that they represent a new class of catalytic materials. Although carbon is used from long time in catalysis as support and electrocatalytic applications, nanocarbons offer unconventional ways for their utilization and to address some of the new challenges deriving from moving to a more sustainable future. This essay comments how nanocarbons are a key element to develop next-generation catalytic materials, but remarking that this goal requires overcoming some of the actual limits in current research. Some aspects are discussed to give a glimpse on new directions and needs for R&D to progress in this direction.

Electrocatalytic conversion of CO_2 to liquid fuels using nanocarbon-based electrodes

Recent advances on the use of nanocarbon-based electrodes for the electrocatalytic conversion of gaseous streams of CO2 to liquid fuels are discussed in this perspective paper. A novel gas-phase electrocatalytic cell, different from the typical electrochemical systems working in liquid phase, was developed. There are several advantages to work in gas phase, e.g. no need to recover the products from a liquid phase and no problems of CO2 solubility, etc. Operating under these conditions and using electrodes based on metal nanoparticles supported over carbon nanotube （CNT） type materials, long C-chain products （in particular isopropanol under optimized conditions, but also hydrocarbons up to C8-C9） were obtained from the reduction of CO2. Pt-CNT are more stable and give in some cases a higher productivity, but Fe-CNT, particular using N-doped carbon nanotubes, give excellent properties and are preferable to noble-metal-based electrocatalysts for the lower cost. The control of the localization of metal particles at the inner or outer surface of CNT is an importact factor for the product distribution. The nature of the nanocarbon substrate also plays a relevant role in enhancing the productivity and tuning the selectivity towards long C-chain products. The electrodes for the electrocatalytic conversion of CO2 are part of a photoelectrocatalytic （PEC） solar cell concept, aimed to develop knowledge for the new generation artificial leaf-type solar cells which can use sunlight and water to convert CO2 to fuels and chemicals. The CO2 reduction to liquid fuels by solar energy is a good attempt to introduce renewables into the existing energy and chemical infrastructures, having a higher energy density and easier transport/storage than other competing solutions （i.e. H2）.

变革性催化过程生产可再生燃料:展望和挑战

利用可再生能源与空气中捕获的CO_(2)合成液体燃料(e-fuels)替代化石燃料,是消除温室气体,应对气候变化所必需的技术.例如,欧盟计划于2050年实现净零排放.e-fuels可以作为化学能载体,克服可再生能源的间歇性和难以储存的不足,并为难以实现电气化的地区供给燃料.e-fuels可作为可持续能源长期储存和远距离运输的载体;同时,与对化石燃料减排所需要进行的基础设施大幅度改造相比,e-fuels节约了经济成本和时间成本.发展新的可持续方法生产e-fuels是加速实现能源转型的关键,这为催化科学提出了新挑战.本视角文章在简要介绍了e-fuels在实现零净排放目标方面的关键作用后,讨论了活性反应催化(电催化、光催化和等离子体催化的统称,三者存在很多共性及相似的问题,为简洁起见,本文聚焦于电催化)和目前应用最多的热催化之间的差异,提出了推动生产e-fuels取得进展的重点不在于扩大实验规模,而很大程度在于转变现有的思路和方法,发展活性反应催化的观点.目前活性反应催化的研究方法是从热催化衍生而来的,为推动合成燃料成为现实,研究人员需要重新思考催化原理,从基本观点和机理研究的角度理解活性反应催化与热催化的不同之处.这是未来催化科学推动可持续合成e-fuels技术发展,加速能源转型所面临的挑战.

Enhanced performance in the direct electrocatalytic synthesis of ammonia from N2 and H2O by an in-situ electrochemical activation of CNT-supported iron oxide nanoparticles

The direct electrocatalytic synthesis of ammonia from N2 and H2O by using renewable energy sources and ambient pressure/temperature operations is a breakthrough technology,which can reduce by over 90%the greenhouse gas emissions of this chemical and energy storage process.We report here an in-situ electrochemical activation method to prepare Fe2O3-CNT(iron oxide on carbon nanotubes)electrocatalysts for the direct ammonia synthesis from N2 and H2O.The in-situ electrochemical activation leads to a large increase of the ammonia formation rate and Faradaic efficiency which reach the surprising high values of 41.6μg mgcat^−1 h^−1 and 17%,respectively,for an in-situ activation of 3 h,among the highest values reported so far for non-precious metal catalysts that use a continuous-flow polymer-electrolytemembrane cell and gas-phase operations for the ammonia synthesis hemicell.The electrocatalyst was stable at least 12 h at the working conditions.Tests by switching N2 to Ar evidence that ammonia was formed from the gas-phase nitrogen.The analysis of the changes of reactivity and of the electrocatalyst characteristics as a function of the time of activation indicates a linear relationship between the ammonia formation rate and a specific XPS(X-ray-photoelectron spectroscopy)oxygen signal related to O2−in iron-oxide species.This results together with characterization data by TEM and XRD suggest that the iron species active in the direct and selective synthesis of ammonia is a maghemite-type iron oxide,and this transformation from the initial hematite is responsible for the in-situ enhancement of 3-4 times of the TOF(turnover frequency)and NH3 Faradaic efficiency.This transformation is likely related to the stabilization of the maghemite species at CNT defect sites,although for longer times of preactivation a sintering occurs with a loss of performances.

Role of size and pretreatment of Pd particles on their behaviour in the direct synthesis of H_2O_2

Two families of catalysts, based on Pd nanoparticles supported on ceramic asymmetric tubular alumina membranes, are studies in the direct synthesis of H2O2. They are prepared by depositing Pd in two ways：（i） reduction with N2H4 in an ultrasonic bath and（ii） by impregnation-deposition. The first preparation leads to larger particles, with average size of around 11 nm, while the second preparation leads to smaller particles, with average size around 4 nm. The catalytic membranes were tested as prepared, after thermal treatment in air and after further pre-reduction with H2 in mild（100 ℃） conditions. Samples were characterized by TEM, CO-chemisorption monitored by DRIFTS method and TPR, while catalytic tests have been performed in a semi-batch recirculation membrane reactor. Experimental catalytic results were analysed using two kinetics models to derive the reaction constants for the parallel and consecutive reactions of the kinetic network. Smaller particles of Pd show lower selectivity due to the higher rate of parallel combustion, even if the better dispersion of Pd and thus higher metal surface area in the sample lead to a productivity in H2O2 similar or even higher than the sample with the larger Pd particles. Independently on the presence of smaller or larger Pd nanoparticles, an oxidation treatment leads to a significant enhancement in the productivity, although the catalyst progressively reduces during the catalytic process. The inhibition of the parallel combustion reaction（to water） induced from the calcination treatment remains after the in-situ reduction of the oxidized Pd species formed during the pre-treatment.This is likely due to the elimination of defect sites which dissociatively activate oxygen, and tentatively attributed to Pd sites able to give three- and four-fold coordination of CO.

The energy-chemistry nexus: A vision of the future from sustainability perspective

The changing energy-chemistry nexus is discussed in this perspective paper about the future of sustainable energy and chemical production to identify the priorities and open issues on which focus research and development. Topics discussed regard （i） the new sustainable energy scenario, （ii） the role of energy storage （from smart grids to chemical storage of energy）, （iii） the outlooks and role of solar （bio）refineries and solar fuels, （iv） how to integrate hio- and solar-refineries to move to new economy, （v） the role of methanol at the crossover of new energy-chemistry nexus, （vi） the role of chemistry in this new scenario, （vii） the role of nanomaterials for a sustainable energy, （viii） the use of nanocarbons to design advanced energy conversion and storage devices, and （ix） possibilities and routes to exploit solar energy and methane （shale gas）. The contribution provides a glimpse of the emerging directions and routes with some elements about their possible role in the future scenario, but does not orovide a detailed analysis of the state of the art in these directions

Semiconductor,molecular and hybrid systems for photoelectrochemical solar fuel production

The paper shortly reviews the basic direct approaches applied in searching for viable solutions to solar fuel production. These are generally distinguished in molecular and semiconductor(non-molecular)systems, however, hybrid strategies, proposed recently, have also been included. The most promising efforts are considered, highlighting key aspects and emerging critical issues. Special attention is paid to aspects such as electrode architecture, device design, and main differences in the scientific vision and challenges to directly produce solar fuels. This overview could be useful to orientate the readers in the wide panorama of research activities concerning water splitting, natural and artificial photosynthesis, and solar fuel production through the identification of common aspects, specialties and potentialities of the many initiatives and approaches that are developing worldwide in this field with the final aim to meet world energy demand.

非晶碳纳米球的低温石墨化(英文)

The investigation by SEM/TEM, porosity, and X-ray diffraction measurements of the graphitization process starting from amorphous carbon nanospheres, prepared by glucose carbonization, is reported. Aspects studied are the annealing temperature in the 750–1000 °C range, the type of inert carrier gas, and time of treatment in the 2–6 h range. It is investigated how these parameters influence the structural and morphological characteristics of the carbon materials obtained as well as their nanostructure. It is shown that it is possible to maintain after graphitization the round-shaped macro morphology, a high surface area and porosity, and especially a large structural disorder in the graphitic layers stacking, with the presence of rather small ordered domains. These are characteristics interesting for various catalytic applications. The key in obtaining these characteristics is the thermal treatment in a flow of N2. It was demonstrated that the use of He rather than N2 does not allow obtaining the same results. The effect is attributed to the presence of traces of oxygen, enough to create the presence of oxygen functional groups on the surface temperatures higher than 750 °C, when graphitization occurs. These oxygen functional groups favor the graphitization process.

Energy and flux measurements of laser-induced silver plasma ions by using Faraday cup

Silver(Ag)plasma has been generated by employing Nd:YAG laser(532 nm,6 ns)laser irradiation.The energy and flux of ions have been evaluated by using Faraday cup(FC)using time of flight(TOF)measurements.The dual peak signals of fast and slow Ag plasma ions have been identified.Both energy and flux of fast and slow ions tend to increase with increasing irradiance from 7 GW cm-2 to 17.9 GW cm-2 at all distances of FC from the target surface.Similarly a decreasing trend of energies and flux of ions has been observed with increasing distance of FC from the target.The maximum value of flux of the fast component is21.2×10^(10) cm^(-2),whereas for slow ions the maximum energy and flux values are 8.8 keV,8.2×10^(10) cm^(-2) respectively.For the analysis of plume expansion dynamics,the angular distribution of ion flux measurement has also been performed.The overall analysis of both spatial and angular distributions of Ag ions revealed that the maximum flux of Ag plasma ions has been observed at an optimal angle of~15°.In order to confirm the ion acceleration by ambipolar field,the self-generated electric field(SGEF)measurements have also been performed by electric probe;these SGEF measurements tend to increase by increasing laser irradiance.The maximum value of 232 V m^(-1) has been obtained at a maximum laser irradiance of 17.9 GW cm^(-2).

Effect of deposition parameters on structural and mechanical properties of niobium nitride synthesized by plasma focus device

Effects of deposition angle and axial distance on the structural and mechanical properties of niobium nitride syn- thesized by a dense plasma focus （DPF） system are studied. The x-ray diffraction （XRD） confirms that the deposition parameters affect the growth of multi-phase niobium nitride. Scanning electron microscopy （SEM） shows the granular surface morphology with strong thermally assisted coagulation effects observed at the 5-cm axial distance. The non-porous granular morphology observed at the 9-cm distance along the anode axis is different from those observed at deposition angles of 10° and 20°. Energy dispersive x-ray （EDX） spectroscopy reveals the maximum nitrogen content at the shortest （5 cm） axial position. Atomic force microscopy （AFM） exhibits that the roughness of coated films varies for coatings synthesized at different axial and angular positions, and the Vickers micro-hardness test shows that a maximum hardness value is （08.44 ±0.01） GPa for niobium nitride synthesized at 5-cm axial distance, which is about 500% more than that of a virgin sample.

Photoactive materials based on semiconducting nanocarbons——A challenge opening new possibilities for photocatalysis

This perspective paper introduces the concept that nanocarbons and related materials such as carbon dots are an interesting intrinsic photocatalytic semiconducting material, and not only a modifier of the existing (semiconducting) materials to prepare hybrid materials. The semiconducting properties of the nanocarbons, and the possibility to have the band gap within the visible-light region through defect band engineering, introduction of light heteroatoms and control/manipulation of the curvature or surface functionalization are discussed. These materials are conceptually different from the 'classical' semiconducting photocatalysts, because semiconductor domains with tuneable characteristics are embedded in a conductive carbon matrix, with the presence of various functional groups (as C=0 groups) enhancing charge separation by trapping electrons. These nanocarbons open a range of new possibilities for photocatalysis both for energetic and environmental applications. The use of nanocarbons as quantum dots and photo luminescent materials was also analysed. (C) 2017 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.

Synthesis of TiN/a-Si_3N_4 thin film by using a Mather type dense plasma focus system

A 2.3 kJ Mather type pulsed plasma focus device was used for the synthesis of a TiN/a-Si3N4 thin film at room temperature. The film was characterized using X-ray diffraction （XRD）, X-ray photoelectron spectroscopy （XPS）, scanning electron microscopy （SEM）, and atomic force microscopy （AFM）. The XRD pattern confirms the growth of polycrystalline TiN thin film. The XPS results indicate that the synthesized film is non-stoichiometric and contains titanium nitride, silicon nitride, and a phase of silicon oxy-nitride. The SEM and AFM results reveal that the surface of the synthesized film is quite smooth with 0.59 nm roughness （root-mean-square）.

Nitriding molybdenum: Effects of duration and fill gas pressure when using 100-Hz pulse DC discharge technique

Molybdenum is nitrided by a 100-Hz pulsed DC glow discharge technique for various time durations and fill gas pressures to study the effects on the surface properties of molybdenum. X-ray diffractometry （XRD）, scanning electron microscopy （SEM）, and atomic force microscopy （AFM） are used for the structural and morphological analysis of the nitrided layers. Vickers＇ microhardness tester is utilized to investigate surface microhardness. Phase analysis shows the formation of more molybdenum nitride molecules for longer nitriding durations at fill gas pressures of 2 mbar and 3 mbar （1 bar = 105 Pa）. A considerable increase in surface microhardness （approximately by a factor of 2） is observed for longer duration （10 h） and 2-mbar pressure. Longer duration （10 h） and 2-mbar fill gas pressure favors the formation of homogeneous, smooth, hard layers by the incorporation of more nitrogen.

Analysis of the factors controlling performances of Au-modified TiO2 nanotube array based photoanode in photo-electrocatalytic(PECa)cells

The efficiency of photo-electrocatalytic（PECa） devices for the production of solar fuels depends on several limiting factors such as light harvesting, charge recombination and mass transport diffusion. We analyse here how they influence the performances in PECa cells having a photo-anode based on Au-modified TiOnanotube（TNT） arrays, with the aim of developing design criteria to optimize the photo-anode and the PECa cell configuration for water photo-electrolysis（splitting） and ethanol photo-reforming processes.The TNT samples were prepared by controlled anodic oxidation of Ti foils and then decorated with gold nanoparticles using different techniques to enhance the visible light response through heterojunction and plasmonic effects. The activity tests were made in a gas-phase reactor, as well as in a PECa cell without applied bias. Results were analysed in terms of photo-generated current, Hproduction rate and photoconversion efficiency. Particularly, a solar-to-hydrogen efficiency of 0.83% and a Faradaic efficiency of 91%were obtained without adding sacrificial reagents.

Electrocatalytic production of glycolic acid via oxalic acid reduction on titania debris supported on a TiO_(2)nanotube array

Electrodes prepared by anodic oxidation of Ti foils are robust and not toxic materials for the electrocatalytic reduction of oxalic acid to glycolic acid, allowing the development of a renewable energy-driven process for producing an alcoholic compound from an organic acid at low potential and room temperature. Coupled with the electrochemical synthesis of the oxalic acid from CO_(2),this process represents a new green and low-carbon path to produce added value chemicals from CO_(2). Various electrodes prepared by anodic oxidation of Ti foils were investigated. They were characterized by the presence of a TiO_(2) nanotube array together with the presence of small patches, debris, or TiO_(2) nanoparticles. The concentration of oxygen vacancies, the amount of Ti^(3+) measured by X-ray photoelectron spectroscopy(XPS) and the intensity of the anodic peak measured by cyclic voltammetry, were positively correlated with the achieved oxalic acid conversion and glycolic acid yield. The analysis of the results indicates the presence of small amorphous TiO_(2) nanoparticles(or surface patches or debris) interacting with TiO_(2) nanotubes, the sites responsible for the conversion of oxalic acid and glycolic acid yield. By varying this structural characteristic of the electrodes, it is possible to tune the glycolic acid to glyoxylic acid relative ratio. A best cumulative Faradaic efficiency(FE) of about 84% with FE to glycolic acid around 60% and oxalic conversion about 30% was observed.

Special Issue on New Concepts and Advances in Photocatalytic Materials for Sustainable Energy

The use of solar energy to drive the chemical and energy processes,and the chemical storage of solar energy are the key elements to move to a low-carbon economy,sustainable society and to foster energy transition.For this reason,there is a fast-growing scientific interest on this subject,which is part of the general effort for a solar-driven chemistry and energy,the chemistry of the future.To realize this

Mechanical properties of Al/a-C nanocomposite thin films synthesized using a plasma focus device

The Al/a-C nanocomposite thin films are synthesized on Si substrates using a dense plasma focus device with alu- minum fitted anode and operating with CH4/Ar admixture. X-ray diffractometer results confirm the formation of metallic crystalline Al phases using different numbers of focus shots. Raman analyses show the formation of D and G peaks for all thin film samples, confirming the presence of a-C in the nanocomposite thin films. The formation of Al/a-C nanocomposite thin films is further confirmed using X-ray photoelectron spectroscopy analysis. The scanning electron microscope results show that the deposited thin films consist of nanoparticles and their agglomerates. The sizes of th agglomerates increase with increasing numbers of focus deposition shots. The nanoindentation results show the variations in hardness and elastic modulus values of nanocomposite thin film with increasing the number of focus shots. Maximum values of hardness and elastic modulus of the composite thin film prepared using 20 focus shots are found to be about 10.7 GPa and 189.2 GPa, respectively.