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Photo-electrochemical production of solar fuels from carbon dioxide, water, and sunlight is an appealing approach. Nevertheless, it remains challenging to scale despite encouraging demonstrations at low power input. Higher current densities require notable voltage input as ohmic losses and activation overpotentials become more significant, resulting in lower solar-to-CO conversion efficiencies. A concentrated photovoltaic cell is integrated into a custom-made heat managed photo-electrochemical device. The heat is transferred from the photovoltaic module to the zero-gap electrolyzer cell by the stream of anodic reactant and produce synergetic effects on both sides. With solar concentrations up to 450suns (i.e., 450kWm−2) applied for the first time to photo-electrochemical reduction of CO2, a partial current for CO production of 4A is achieved. At optimal conditions, the solar-to-CO conversion efficiency reaches 17% while maintaining a current density of 150mAcm−2in the electrolyzer and a CO selectivity above 90%, representing an overall 19% solar-to-fuel conversion efficiency. This study represents a first demonstration of photo-electrochemical CO2reduction under highly concentrated light, paving the way for resource efficient solar fuel production at high power input.

We demonstrate the dynamic operation of CO

Continuous-flow electrolyzers allow CO2 reduction at industrially relevant rates, but long-term operation is still challenging. One reason for this is the formation of precipitates in the porous cathode from the alkaline electrolyte and the CO2 feed. Here we show that while precipitate formation is detrimental for the long-term stability, the presence of alkali metal cations at the cathode improves performance. To overcome this contradiction, we develop an operando activation and regeneration process, where the cathode of a zero-gap electrolyzer cell is periodically infused with alkali cation-containing solutions. This enables deionized water-fed electrolyzers to operate at a CO2 reduction rate matching that of those using alkaline electrolytes (CO partial current density of 420 ± 50 mA cm-2 for over 200 hours). We deconvolute the complex effects of activation and validate the concept with five different electrolytes and three different commercial membranes. Finally, we demonstrate the scalability of this approach on a multi-cell electrolyzer stack, with a 100 cm2 / cell active area.

This is a perspective of the role that combustion synthesis, specifically solution combustion synthesis, has played in the development of ternary and quaternary metal oxide semiconductors, and materials derived from these compounds such as composites, solid solutions, and doped samples. The attributes of materials, collectively termed ‘complex oxides’ within the context of this discussion, are discussed in terms of their applicability in the generation of solar fuels from water splitting and CO2 reduction, and environmental pollution remediation via heterogeneous photocatalysis.

The “build-up” methodology, the importance of the order of the semiconductor layers in WO3‐TiO2/MWCNT composite materials was studied in terms of the applied synthesis pathway, morpho-structural parameters (mean crystallite size, crystal phase composition, morphology) and photocatalytic efficiency (using oxalic acid as model pollutant). The appearance of TiWOx phase in the composites contributed to the enhancement of the photocatalytic efficiencies, as different synthesis approaches led to different crystal phase compositions. Although, it was proven that a beneficial phase’s presence can be hindered if an excess of MWCNT or WO3 was applied. As the ratio of the mentioned materials was reduced, active composites were obtained, but the previously noticed TiWOx disappeared. Therefore, it was proven, that in the case of WO3-TiO2/MWCNT nanocomposite system several photocatalytic activity enhancement factors can be introduced, but not simultaneously (the disappearance of TiWOx at low MWCNT and WO3 contents and the appearance of highly crystalline anatase).

Syntheses of highly ordered carbon nanotube (CNT) forests were studied from the aspect of the quality of CNTs and the properties of Fe-Co catalyst. CNT forests were grown by catalytic chemical vapor deposition. The amount of catalyst was varied in two ways: (1) catalyst layers with different nanostructure were produced with pulsed laser deposition by applying different argon pressures in the deposition chamber, and (2) compact catalyst layers were deposited with different thickness in 1–5 nm range. Our results show that both the nanostructure of the catalyst layer and the layer thickness have a significant role in the formation of catalytic particles, therefore also on the character of CNT growth.

Electrochemical reduction of CO2 is a promising method for converting a greenhouse gas into value-added products, utilizing renewable energy. Novel catalysts, electrode assemblies, and cell configurations are all necessary to achieve economically appealing performance. In this talk, I am going to present a zero gap electrolyzer cell, which converts gas phase CO2 to products without the need for any liquid catholyte. I will show how to optimize the cell components, to simultaneously provide industrially relevant performance, such as high partial current density (up to 800 mA cm-2), low cell voltage (−2.8-3.2 V), high conversion efficiency (up to 45 %), and high selectivity for CO production (over 95%). I will also demonstrate our CO2 electrolyzer cell, where multiple layers are connected into an electrolyzer stack, thus scaling up the electrolysis process. The operation of the cell was validated using both silver nanoparticle and copper nanocube catalysts. Evenly distributing the CO2 gas among the layers (parallel connection), the operation of the cell stack was identical to the sum of multiple single-layer cells. When passing the CO2 gas through the layers one after the other (serial gas connection), the CO2 conversion efficiency was increased remarkably. Finally, I will show how the cell can operate with pure water feed on the anode side, therefore avoiding the use of alkaline anolyte. A carefully designed activation protocol will be presented, which allows the cell to operate at high current density, using pure water feed. The effect of temperature and flow rate on the operation will also be presented. Finally, the nature of ion-transport through the anion exchange membrane as a function of the operational conditions will be discussed.

We report electrical conductivity measurements of Polymethyl-methacrylate filled by onion-like carbon particles with primary particle size of $\approx 5$ nm. We shown that the conductivity $\sigma$ is exceptionally high even at very low loadings, and that its low-temperature dependence follows a Coulomb gap regime at atmospheric pressure and an activated behavior at a pressure of $2$ GPa. We interpret this finding in terms of the enhancement under the applied pressure of the effective dielectric permittivity within the aggregates of onion-like carbons, which improves the screening of the Coulomb interaction and reduces the optimal hopping distance of the electrons., Comment: 4 pages, 3 figures, 1 page of supplementary material

In this study, the photoelectrochemical behavior of electrodeposited FeNiOOH/Fe2O3/graphene nanohybrid electrodes is investigated, which has precisely controlled structure and composition. The photoelectrode assembly is designed in a bioinspired manner where each component has its own function: Fe2O3 is responsible for the absorption of light, the graphene framework for proper charge carrier transport, while the FeNiOOH overlayer for facile water oxidation. The effect of each component on the photoelectrochemical behavior is studied by linear sweep photovoltammetry, incident photon-to-charge carrier conversion efficiency measurements, and long-term photoelectrolysis. 2.6 times higher photocurrents are obtained for the best-performing FeNiOOH/Fe2O3/graphene system compared to its pristine Fe2O3 counterpart. Transient absorption spectroscopy measurements reveal an increased hole-lifetime in the case of the Fe2O3/graphene samples. Long-term photoelectrolysis measurements in combination with Raman spectroscopy, however, prove that the underlying nanocarbon framework is corroded by the photogenerated holes. This issue is tackled by the electrodeposition of a thin FeNiOOH overlayer, which rapidly accepts the photogenerated holes from Fe2O3, thus eliminating the pathway leading to the corrosion of graphene.

Electrochemical reduction of CO2 is a promising method for converting a greenhouse gas into value-added products, utilizing renewable energy. Novel catalysts, electrode assemblies, and cell configurations are all necessary to achieve economically appealing performance. In this talk, I am going to present a zero gap electrolyzer cell, which converts gas phase CO2 to products without the need for any liquid catholyte. This is the first report of a CO2 electrolyzer cell, where multiple stacks are connected, thus scaling up the electrolysis process. The operation of the cell was validated using both silver nanoparticle and copper nanocube catalysts, and the first was employed for the optimization of the electrolysis conditions. Upon this, CO formation with partial current densities above 250 mA cm−2 were achieved routinely, which was further increased to 300 mA cm−2 (with ~95 % Faradaic efficiency) by pressurizing the CO2 inlet. Evenly distributing the CO2 gas among the stacks (parallel connection), the operation of the multi-stack cell was identical to the sum of multiple single-stack cells. When passing the CO2 gas through the stacks one after the other (serial gas connection), the CO2 conversion efficiency was increased remarkably. Importantly, the presented electrolyzer simultaneously provides high partial current density, low cell voltage (−3.0 V), high conversion efficiency (up to 40 %), and high selectivity for CO production; while operating at up to 10 bar differential pressure. In the second part of the talk I will show how the cell can operate with pure water feed on the anode side, therefore avoiding the use of alkaline anolyte. A carefully designed activation protocol will be presented, which allows the cell to operate at high current density, using pure water feed. The effect of temperature and flow rate on the operation will also be presented. Finally, the nature of ion-transport through the anion exchange membrane as a function of the operational conditions will be discussed.

[Image: see text] Electrochemical reduction of CO(2) is a value-added approach to both decrease the atmospheric emission of carbon dioxide and form valuable chemicals. We present a zero gap electrolyzer cell, which continuously converts gas phase CO(2) to products without using any liquid catholyte. This is the first report of a multilayer CO(2) electrolyzer stack for scaling up the electrolysis process. CO formation with partial current densities above 250 mA cm(–2) were achieved routinely, which was further increased to 300 mA cm(–2) (with ∼95% faradic efficiency) by pressurizing the CO(2) inlet (up to 10 bar). Evenly distributing the CO(2) gas among the layers, the electrolyzer operates identically to the sum of multiple single-layer electrolyzer cells. When passing the CO(2) gas through the layers consecutively, the CO(2) conversion efficiency increased. The electrolyzer simultaneously provides high partial current density, low cell voltage (−3.0 V), high conversion efficiency (up to 40%), and high selectivity for CO production.

Vertically aligned CNT carpets combined with inorganic semiconductors are expected good prospect in practical applications, especially in photocatalysis. If these devices are in production, a fast and non-invasive characterization method will be required. Ellipsometry is widely used in industry as an in-line monitoring tool, so in this study the applicability of ellipsometry for characterizing CNT carpets is investigated. It is shown that ellipsometric evaluation can provide information about the density and the optical properties of the nanotubes; however, the properties of the individual nanotubes (diameter, wall number) can not be taken into account during ellipsometric modeling. To overcome these limitations, numerical simulations are also presented.

Photoelectrochemical reduction of CO2 to form useful chemicals is an increasingly studied avenue for harnessing and storing solar energy. In the quest for efficient and stable photocathode materials, nanostructured hybrid assemblies are eminently attractive candidates, because they exhibit multiple favorable properties that cannot be expected from a single material. One possible direction is to combine p-type inorganic semiconductors with highly conductive large surface area electrodes such as carbon nanotube networks. In this work, the controlled synthesis and photoelectrochemical behavior of CNT/Cu2O films was reported for the first time for CO2 reduction applications. A carefully designed, multiple-step electrodeposition protocol was developed that ensured homogeneous coating of CNTs with Cu2O nanocrystals. The hybrid materials were characterized by electron microscopy, X-ray diffraction, Raman spectroscopy, electrochemical impedance spectroscopy, and photoelectrochemical methods. The hybrid films had five-fold higher electrical conductivity compared to their pure Cu2O counterparts. This enhanced charge transport property resulted in a drastic increase in the photocurrents measured for CO2 reduction. In addition to this superior performance, long term photoelectrolysis measurements proved that the CNT/Cu2O hybrids were more stable than the oxide alone. These observations, together with the established structure/property relationships, may contribute to the rational design of nanocarbon/inorganic semiconductor hybrid photocathodes for deployment in photoelectrochemical cells.

With the rapid development of renewable energy technologies there is an urgent need to find synthesis routes that address the needs of materials in a reproducible and affordable way. In this study, we present a one-step electrochemical method for the deposition of nanocrystalline titanium dioxide films on different carbon substrates. By optimizing the synthetic conditions, electrodeposition of nanocrystalline and porous titanium dioxide layers was achieved in only a few minutes. To deconvolute the complex effect of the solution pH and temperature, as well as the deposition potential, a set of systematic experiments was carried out on glassy carbon electrodes. The robustness and general applicability of this synthetic approach is demonstrated by extending it to graphene film electrodes. The phase composition of TiO2 was controlled by varying the solution composition. The photoelectrochemical performance of the electrodeposited titanium dioxide films was better than, or at least comparable to the benchmark...

Efficient and reproducible growth of vertically aligned carbon nanotube (CNT) forests by catalytic chemical vapor deposition (CVD) requires precise setting of the properties of the catalyst thin films and CVD conditions. In this work, super growth of vertically aligned CNTs onto Al2O3 support and Fe–Co catalyst layer system is presented. The layers were grown by pulsed laser deposition (PLD) onto silicon wafer pieces. Their thickness and optical properties were controlled by spectroscopic ellipsometry. The effect of heat treatment at 750 °C in nitrogen and in hydrogen of these PLD layers was compared. High-resolution electron microscopic images showed that treatment of catalyst layers in H2 resulted in finer and denser catalytic particles. As a result, well-aligned, dense and few-walled CNT forests with 1–1.5 mm height were deposited by water-vapor-assisted CVD on the hydrogen-treated films, while without hydrogen treatment defected CNT structures were grown. According to these observations, Raman spectroscopy showed a higher degree of crystallinity in case of CNT-s, where reduction by hydrogen influenced the oxidation state of the metallic catalytic particles in a beneficial way.

In the past two decades, important results have been achieved in the field of carbon nanotube (CNT) research, which revealed that carbon nanotubes have extremely good electrical and mechanical properties The range of applications widens more, if CNTs form a forest-like, vertically aligned structure (VACNT) Although, VACNT-conductive substrate structure could be very advantageous for various applications, to produce proper system without barrier films i.e. with good electrical contact is still a challenge. The aim of the current work is to develop a cheap and easy method for growing carbon nanotubes forests on conductive substrate with the CCVD (Catalytic Chemical Vapor Deposition) technique at 640 °C. The applied catalyst contained Fe and Co and was deposited via dip coating onto an aluminum substrate. In order to control the height of CNT forest several parameters were varied during the both catalyst layer fabrication (e.g. ink concentration, ink composition, dipping speed) and the CCVD synthesis (e.g. gas feeds, reaction time). As-prepared CNT forests were investigated with various methods such as scanning electron microscopy, Raman spectroscopy, and cyclic voltammetry. With such an easy process it was possible to tune both the height and the quality of carbon nanotube forests.

Bamboo-like carbon nanotubes (BCNTs) are special nanotubes with unique morphology and properties. Until now BCNTs could be fabricated mostly by nitrogen doping, but the use of nitrogen-containing organic compound is toxic and it makes the synthesis more complicated. Here, we present a simple method for the selective growth of bamboo-like CNTs. We employed high energy ball milling method for preparing Fe–Co–Cu (2.5–2.5–1 wt%) catalysts on Al2O3 support to synthesize bamboo-like CNTs by hydrogen-assisted catalytic chemical vapor deposition (CCVD) from acetylene at 720 °C. The effect of milling time on the growth of bamboo-like CNTs was investigated. Morphology and structure of the carbon deposits were characterized by transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), and Raman spectroscopy. The growth mechanism of the as-prepared bamboo-like CNTs, and the role of copper containing catalyst were studied. Their properties theoretically make them ideal for gas storage and can be used as matrix fillers in composite materials, where the improved electrical conductivity with the mechanical properties of the tubes are the novel factor. HRTEM image of bamboo-like carbon nanotube (the scalebar is 50 nm).

Combination of an oxide semiconductor with a highly conductive nanocarbon framework (such as graphene or carbon nanotubes) is an attractive avenue to assemble efficient photoelectrodes for solar fuel generation. To fully exploit the possible synergies of the hybrid formation, however, precise knowledge of these systems is required to allow rational design and morphological engineering. In this paper, we present the controlled electrochemical deposition of nanocrystalline p-Cu2O on the surface of different graphene substrates. The developed synthetic protocol allowed tuning of the morphological features of the hybrids as deduced from electron microscopy. (Photo)electrochemical measurements (including photovoltammetry, electrochemical impedance spectroscopy, photocurrent transient analysis) demonstrated better performance for the 2D graphene containing photoelectrodes, compared to the bare Cu2O films, the enhanced performance being rooted in suppressed charge carrier recombination. To elucidate the precise role of graphene, comparative studies were performed with carbon nanotube (CNT) films and 3D graphene foams. These studies revealed, after allowing for the effect of increased surface area, that the 3D graphene substrate outperformed the other two nanocarbons. Its interconnected structure facilitated effective charge separation and transport, leading to better harvesting of the generated photoelectrons. These hybrid assemblies are shown to be potentially attractive candidates in photoelectrochemical energy conversion schemes, namely CO2 reduction.

Given that CO2 is a greenhouse gas, using the energy of sunlight to convert CO2 to transportation fuels (such as methanol or methane) represents a value-added approach to the simultaneous generation of alternative fuels and environmental remediation of carbon emissions. Electrochemistry and photoelectrochemistry have been proven to be a useful avenue for solar water splitting. CO2 reduction, however, is multi-electron in nature (e.g., 6 e- to methanol) with considerable kinetic barriers to electron transfer. It therefore requires the use of carefully designed electrode surfaces to accelerate e- transfer rates to levels that make practical sense. In this talk I will present hybrid photoelectrodes leading to enhanced efficiency, selectivity, and stability. First, I will present the use of electrosynthetic (and photoelectrosynthetic) methods for preparing semiconductors on nanocarbon-modified electrode surfaces. Composites of nanocarbons with both inorganic and organic semiconductors represent an interesting class of new functional materials. Therefore, I will show how electrodeposition can be used to tune composition, crystal structure, and morphology of the nanocomposites for targeted applications. In the second part of my talk, selected examples will be given for how these electrosynthesized hybrid assemblies can be deployed in various photoelectrochemical application schemes, most importantly CO2 conversion. I will present the controlled synthesis and photoelectrochemical behavior of Cu2O/CNT and Cu2O/graphene composites. A carefully designed, multiple-step electrodeposition protocol was developed that ensured homogeneous coating of the CNTs with the Cu2O nanocrystals. TiO2/ graphene nanocomposites were also obtained in a similar manner. This enhanced charge transport property for the hybrids resulted in a drastic increase in the photocurrents measured for the CO2 reduction. In addition to this superior performance, long term photoelectrolysis measurements proved that the Cu2O/nanocarbon hybrids were more stable than the oxide alone. Taking these observations together as a whole, a general model will be presented on the role of the nanocarbon scaffold. Acknowledgements This research was partially supported by the “Széchenyi 2020” program in the framework of GINOP-2.3.2-15-2016-00013 “Intelligent materials based on functional surfaces – from syntheses to applications” project.

Micro- and nanosized carbon fibers with special helical structure have many promising applications. These structures can be used as reinforcing materials in polymer composites, wave absorption or tactile sensor elements. In this fiber preparation method the applied catalyst precursor were nickel (II) oxide nanoparticles. Sulfuric modification of nickel containing catalyst grain yields carbon fibers with special coiled structures in acetylene decomposition. The preparation of carbon fiber coils by the CCVD method was carried out between 700– 800 C using thiophene impurity. The catalyst particles and the observed structures were studied by X-ray diffractometry (XRD) and scanning electron microscopy (SEM). The lengths of fibers can even reach millimeter size and the average fiber diameter is 1 µm. The diameter of coils is 1–20 µm, the coil pitch is 0.5–1.5 µm. Carbon microcoils might have interesting applications in the near future.

Carbon nanomaterials, especially carbon nanotubes and graphene (either alone, or as building blocks of organized 3-D superstructures), are attracting significant attention as large surface area electrode support materials. Their composites with both inorganic and organic semiconductors represent an interesting class of new functional materials. In the first part of my talk I will briefly focus on the use of electrosynthetic (and photoelectrosynthetic) methods for preparing semiconductors on nanocarbon-modified electrode surfaces.1,2I will show how electrodeposition can be used to tune composition, crystal structure, and morphology of the nanocomposites for targeted applications. In the second part of my talk, selected examples will be given for how these electrosynthesized hybrid assemblies can be deployed in photoelectrochemical CO2 conversion. Given that CO2 is a greenhouse gas, using sunlight to convert CO2 to transportation fuel (such as methanol) represents a value-added approach to the simultaneous generation of alternative fuels and environmental remediation of carbon emissions from the continued use of conventional fuels.3 I will present the controlled synthesis and photoelectrochemical behavior of Cu2O/CNT4 and Cu2O/3D graphene composites for the CO2 reduction application. A carefully designed, multiple-step electrodeposition protocol was developed that ensured homogeneous coating of the CNTs with the Cu2O nanocrystals. This enhanced charge transport property for the hybrids resulted in a drastic increase in the photocurrents measured for the CO2 reduction. In addition to this superior performance, long term photoelectrolysis measurements proved that the Cu2O/CNT hybrids were more stable than the oxide alone. Structure property relationships will be shown, which may act as guidelines for the rational design of nanocomposite photoelectrodes. Figure 1. Illustration of the structure of the Cu2O/CNT composite and the increasing photocurrent with the increasing CNT-content. [1] C. Janáky and K. Rajeshwar: The Role of (Photo)electrochemistry in the Rational Design of Hybrid Conducting Polymer / Semiconductor Assemblies: From Fundamental Concepts to Practical Applications, Prog Pol Sci, 43 (2015) 396-435 [2] C. Janáky, E. Kecsenovity, K. Rajeshwar: Electrodeposition of Inorganic Oxide/ Nanocarbon Composites: Opportunities and Challenges, ChemElectroChem, 3 (2016) 181-192 [3] G. Ghadimkhani, N. R. De Tacconi, W. Chanmanee, C. Janaky, K. Rajeshwar: Efficient solar photoelectrosynthesis of methanol from carbon dioxide using hybrid CuO/Cu2O semiconductor nanorod arrays, Chem. Commun. 49 (2013) 1297–1299 [4] E. Kecsenovity, B. Endrődi, Z. Pápa, K. Hernádi, K. Rajeshwar, C. Janáky: Decoration of ultralong carbon nanotubes with Cu2O nanocrystals: a hybrid platform for enhanced photoelectrochemical CO2 reduction, J Mater Chem A, 4 (2016) 3139-3147 Figure 1

A poly(aryl piperidinium)-based anion exchange membrane (PiperION) with high carbonate conductance is employed for CO2 electrolysis to CO in conjunction with a tailored electrolyzer cell structure. This combination results in unprecedentedly high partial current densities in zero-gap cells (jCO > 1.0 A cm−2), while maintaining high conversion (20–45%), selectivity (up to 90%) and low cell voltage (2.6–3.4 V).

Photo-electrochemical production of solar fuels from carbon dioxide, water, and sunlight is an appealing approach. Nevertheless, it remains challenging to scale despite encouraging demonstrations at low power input. Higher current densities require notable voltage input as ohmic losses and activation overpotentials become more significant, resulting in lower solar-to-CO conversion efficiencies. A concentrated photovoltaic cell is integrated into a custom-made heat managed photo-electrochemical device. The heat is transferred from the photovoltaic module to the zero-gap electrolyzer cell by the stream of anodic reactant and produce synergetic effects on both sides. With solar concentrations up to 450 suns (i.e., 450 kW m−2) applied for the first time to photo-electrochemical reduction of CO2, a partial current for CO production of 4 A is achieved. At optimal conditions, the solar-to-CO conversion efficiency reaches 17% while maintaining a current density of 150 mA cm−2 in the electrolyzer and a CO selectivity above 90%, representing an overall 19% solar-to-fuel conversion efficiency. This study represents a first demonstration of photo-electrochemical CO2 reduction under highly concentrated light, paving the way for resource efficient solar fuel production at high power input.