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Two coordination complexes have been made by combining the dithiolene complexes [M(mnt)2]2- (mnt = maleonitriledithiolate; M = Ni2+ or Cu2+) as anion, with the copper(II) coordination complex [Cu(Stetra)] (Stetra = 6,6'-bis(4,5-dihydrothiazol-2-yl)-2,2'-bipyri-dine) as cation. The variation of the metal centers leads to a dramatic change in the conductivity of the materials, with the M = Cu2+ variant (Cu-Cu) displaying semiconductor behavior with a conductivity of approximately 2.5 × 10-8 S cm-1, while the M = Ni2+ variant (Ni-Cu) displayed no observable conductivity. Computational studies found Cu-Cu enables a minimization of reorganization energy losses and, as a result, a lower barrier to the charge transfer process, resulting in the reported higher conductivity.

In an effort to support the large-scale implementation of clean hydrogen in industry and society, the electrolytic decomposition of water is considered a realistically enticing prospect, provided the guarantee of affordable and durable material components. Within alkaline systems, earth-abundant electrocatalysts could provide both these requirements. However, a continued exploration of the reactivity and the causes behind different behaviors in performance are necessary to guide optimization and design. In this paper, Ta-doped NiO thin films are prepared via DC magnetron sputtering (1–2–4 at % Ta) to demonstrate the effect of surface electronic modulation by non-3d elements on the catalysis of the oxygen evolution reaction (OER). Material properties of the catalysts are analyzed via Rutherford backscattering spectrometry, X-ray diffractometry, photoelectron spectroscopy, and Raman spectroscopy. Ta impurities are shown to be directly responsible for increasing the valence state of Ni sites and enhancing reaction kinetics, resulting in performance improvements of up to 64 mV at 10 mA cm–2 relative to pristine NiO. Particularly, we show that by applying operando Raman spectroscopy, Ta enhances the ability to create high-valence Ni in γ-NiOOH at a lower overpotential compared to the undoped sample. The lowered overpotentials of the OER can thus be attributed to the energetically less hindered advent of the creation of γ-NiOOH species on the pre-catalyst surface: a phenomenon otherwise unresolved through simple voltammetry.

Summary Conventional redox mediators based on metal coordination complexes undergo electron transfer through the change in oxidation state of the metal center. However, electron transfer kinetics are offset toward preferred oxidation states when preorganized ligands constrain the reorganization of the coordination sphere. In contrast, we report here on dimeric copper(II/I) redox couples, wherein the extent of oxidation/reduction of two metal centers dictates the dynamic formation of dimer and monomer complexes: the dimeric (Cu(I))2 transitions to monomers of Cu(II). The bis(thiazole/pyrrole)-bipyridine tetradentate ligands stabilize both oxidation states of the unique redox systems. The dynamic dimer redox mediators offer a viable two-electron redox mechanism to develop efficient hybrid solar cells through inhibited recombination and rapid charge transport. Density functional theory calculations reveal inner reorganization energies for single-electron transfer as low as 0.27 eV, marking the dimeric complexes superior redox systems over single complexes as liquid and potentially solid-state electrolytes.

Emerging technologies in solar energy will be critical in enabling worldwide society in overcoming the present energy challenges and reaching carbon net zero. Inefficient and unstable charge transport materials limit the current emerging energy conversion and storage technologies. Low-dimensional coordination polymers represent an alternative, unprecedented class of charge transport materials, comprised of molecular building blocks. Here, we provide a comprehensive study of mixed-valence coordination polymers from an analysis of the charge transport mechanism to their implementation as hole-conducting layers. CuII dithiocarbamate complexes afford morphology control of 1D polymer chains linked by (CuI2X2) copper halide rhombi. Concerted theoretical and experimental efforts identified the charge transport mechanism in the transition to band-like transport with a modeled effective hole mass of 6me. The iodide-bridged coordination polymer showed an excellent conductivity of 1 mS cm−1 and a hole mobility of 5.8 10−4 cm2 (V s)−1 at room temperature. Nanosecond selective hole injection into coordination polymer thin films was captured by nanosecond photoluminescence of halide perovskite films. Coordination polymers constitute a sustainable, tunable alternative to the current standard of heavily doped organic hole conductors.

A theoretical framework and analysis are presented that can be generally used for any complex material surface where an adsorption or interaction at single sites can be modulated by the electronic structure of the local environment.

The ability to control electronic states by utilizing quantum confinement of one of the material components in heterojunctions is a promising approach to perform energy-level matching. In this work, we report the possibility to achieve optimum energy alignment in heterojunctions made from size-controlled quantum dots (Q-dots) of ZnO in combination with three copper oxides: Cu2O, Cu4O3, and CuO. Quantum confinement effects on the ZnO nanoparticles in the diameter range 2.6–7.4 nm showed that the direct optical band gap decreased from 3.99 to 3.41 eV, with a dominating shift occurring in the conduction band (CB) edge, and thus the possibility to obtain close to 0.6 eV CB edge shift by controlling the size of ZnO. The effect was utilized to align the electronic bands in the ZnO Q-dot/copper oxide heterojunctions to allow for charge transfer between the materials and to test the ability to improve the photocatalytic performance for the system, evaluated by the transformation of a dye molecule in water. The catalyst materials were investigated by X-ray diffraction, scanning electron microscopy, ultraviolet–visible (UV–vis), photoluminescence, and Raman spectroscopy. The most promising material combination was found to be the Cu2O copper oxide in combination with an energy aligned ZnO Q-dot system with approximately 7 nm diameter, showing strong synergy effects in good agreement with the energy-level analysis, outperforming the added effect of its individual components, ZnO-Q-dots and Cu2O, by about 140%. The results show that utilization of a heterojunction with controllable energy alignment can provide a drastically improved photocatalytic performance. Apart from increased photocatalytic activity, specific surface states of ZnO are quenched when the heterojunction is created. It is anticipated that the same approach can be utilized in several material combinations with the added benefit of a system with controllable overpotential and thus added specificity for the targeted reduction reaction.

A molecular precursor approach to titania (anatase) nanopowders modified with different amounts of rare-earth elements (REEs: Eu, Sm, and Y) was developed using the interaction of REE nitrates with titanium alkoxides by a two-step solvothermal–combustion method. The nature of an emerging intermetallic intermediate was revealed unexpectedly for the applied conditions via a single-crystal study of the isolated bimetallic isopropoxide nitrate complex [Ti2Y(iPrO)9(NO3)2], a nonoxo-substituted compound. Powders of the final reaction products were characterized by powder X-ray diffraction, scanning electron microscopy–energy-dispersive spectroscopy, Fourier transform infrared, X-ray photoelectron spectroscopy, Raman spectroscopy, and photoluminescence (PL). The addition of REEs stabilized the anatase phase up to ca. 700 °C before phase transformation into rutile became evident. The photocatalytic activity of titania modified with Eu3+ and Sm3+ was compared with that of Degussa P25 titania as the control. PL studies indicated the incorporation of Eu and Sm cations into titania (anatase) at lower annealing temperatures (500 °C), but an exclusion to the surface occurred when the annealing temperature was increased to 700 °C. The efficiency of the modified titania was inferior to the control titania while illuminated within narrow wavelength intervals (445–465 and 510–530 nm), but when subjected to a wide range of visible radiation, the Eu3+- and Sm3+-modified titania outperformed the control, which was attributed both to doping of the band structure of TiO2 with additional energy levels and to the surface chemistry of the REE-modified titania., Molecular insight into the mechanism of solution−combustion synthesis provided clues to understanding the photocatalytic properties of rare-earth-doped nanotitania.

We have investigated the doping-induced local structural and electronic effects in the recently developed low band gap room temperature ferroelectric Mn-Nb co-doped BaTiO3. Experimental and theoretical Raman spectroscopies are utilized to quantify the Ti off-centering, identified to be the intrinsic origin of ferroelectricity in these systems. Mn and Nb exhibit contrasting doping behaviors that have remarkable effects on BaTiO3 functionality. Jahn-Teller distorted Mn3+ is primarily associated with lowering of the bulk band gap, while charge-compensating Nb5+ off-centers within the O-6 octahedra, creating a polar mode that stabilizes the ferroelectric ground state. The charge neutral aliovalent Mn3+-Nb5+ pair effectively couples to the inherent ferroelectric instability of the BaTiO3 lattice, restoring some spontaneous polarization lost by doping Mn3+ (d(4)) ions at Ti4+ (d(0)) sites.

Interaction of surface adsorbate vibration and intraband electron absorption in nanocrystals has been reported to affect the photophysical properties of both nanocrystals and surface adsorbates and may affect the performance of hybrid photocatalysts composed of semiconductor nanocrystals and molecular catalysts. Here, by combining ultrafast transient visible and IR spectroscopic measurements, we report the observation of Fano resonances between the intraband transition of the photogenerated electrons in CdS and CdSe nanocrystals and CO stretching vibrational modes of adsorbed molecular catalysts, [Fe2(cbdt)(CO)6] (FeFe; cbdt = 1-carboxyl-benzene-2,3-dithiolate), a molecular mimic for the active site of FeFe-hydrogenase. The occurrence of Fano resonances is independent of nanocrystal types (rods vs dots) or charge transfer character between the nanocrystal and FeFe, and is likely a general feature of nanocrystal and molecular catalyst hybrid systems. These results provide new insights into the fundamental interactions in these hybrid assemblies for artificial photosynthesis.

Mixed-cation perovskite materials have shown great potential for sunlight harvesting and have surpassed unmixed perovskite materials in solar cell efficiency and stability. The role of mixed monovalent cations in the enhanced optoelectronic properties and excited state response, however, are still elusive from a theoretical perspective. Herein, through time dependent density functional theory calculations of mixed cation perovskites, we report the electronic structure of Cs formamidinium (FA) mixed cationic lead iodide (Cs

Analysis and determination of crystal orientation and exposed surface facets remain a challenge in nanomaterial science. In this work we show that polarized and non-polarized Raman spectroscopy can be useful tools to determine crystal plane orientation and conveniently be applied to spatial dimensions limited only by the diffraction limit of the excitation laser. The methodology is exemplified for wurtzite structured ZnO. Three different crystal facets, (0001), (1-100), and (11-20) of ZnO are investigated with angle resolved polarized Raman spectroscopy. The polarization direction dependences of the main Raman peaks are characterized and related to the experimental vibrational modes in the crystal lattice and corroborated by density functional theory (DFT) calculations using two different hybrid functionals. By exploiting the symmetry of the modes and differences in Raman intensity of the optically activated phonons, a simple model is derived for determining the relation between the polar and non-polar crystal orientation. The results are generalized to allow peak intensity ratio analysis using Raman spectroscopy with a non-polarized light source, making it compatible with Raman mapping, as well as to include a critical discussion on the ability to determine the crystal plane orientation and exposed crystal facets using this model for nano dimensional ZnO and equivalent models for other nanomaterials. As the approach allows for use of non-polarized light sources, near-field excitations and local plasmons can in an extension be utilized for determination of crystal orientation and exposed planes in dimensions much smaller than the diffraction limit.

ChemSusChem 13, 5901 - 5909 (2020). doi:10.1002/cssc.202001716, Tuning the local environment of nanomaterial‐based catalysts has emerged as an effective approach to optimize their oxygen evolution reaction (OER) performance, yet the controlled electronic modulation around surface active sites remains a great challenge. Herein, directed electronic modulation of NiO nanoparticles was achieved by simple surface molecular modification with small organic molecules. By adjusting the electronic properties of modifying molecules, the local electronic structure was rationally tailored and a close electronic structure‐activity relationship was discovered: the increasing electron‐withdrawing modification readily decreased the electron density around surface Ni sites, accelerating the reaction kinetics and improving OER activity, and vice versa. Detailed investigation by operando Raman spectroelectrochemistry revealed that the electron‐withdrawing modification facilitates the charge‐transfer kinetics, stimulates the catalyst reconstruction, and promotes abundant high‐valent γ‐NiOOH reactive species generation. The NiO−C$_6$F$_5$ catalyst, with the optimized electronic environment, exhibited superior performance towards water oxidation. This work provides a well‐designed and effective approach for heterogeneous catalyst fabrication under the molecular level., Published by Wiley-VCH, Weinheim

A damping-like spin-orbit torque (SOT) is a prerequisite for ultralow-power spin logic devices. Here, we report on the damping-like SOT in just one monolayer of the conducting transition-metal dichalcogenide (TMD) TaS2 interfaced with a NiFe (Py) ferromagnetic layer. The charge-spin conversion efficiency is found to be 0.25 +/- 0.03 in TaS2(0.88)/Py(7), and the spin Hall conductivity (14.9 x 10(s) h/2e Omega(-1) m(-1) is found to be superior to values reported for other TMDs. We also observed sizable field-like torque in this heterostructure. The origin of this large damping-like SOT can be found in the interfacial properties of the TaS2/Py heterostructure, and the experimental findings are complemented by the results from density functional theory calculations. It is envisioned that the interplay between interfacial spinorbit coupling and crystal symmetry yielding large damping-like SOT. The dominance of damping-like torque demonstrated in our study provides a promising path for designing the next-generation conducting TMD-based low-powered quantum memory devices.

Carbon-rich biochar can be produced by pyrolysis of biomass. Depending on the precise production pathway, the surface chemistry and porosity can be tuned and made compatible for a defined application. This shear benefit has persuaded researcher to explore its suitability in various electrochemical applications related to energy storage and conversion. In this article, we succinctly discuss the potentials of biochar in electrocatalysis, fuel cell, supercapacitors, and rechargeable batteries. We have concluded this article with recommendations for future research.

Zinc oxide is a well-known metal oxide semiconductor with a wide direct band gap that offers a promising alternative to titanium oxide in photocatalytic applications. ZnO is studied here as quantum ...

Earth abundant iron pyrite (FeS2) has attracted considerable attention as a potential non-toxic absorber material in lieu of widely used but toxic and relatively rare Indium containing CIGS and CdTe for thin-film solar cells. Research in this regard has been progressed in understanding its fundamental electronic, optical and chemical properties, while its surface polarity is rarely been studied. In this contribution, we have investigated the adhesion of water to determine the wettability (i.e. hydrophilic or hydrophobic) of naturally grown FeS2, and thereof, the polarity of the surface. FeS2 has a cubic crystal structure that grows and cleaves along its cubic faces. Based on the measurements using Sessile drop method, we have found that the surfaces of the pyrite phase of FeS2 crystals are intrinsically super-hydrophilic and highly polar. Our finding is corroborated with X-ray diffraction, Fourier Transform Infrared, Raman Spectroscopy, particle size determination, and contact angle measurements of the pyrite phase. The surface polarity would be a critical factor for choosing surface passivation protocols and type of contact materials as well as for interpreting surface field effects in the system for solar cell application with material heterojunctions.

C-18 is a cyclo[18]carbon that consists of 18 carbon atoms. Beyond the detection of an intermediate gas phase species, the synthesis of a solid-state C-18 and elucidation of its bonding structure have remained significant scientific challenges over the past half century. Until recently, this unorthodox carbon allotrope was conceptually feasible, while experimentally elusive in the solid state. Finally, this carbon allotrope has made its long-awaited debut when a collaborative research effort successfully synthesized and revealed the structure of cyclocarbon. The long 50 years of waiting is now over with the unveiling of this new form of chemistry's most celebrated element. This article highlights the discovery of this new allotrope from the carbon family, and discusses its chemical structure, potential applications, and challenges for future research.

Structural characterization of transient electrochemical species in the sub-millisecond time scale is the holy grail of electrochemistry. Presently, common time resolution of structural spectro-electrochemical methods is about 0.1 seconds. Herein, a transient spectro-electrochemical Raman setup of easy implementation is described which allows sub-ms time resolution. The technique studies electrochemical processes by initiating the reaction with an electric potential (or current) pulse and analyses the product with a synchronized laser pulse of the modified Raman spectrometer. The approach was validated by studying a known redox driven isomerization of a Ru-based molecular switch grafted, as monolayer, on a SERS active Au microelectrode. Density-functional-theory calculations confirmed the spectral assignments to sub-ms transient species. This study paves the way to a new generation of time-resolved spectro-electrochemical techniques which will be of fundamental help in the development of next generation electrolizers, fuel cells and batteries.

et al., Large datasets are now ubiquitous as technology enables higher-throughput experiments, but rarely can a research field truly benefit from the research data generated due to inconsistent formatting, undocumented storage or improper dissemination. Here we extract all the meaningful device data from peer-reviewed papers on metal-halide perovskite solar cells published so far and make them available in a database. We collect data from over 42,400 photovoltaic devices with up to 100 parameters per device. We then develop open-source and accessible procedures to analyse the data, providing examples of insights that can be gleaned from the analysis of a large dataset. The database, graphics and analysis tools are made available to the community and will continue to evolve as an open-source initiative. This approach of extensively capturing the progress of an entire field, including sorting, interactive exploration and graphical representation of the data, will be applicable to many fields in materials science, engineering and biosciences., Open access funding provided by Helmholtz-Zentrum Berlin für Materialien und Energie GmbH., The core funding of the project has been received from the European Union’s Horizon 2020 research and innovation programme under grant agreement no. 787289. We acknowledge the following sources for individual funding. Cambridge India Ramanujan Scholarship, China Scholarship Council, Deutscher Akademischer Austauschdienst (DAAD), EPSRC (grant no. EP/S009213/1), European Union’s Horizon 2020 research and innovation programme (grant no. 764787, EU Project ‘MAESTRO’), (grant no. 756962, ERC Project ‘HYPERION’), (grant no. 764047, EU Project ‘ESPResSo’ and grant no. 850937), GCRF/EPSRC SUNRISE (EP/P032591/1), German Federal Ministry for Education and Research (BMBF), HyPerFORME, NanoMatFutur (grant no. 03XP0091). PEROSEED (ZT-0024), Helmholtz Energy Materials Foundry, The Helmholtz Innovation Laboratory HySPRINT. BMBF (grant nos. 03SF0540, 03SF0557A), HyPerCells graduate school, Helmholtz Association, Helmholtz International Research School (HI-SCORE), the Erasmus programme (CDT-PV, grant no. EP/L01551X/1), the European Union’s Horizon 2020 research and innovation programme (Marie Skłodowska-Curie grant agreement nos. 841386, 795079 and 840751), Royal Society University Research Fellowship (grant no. UF150033). SNaPSHoTs (BMBF), SPARC II, German Research Foundation (DFG, grant no. SPP2196), The National Natural Science Foundation of China (grant no. 51872014), the Recruitment Programme of Global Experts, Fundamental Research Funds for the Central Universities and the ‘111’ project (grant no. B17002), the US Department of Energy’s Office of Energy Efficiency and Renewable Energy under Solar Energy Technologies Office (SETO) agreement no. DE-EE0008551, the Colombia Scientific Programme in the framework of the call Ecosistema Cientifíco (Contract no. FP44842-218-2018), the committee for the development of research (CODI) of the Universidad de Antioquia (grant no. 2017-16000), Spanish MINECO (Severo Ochoa programme, grant no. SEV‐2015‐0522), the Swedish research council (VR, grant no. 2019-05591) and the Swedish Energy Agency (grant no. 2020-005194).

Two-dimensional (2D) lead perovskite materials are of interest and under investigation in the solar cell and light-emitting device research community stemming from their high stability and intriguing anisotropic properties. Here we report electronic properties with and without spin–orbit coupling (SOC) together with the influence of van der Waals interaction. Particular attention is given to Rashba SOC, anisotropic band structure effects, and the impact of the electronic structure as a function of interlayer spacing with successively longer organic cations. The results show that larger cations, with a series from butyl-, hexyl-, octyl-, and decyl-diammonium, decrease the electrostatic interaction between the PbI4 planes in the 2D layered perovskites. SOC splitting of the conduction band states lowers the bandgap from 2.21 eV to 1.43 eV in the butyl-diammonium layered perovskite and results in a bandgap of about 1.5 eV in the analogs with longer cation chains. The k-dependent SOC effects (Rashba and Dresselhaus SOC) in the 2D and 3D structures are smaller than the k-independent SOC and are compared to Rashba SOC in III–V semiconductors, SrTiO3, and other 2D hybrid perovskites with respect to symmetry and I–Pb–I angles. The symmetry of the p-orbitals and the bandgap shifts were utilized to perform an analysis of the SOC coupling parameter in the structures in comparison with relativistic effects of isolated Pb. We also report that spacing directly affects the curvature of the bands and the charge carrier mobility perpendicular to the inorganic planes and thus affects the directional charge transport in the 2D perovskite. A distance of 6 nm is the maximum length between the 2D layers to retain a similar effective mass of holes (3m0) in-plane as out-of-plane to allow effective hole charge carrier transport perpendicular to the inorganic layer.

Photovoltaic (PV) electrolysis is an important and powerful technology for environmentally-friendly fuel production based on solar energy. By directly coupling solar cell materials to electrochemical systems to perform water electrolysis, solar energy can be converted into hydrogen fuel utilizing locally-generated heat and avoid losses from DC-DC convertors and power grid transmission. Although there have been significant contributions to the photoelectrochemical and PV-electrolysis field using isolated laboratory cells, the capacity to upscale and retain high levels of efficiency in larger modules remains a critical issue for widespread use and application. In this study, we develop thermally-integrated, solar-driven water-splitting device modules using AgCu(In,Ga)Se-2 (ACIGS) and an alkaline electrolyzer system with NiFe-layered double hydroxide (LDH) nanocatalysts with devices of 82-100 cm(2) area. The Ga-content in the ACIGS solar cells is tuned to achieve an optimal voltage for the catalyst system, and the average efficiencies and durability of the PV-electrolyzer were tested in up to seven-day indoor and 21 day outdoor operations. We achieved a solar-to-hydrogen (STH) module efficiency of 13.4% from gas volume measurements for the system with a six-cell CIGS-electrolyzer module with an active area of 82.3 cm(2) and a 17.27% PV module efficiency under 100 mW cm(-2) illumination, and thus 77% electricity-to-hydrogen efficiency at one full sun. Outdoor tests under mid-Europeen winter conditions exhibited an STH efficiency between 10 and 11% after the initial activation at the installation site in Julich, Germany, in December 2020, despite challenging outdoor-test weather conditions, including sub-zero temperatures.

Direct solar hydrogen generation via a combination of photovoltaics PV and water electrolysis can potentially ensure a sustainable energy supply while minimizing greenhouse emissions. The PECSYS project aims at demonstrating a solar driven electrochemical hydrogen generation system with an area gt;10 amp; 8201;m2 with high efficiency and at reasonable cost. Thermally integrated PV electrolyzers ECs using thin film silicon, undoped, and silver doped Cu In,Ga Se2 and silicon heterojunction PV combined with alkaline electrolysis to form one unit are developed on a prototype level with solar collection areas in the range from 64 to 2600 amp; 8201;cm2 with the solar to hydrogen StH efficiency ranging from amp; 8776;4 to 13 . Electrical direct coupling of PV modules to a proton exchange membrane EC to test the effects of bifaciality 730 amp; 8201;cm2 solar collection area and to study the long term operation under outdoor conditions 10 amp; 8201;m2 collection area is also investigated. In both cases, StH efficiencies exceeding 10 can be maintained over the test periods used. All the StH efficiencies reported are based on measured gas outflow using mass flow meters

Download : Download high-res image (160KB) Download : Download full-size image Dr. Mohammad Ziaur Rahman is an expert in low-dimensional materials synthesis, characterization, and application in solar energy conversion and storage. His current research is on making FeS2 a better solar cell material. Download : Download high-res image (174KB) Download : Download full-size image Professor Tomas Edvinsson is directing a research group that is working on low-dimensional materials for solar cells (FeS2, CIGS, DSSc, and perovskites) and photocatalysis. He is a principal investigator and project leader for several national projects from the Swedish Research Council, Swedish Energy Agency, and part of the Swedish node for a European H2020 project within solar fuels.

Negative thermal expansion is an elusive property found among certain materials, whose potential applications have remained limited due to the many challenges faced in their synthesis. Herein, we report the successful formation of aluminium titanate-based coatings (Al2TiO5), a material renowned for its low-to-negative thermal expansion, by the co-deposition of aluminium-isopropoxide and titanium-isopropoxide in a hot-wall chemical vapour deposition instrument. While coatings grown at 450 °C were amorphous as-deposited, a short-range order into the Al2TiO5-phase was found and analysed by using Raman spectroscopy. Upon subsequent annealing at 700 °C for 3 hours, crystalline coatings were achieved without forming any binary phases. The selective synthesis of the Al2TiO5 phase is ascribed to the precursors’ inherent chemical similarities, resulting in a kinetic targeting of this phase and a short-range homogeneity, entailing its preferred crystallisation. The role of local coordination is expressed by demonstrating the formation of intergrowth phases ascribed to lower coordinating interstices in the compound. Both the formation and crystallisation temperatures reported herein, as well as the timescales needed for the synthesises, are considerably lower than any conventional adopted solid-state techniques used so far to attain the Al2TiO5 phase.

Water electrolysis powered by renewable energies is a promising technology to produce sustainable fossil free fuels. The development and evaluation of effective catalysts are here imperative; however, due to the inclusion of elements with different redox properties and reactivity, these materials undergo dynamical changes and phase transformations during the reaction conditions. NiMoO4 is currently investigated among other metal oxides as a promising noble metal free catalyst for the oxygen evolution reaction. Here we show that at applied bias, NiMoO4·H2O transforms into γ-NiOOH. Time resolved operando Raman spectroscopy is utilized to follow the potential dependent phase transformation and is collaborated with elemental analysis of the electrolyte, confirming that molybdenum leaches out from the as-synthesized NiMoO4·H2O. Molybdenum leaching increases the surface coverage of exposed nickel sites, and this in combination with the formation of γ-NiOOH enlarges the amount of active sites of the catalyst, leading to high current densities. Additionally, we discovered different NiMoO4 nanostructures, nanoflowers, and nanorods, for which the relative ratio can be influenced by the heating ramp during the synthesis. With selective molybdenum etching we were able to assign the varying X-ray diffraction (XRD) pattern as well as Raman vibrations unambiguously to the two nanostructures, which were revealed to exhibit different stabilities in alkaline media by time-resolved in situ and operando Raman spectroscopy. We advocate that a similar approach can beneficially be applied to many other catalysts, unveiling their structural integrity, characterize the dynamic surface reformulation, and resolve any ambiguities in interpretations of the active catalyst phase. Addition/correction: This article has been corrected. Correction in: ACS Nano 2021, 15, 12, 20693-20693. DOI: 10.1021/acsnano.1c10145Title in Web of Science: From NiMoO4 to gamma-NiOOH: Detecting the Active Catalyst Phase by Time Resolved in Situ and Operando Raman Spectroscopy

Mixed nickel-iron (Ni-Fe) compounds have recently emerged as promising non-precious electrocatalysts for alkaline water splitting. The understanding of the charge-transfer mechanism involved in the multi-step Faradic reaction, however, is still limited for the overall electrochemical process. In this paper, electrochemical impedance spectroscopy (EIS) measurements of Fe incorporated Ni oxide nanosheets were used to study the reaction kinetics for both hydrogen (HER) and oxygen (OER) evolution reactions in alkaline media. Our results showed that Fe incorporation improves the catalytic property of NiO nanosheets because of the lower reaction resistance and faster intermediate transformations. Detailed EIS modeling enables a separation of the surface coverage relaxation from the charge transfer resistance, with an inductive behavior observed in the low-frequency range for HER, holding important information on the dominating reaction mechanism. For OER, the good agreement between the EIS experimental results and a model with an inductance loop indicated that similar inductive behavior would be determining the EIS response at very low frequencies. The physical significance of the elementary steps gives insight into the governing reaction mechanisms involved in the electron and hole charge transfer, as well as the inherent properties of catalysts and their surface coverage relaxation. Title in thesis list of papers: An electrochemical impedance study of alkaline water splitting using nickel (iron) oxides nanosheets

Summary In this work, a trimetallic NiMoV catalyst is developed for the hydrogen evolution reaction and characterized with respect to structure, valence, and elemental distribution. The overpotential to drive a 10 mA cm−2 current density is lowered from 94 to 78 mV versus reversible hydrogen electrode by introducing V into NiMo. A scalable stand-alone system for solar-driven water splitting was examined for a laboratory-scale device with 1.6 cm2 photovoltaic (PV) module area to an up-scaled device with 100 cm2 area. The NiMoV cathodic catalyst is combined with a NiO anode in alkaline electrolyzer unit thermally connected to synthesized (Ag,Cu) (In,Ga)Se2 ((A)CIGS) PV modules. Performance of 3- and 4-cell interconnected PV modules, electrolyzer, and hydrogen production of the PV electrolyzer are examined between 25°C and 50°C. The PV-electrolysis device having a 4-cell (A)CIGS under 100 mW cm−2 illumination and NiMoV-NiO electrolyzer shows 9.1% maximum and 8.5% averaged efficiency for 100 h operation., Graphical Abstract, Highlights • A new catalyst NiMoV is reported for the hydrogen evolution reaction • A scalable thermally integrated PV-electrolyzer is designed for solar water splitting • Interconnected PV-electrolyzer modules provide STH efficiency between 8 and 11% • An upscaled CIGS-NiMoV-NiO device provides 8.5% STH for 100 h operation, Chemistry; Electrochemistry; Engineering; Materials Science; Energy Materials

In pursuit of inexpensive and earth abundant photocatalysts for solar hydrogen production from water, conjugated polymers have shown potential to be a viable alternative to widely used inorganic counterparts. The photocatalytic performance of polymeric photocatalysts, however, is very poor in comparison to that of inorganic photocatalysts. Most of the organic photocatalysts are active in hydrogen production only when a sacrificial electron donor (SED) is added into the solution, and their high performances often rely on presence of noble metal co‐catalyst (e.g. Pt). For pursuing a carbon neutral and cost‐effective green hydrogen production, unassisted hydrogen production solely from water is one of the critical requirements to translate a mere bench‐top research interest into the real world applications. Although this is a generic problem for both inorganic and organic types of photocatalysts, organic photocatalysts are mostly investigated in the half‐reaction, and have so far shown limited success in hydrogen production from overall water‐splitting. To make progress, this article exclusively discusses critical factors that are limiting the overall water‐splitting in organic photocatalysts. Additionally, we also have extended the discussion to issues related to stability, accurate reporting of the hydrogen production as well as challenges to be resolved to reach 10 % STH (solar‐to‐hydrogen) conversion efficiency., While half‐reactions using organic photocatalysts for hydrogen production are encouraging, systems with high efficiency without using sacrificing electron donors (SED) and showing full overall water‐splitting are still largely absent. Critical factors that are limiting the overall water‐splitting using organic photocatalysts are summarized, with a supplementary discussion on remaining challenges.

Graphene, with its excellent electrical, mechanical, and optical properties, has emerged as an exceptional material for flexible and transparent nanoelectronics. Such versatility makes it compelling to find new pathways to lay graphene sheets onto smooth, flexible substrates to create large-scale flexible transparent graphene conductors. Here, we report the realization of flexible transparent graphene laminates by direct adhesion of chemical vapor deposition (CVD) graphene on a polyethylene naphthalate (PEN) substrate, which is an emerging standard for flexible electronics. By systematically optimizing the conditions of a hot-press technique, we have identified that applying optimum temperature and pressure can make graphene directly adhere to flexible PEN substrates without any intermediate layer. The resultant flexible graphene films are transparent, have a standard sheet resistance of 1 kΩ with high bending resilience, and high optical transmittance of 85%. Our direct hot-press method is achieved below the glass transition temperature of the PEN substrate. Furthermore, we demonstrate press-assisted embossing for patterned transfer of graphene, and hence it can serve as a reliable new means for creating universal, transparent conducting patterned films for designing flexible nanoelectronic and optoelectronic components.

The Horizon 2020 project PECSYS aims to build a large area demonstrator for hydrogen production from solar energy via integrated photovoltaic (PV) and electrolysis systems of different types. In this study, Si- and CIGS-based photovoltaics are developed together with three different electrolyzer systems for use in the corresponding integrated devices. The systems are experimentally evaluated and a general model is developed to investigate the hydrogen yield under real climatic conditions for various thin film and silicon PV technologies and electrolyser combinations. PV characteristics using a Si heterojunction (SHJ), thin film CuInxGa1-xSe2, crystalline Si with passivated emitter rear totally diffused and thin film Si are used together with temperature dependent catalyst load curves from both acidic and alkaline approaches. Electrolysis data were collected from (i) a Pt-IrO2-based acidic electrolysis system, and (ii) NiMoW-NiO-based and (iii) Pt-Ni foam-based alkaline electrolysis systems. The calculations were performed for mid-European climate data from Julich, Germany, which will be the installation site. The best systems show an electricity-to-hydrogen conversion efficiency of 74% and over 12% solar-to-hydrogen (STH) efficiencies using both acidic and alkaline approaches and are validated with a smaller lab scale prototype. The results show that the lower power delivered by all the PV technologies under low irradiation is balanced by the lower demand for overpotentials for all the electrolysis approaches at these currents, with more or less retained STH efficiency over the full year if the catalyst area is the same as the PV area for the alkaline approach. The total yield of hydrogen, however, follows the irradiance, where a yearly hydrogen production of over 35 kg can be achieved for a 10 m(2) integrated PV-electrolysis system for several of the PV and electrolyser combinations that also allow a significant (100-fold) reduction in necessary electrolyser area for the acidic approach. Measuring the catalyst systems under intermittent and ramping conditions with different temperatures, a 5% lowering of the yearly hydrogen yield is extracted for some of the catalyst systems while the Pt-Ni foam-based alkaline system showed unaffected or even slightly increased yearly yield under the same conditions.

Energy efficient synthesis providing high quality crystalline thin films are highly desired in many applications. Here we devise a non-toxic solvent approach for production of highly crystalline MAPbI3 perovskite by exploiting diffusion aggregation processes. Isopropanol solution based methylammonium lead triiodide (MAPbI3) is used in this context, where the crystal growth initiation starts in an unstable suspension far from equilibrium and the subsequent crystallization is driven by the solubility parameters. The crystal formation is monitored by scanning transmission electron microscope (STEM), observing small crystallization centers growing as time evolves to large grains with high crystal purity. Energy dispersive X-ray spectroscopy (EDS) in STEM mode revealed a Pb rich core-shell structure in newly formed grains. Nano-beam Electron Diffraction (NBED) scan defined PbI2 crystallites in the Pb rich shell with a single crystal MAPbI3 core in newly formed grains. After a week stirring, the same aggregated suspension exhibited grains with only single crystal MAPbI3 structure. The NBED analysis shows a kinetically slow transition from a core shell structure to a single crystal grain. This research presents an impactful insight on the factors that may cause sub-stoichiometric grain boundary effects which can influence the solar cell performance. In addition, the structure, morphology and optical properties of the perovskite grains have been presented. A powder of highly crystalline particles was subsequently prepared by evaporation of the solvent in a low-vacuum oven. Thin film MAPbI3 solar cells were fabricated by dissolving the powder and applying it in a classical fabrication route. The MAPbI3 solar cells gave a champion efficiency of 20% (19.9%) and an average efficiency at approximately 17% with low hysteresis effects. Here a strategy to manufacture the material structure without toxic solvents is highlighted. The single-crystal growth devised here opens both for shelf storage of materials as well as a more flexible manufacturing of devices. The process can likely be extended to other fields, where the intermediate porous framework and large surface area would be beneficial for battery or super capacitor materials.

Interaction of light with magnetic nanoparticles, dispersed insolution or embedded in other materials, is of major interest in a range of applications, one example being optomagnetic sensors. In applied research, light absorption and scattering of nanoparticle composites are often quantified by the Kubelka−Munk two-flux radiative transfer model. In this paper, we synthesized magnetite (Fe3O4) nanospheres with different diameters and encapsulated them into a polymer matrix. Their spectral transmittance and reflectance were investigated by spectrophotometry, together with measurements of angle-resolved scattering in the forward and backward hemispheres. The measured angular distribution was applied to approximate the scattering-phase function inside the film, which could be well described by the revised Reynolds−McCormick model. The backscattering and absorption coefficients were derived by inversion of the Kubelka−Munk relations, using the interface reflectances obtained from angle-dependent measurements. We present detailed optical properties for samples with various particle concentrations and scattering layer thicknesses, consisting of the magnetite and polymer composites. The absorption and backscattering coefficients for particles of diameter 458 nm showed qualitative agreement with single-scattering Mie calculations. The optical properties of composites with smaller particles might beinfluenced by an oxidized Fe2O3-like surface layer. The present approach can be used to study different kinds of magnetic nanoparticle clusters, dispersed in a supporting medium, and thus provide optical parameters of relevance for interpreting results ofoptomagnetic sensing experiments.

ZnO is a promising material for photoanodes and applications within photocatalysis, due to its controllable morphology, excellent stability, and high velocity (>100 cm2 V−1·s−1) for charge carrier migration. In addition, the deep lying valence band edge provides a high driving force for many oxidation reactions, including water oxidation. For a tailored artificial light such as UV light–emitting diodes, ZnO photocatalysis can be very effective while the relatively wide bandgap of ∼3.3 eV yields a limitation in utilizing the full potential of the solar spectrum for photocatalysis. A lot of effort has been made to enhance the photocatalytic (PC) activity of ZnO, either by extending the absorption into the visible range by doping or by more efficient use of the absorbed photons in the UV range. In our previous studies, we have demonstrated that the PC activity of ZnO nanocrystals could be enhanced via morphology tuning, the formation of a Schottky junction with Au or Ag nanoparticles, and the combination with narrow-bandgap semiconductors. We have also shown the photoelectrochemical activity of ZnO nanorod arrays can be improved through thermal treatment or being modified with a ZnS thin layer. Another strategy is to control the electronic properties in ZnO by quantum confinement, which provides tunability of the electronic levels and introduces the ability to target specific reactions at the expense of widening the bandgap. In this chapter, we succinctly present the current progress in ZnO photocatalysis, strategies to improve and control the PC activity, and bring up the present and future prospect of ZnO as a photocatalyst.

Lead halide perovskites (LHPs) have recently emerged as promising materials for solar energy conversions. Here, the underlying optoelectronic properties, charge transport abilities, energy level positions for alignment of contact materials, and the stability of LHPs are all dependence on the material composition and structure. Therefore, understanding the structure-to-property relationships is crucial from both a fundamental perspective as well as for constructing efficient and stable devices based on LHPs. XRD is a century old powerful tool to extract the structure of crystalline materials. It provides means to quantify atomic level distances, extraction of symmetries, densities, compositional and temperature dependent phase transitions as well as orientation and size of crystallites in polycrystalline films. Raman spectroscopy is a versatile characterization technique that provides information about the chemical composition and phases in crystalline materials, as well as the local vibration found in amorphous structures, molecular materials, solvents, and gases. With this knowledge, one can extract chemical identities via observed vibrations, bonding interactions, orientations, symmetries, local and lattice vibrations in a crystalline materials. In this contribution, we succinctly discuss the latest progress in understanding the physical properties of LHPs using XRD and Raman Spectroscopy.

Graphene, with its excellent electrical, mechanical, and optical properties, has emerged as an exceptional material for flexible and transparent nanoelectronics. Such versatility makes it compelling to find new pathways to lay graphene sheets onto smooth, flexible substrates to create large-scale flexible transparent graphene conductors. Here, we report the realization of flexible transparent graphene laminates by direct adhesion of chemical vapor deposition (CVD) graphene on a polyethylene naphthalate (PEN) substrate, which is an emerging standard for flexible electronics. By systematically optimizing the conditions of a hot-press technique, we have identified that applying optimum temperature and pressure can make graphene directly adhere to flexible PEN substrates without any intermediate layer. The resultant flexible graphene films are transparent, have a standard sheet resistance of 1 k Omega with high bending resilience, and high optical transmittance of 85%. Our direct hot-press method is achieved below the glass transition temperature of the PEN substrate. Furthermore, we demonstrate press-assisted embossing for patterned transfer of graphene, and hence it can serve as a reliable new means for creating universal, transparent conducting patterned films for designing flexible nanoelectronic and optoelectronic components.

The perovskite layer is the photoactive material within the hybrid perovskite solar cell (HPSC) device by which the incoming photon energies are absorbed and transformed into charge carriers, and after the charge separation, the corresponding charge carriers are transported via the selective contacts for the photovoltaic operation. Optical fingerprints of these physical processes i.e. the spectral response during light absorption, charge separation, transport, recombination as well as other important phenomena such as Stark effects, electron-phonon interactions, ionic movement and Frenkel defect annihilation can be studied within the scope of time resolved photo-induced optical spectroscopy. The time scales of the main fundamental processes within perovskite solar cells directly affect the device performance, and can differ significantly from conventional solar cell technology devices. The processes varies from femtosecond to several seconds and many are strongly dependent on the chemical composition and crystal quality of the material. Full characterization of the physical properties of the device, implies a careful attention to the lifetime and amplitudes of the processes, as well as experimental design for distinguishing the processes by considering the appropriate method and/or variation in the chemical composition of the materials. Here we briefly review the relevant underlying physical processes occurring in the system, their fingerprints and how they can be detected by different spectroscopic tools, together with the methodological scopes and limitations.

The field of photovoltaics gives the opportunity to make our buildings ‘‘smart’’ and our portable devices “independent”, provided effective energy sources can be developed for use in ambient indoor conditions. To address this important issue, ambient light photovoltaic cells were developed to power autonomous Internet of Things (IoT) devices, capable of machine learning, allowing the on-device implementation of artificial intelligence. Through a novel co-sensitization strategy, we tailored dye-sensitized photovoltaic cells based on a copper(ii/i) electrolyte for the generation of power under ambient lighting with an unprecedented conversion efficiency (34%, 103 μW cm−2 at 1000 lux; 32.7%, 50 μW cm−2 at 500 lux and 31.4%, 19 μW cm−2 at 200 lux from a fluorescent lamp). A small array of DSCs with a joint active area of 16 cm2 was then used to power machine learning on wireless nodes. The collection of 0.947 mJ or 2.72 × 1015 photons is needed to compute one inference of a pre-trained artificial neural network for MNIST image classification in the employed set up. The inference accuracy of the network exceeded 90% for standard test images and 80% using camera-acquired printed MNIST-digits. Quantization of the neural network significantly reduced memory requirements with a less than 0.1% loss in accuracy compared to a full-precision network, making machine learning inferences on low-power microcontrollers possible. 152 J or 4.41 × 1020 photons required for training and verification of an artificial neural network were harvested with 64 cm2 photovoltaic area in less than 24 hours under 1000 lux illumination. Ambient light harvesters provide a new generation of self-powered and “smart” IoT devices powered through an energy source that is largely untapped., Indoor light harvesters enable machine learning on fully autonomous IoT devices at 2.72 × 1015 photons per inference.

Plasmonics nanoparticles gained prominence in the last decade in fields of photonics, solar energy conversion and catalysis. It has been shown that anchoring the plasmonics nanoparticles on semiconductors via a molecular linker reduces band bending and increases hot carriers&rsquo, lifetime, which is essential for the development of efficient photovoltaic devices and photocatalytic systems. Aminobenzoic acid is a commonly used linker to connect the plasmonic metal to an oxide-based semiconductor. The coordination to the oxide was established to occur via the carboxylic functional group, however, it remains unclear what type of coordination that is established with the metal site. Herein, it is demonstrated that metal is covalently bonded to the linker via the amino group, as supported by Surface-Enhanced Resonant Raman and infrared spectroscopies. The covalent linkage increases significantly the amount of silver grafted, resulting in an improvement of the system catalytic proficiency in the 4-nitrophenol (4-NP) photoreduction.

Layered two-dimensional (2D) hybrid organic-inorganic perovskites (HOP) are promising materials for light-harvesting applications because of their chemical stability, wide flexibility in compositio ...