Tandem nanostructures: a prospective platform for photoelectrochemical water splitting. - In: Solar RRL, ISSN 2367-198X, Bd. 6 (2022), 9, 2200181, S. 1-33
A platform for efficient photoelectrochemical (PEC) water splitting must fulfil different requirements: the absorption of the solar spectrum should be maximized in use for charge carrier generation. To avoid recombination, fast separation of charge carriers is required and the energetic positions of the band structure(s) must be optimized with respect to the water splitting reactions. In these respects, constructing tandem nanostructures with rationally designed nanostructured units offers a potential opportunity to break the performance bottleneck imposed by the unitary nanostructure. So far, quite a few tandem nanostructures have been designed, fabricated, and employed to improve the efficiency of PEC water splitting, and significant achievements have been realized. This review focuses on the current advances in tandem nanostructures for PEC water splitting. Firstly, the state of the art for tandem nanostructures applied in PEC water splitting is summarized. Secondly, the advances in this field and advantages arising of employing tandem nanostructures for PEC water splitting are outlined. Subsequently, different types of tandem nanostructures are reviewed, including core-shell tandem nanostructured photoelectrode, the two-photoelectrode tandem cell, and the tandem nanostructures of plasmon related devices for PEC water splitting. Based on this, the future perspective of this field is proposed.
https://doi.org/10.1002/solr.202200181
Evaluating the optical response of heavily decorated black silicon based on a realistic 3D modeling methodology. - In: ACS applied materials & interfaces, ISSN 1944-8252, Bd. 14 (2022), 31, S. 36189-36199
Combining black silicon (BS), a nanostructured silicon containing highly roughened surface morphology with plasmonic materials, is becoming an attractive approach for greatly enhancing light-matter interactions with promising applications of sensing and light harvesting. However, precisely describing the optical response of a heavily decorated BS structure is still challenging due to the increasing complexity in surface morphology and plasmon hybridization. Here, we propose and fully characterize BS-based multistacked nanostructures with randomly distributed nanoparticles on the highly roughened nonflat surface. We demonstrate a realistic 3D modeling methodology based on parametrized scanning electron microscopy images that provides high-precision morphology details, successfully linking the theoretical analysis with experimental optical response of the complex nanostructures. Far-field calculations very nicely reproduce experimental reflectance spectra, revealing the dependency of light trapping on the thickness of the conformal reflector and the atop nanoparticle size. Near-field analysis clearly identifies three types of stochastic “hotspots”. Their contribution to the overall field enhancement is shown to be very much sensitive to the nanoscale surface morphology. The simulated near-field property is then used to examine the measured surface-enhanced Raman scattering (SERS) response on the multistacked structures. The present modeling approach combined with spectroscopic characterizations is expected to offer a powerful tool for the precise description of the optical response of other large-scale highly disordered realistic 3D systems.
https://doi.org/10.1021/acsami.2c05652
Plasma-assisted fabrication of molecularly imprinted NiAl-LDH layer on Ni nanorod arrays for glyphosate detection. - In: ACS applied materials & interfaces, ISSN 1944-8252, Bd. 14 (2022), 31, S. 35704-35715
An inorganic-framework molecularly imprinted NiAl layered double hydroxide (MI-NiAl-LDH) with specific template molecule (glyphosate pesticide, Glyp) recognition ability was prepared on Ni nanorod arrays (Ni NRAs) through electrodeposition followed by a low-temperature O2 plasma treatment. The freestanding Ni/MI-NiAl-LDH NRA electrode had highly enhanced sensitivity and selectivity. The electrocatalytic oxidation of Glyp was proposed to occur at Ni3+ centers in MI-NiAl-LDH, and the current response depended linearly on the Glyp concentration from 10.0 nmol/L to 1.0 μmol/L (R2 = 0.9906), with the limit of detection (LOD) being 3.1 nmol/L (S/N = 3). An exceptional discriminating capability with tolerance for other similar organophosphorus compounds was achieved. Molecular imprinting (N and P residues) affected the electronic structure of NiAl-LDH, triggering the formation of highly active NiOOH sites at relatively lower anodic potentials and substantially enhancing the electrocatalytic oxidation ability of the NiAl-LDH interface toward the C-N bonds in Glyp. In combination with the surface enrichment effect of MI-NiAl-LDH toward template molecules, the electrochemical oxidation signal intensity of Glyp increased significantly, with a greater peak separation from interfering molecules. These results challenge the common belief that the excellent performance of inorganic-framework molecularly imprinted interfaces arises from their specific adsorption of template molecules, providing new insight into the development of high-performance organic-pollutant-sensing electrodes.
https://doi.org/10.1021/acsami.2c08500
Improving silicon photocathode performance for water reduction through dual interface engineering and integrating ReS2 photocatalyst. - In: ACS applied energy materials, ISSN 2574-0962, Bd. 5 (2022), 7, S. 8222-8231
Photoelectrochemical (PEC) water splitting for H2 production is a possible alternative for fossil energy in the future. However, there exists three problems in PEC water splitting with the silicon (Si) photocathode: poor light absorption of the untreated Si substrate, bad stability in strong acid solution, and poor photocatalytic activity of Si. Here, a strategy of dual interface engineering and photocatalyst deposition is proposed to improve the PEC performance, which consists of fabricating black Si (b-Si) by reactive ion etching, depositing of TiO2 on the b-Si by atomic layer deposition, and growing ReS2 on top of the TiO2 by chemical vapor deposition. Owing to the suitable band alignment of b-Si, TiO2, and ReS2, the ReS2/TiO2/b-Si shows obviously enhanced PEC performance compared to b-Si, TiO2/b-Si, and ReS2/b-Si photocathodes. Results of electrochemical impedance spectroscopy and Mott-Schottky plot analysis demonstrate that the TiO2 layer plays an important role and the charge-transfer kinetics of the system is clearly improved. Transient photocurrent measurements indicate that the ReS2/TiO2/b-Si photocathode has the most remarkable photocurrent response. In addition, the ReS2/TiO2/b-Si photocathode also shows excellent stability after being operated for 25 h.
https://doi.org/10.1021/acsaem.2c00761
Anisotropy of the electric field gradient in two-dimensional α-MoO3 investigated by 57Mn(57Fe) emission Mössbauer spectroscopy. - In: Crystals, ISSN 2073-4352, Bd. 12 (2022), 7, 942, S. 1-13
Van der Waals α-MoO3 samples offer a wide range of attractive catalytic, electronic, and optical properties. We present herein an emission Mössbauer spectroscopy (eMS) study of the electric-field gradient (EFG) anisotropy in crystalline free-standing α-MoO3 samples. Although α-MoO3 is a two-dimensional (2D) material, scanning electron microscopy shows that the crystals are 0.5-5-µm thick. The combination of X-ray diffraction and micro-Raman spectroscopy, performed after sample preparation, provided evidence of the phase purity and crystal quality of the samples. The eMS measurements were conducted following the implantation of 57Mn (t1/2 = 1.5 min), which decays to the 57Fe, 14.4 keV Mössbauer state. The eMS spectra of the samples are dominated by a paramagnetic doublet (D1) with an angular dependence, pointing to the Fe2+ probe ions being in a crystalline environment. It is attributed to an asymmetric EFG at the eMS probe site originating from strong in-plane covalent bonds and weak out-of-plane van der Waals interactions in the 2D material. Moreover, a second broad component, D2, can be assigned to Fe3+ defects that are dynamically generated during the online measurements. The results are compared to ab initio simulations and are discussed in terms of the in-plane and out-of-plane interactions in the system.
https://doi.org/10.3390/cryst12070942
Compositional dependence of epitaxial L10-Mnx Ga magnetic properties as probed by 57Mn/Fe and 119In/Sn emission Mössbauer spectroscopy. - In: Physica status solidi, ISSN 1521-3951, Bd. 259 (2022), 7, 2200121, S. 1-11
The magnetic properties of Mn x Ga alloys critically depend on composition x, and the atomic-scale origin of those dependences is still not fully disclosed. Molecular beam epitaxy has been used to produce a set of Mn x Ga samples (x = 0.7 ÷ 1.9) with strong perpendicular magnetic anisotropy, and controllable saturation magnetization and coercive field depending on x. By conducting 57Mn/Fe and 119In/Sn emission Mössbauer spectroscopy at ISOLDE/CERN, the Mn and Ga site-specific chemical, structural, and magnetic properties of Mn x Ga are investigated as a function of x, and correlated with the magnetic properties as measured by superconducting quantum interference device magnetometry. Hyperfine magnetic fields of Mn/Fe (either at Mn or Ga sites) are found to be greatly influenced by the local strain induced by the implantation. However, In/Sn probes show clear angular dependence, demonstrating a huge transferred dipolar hyperfine field to the Ga sites. A clear increase of the occupancy of Ga lattice sites by Mn for x > 1 is observed, and identified as the origin for the increased antiferromagnetic coupling between Mn and Mn at Ga sites that lowers the samples' magnetization. The results shed further light on the atomic-scale mechanisms driving the compositional dependence of magnetism in Mn x Ga.
https://doi.org/10.1002/pssb.202200121
Hydrogenated TiO2 nanoparticles loaded with Au nanoclusters demonstrating largely enhanced performance for electrochemical reduction of nitrogen to ammonia. - In: Energy technology, ISSN 2194-4296, Bd. 10 (2022), 7, 2200085, S. 1-9
Pristine TiO2/Au (P-TiO2/Au) is modified by hydrogen plasma (H-TiO2/Au) or hydrogen and oxygen plasma (H-O-TiO2/Au) treatment, and then used as electrochemical catalysts for nitrogen reduction reaction (NRR). H-TiO2/Au shows enhanced performance for the NRR process compared with both P-TiO2/Au and H-O-TiO2/Au. After hydrogenation treatment, some disordered regions on the surface of TiO2 nanoparticles are formed, and a large number of oxygen vacancies are incorporated into the TiO2 crystalline structures. When the samples are used as catalysts for electrochemical NRR, the yield of NH3 of H-TiO2/Au is about ten times compared to that of P-TiO2/Au and about three times that of H-O-TiO2/Au, while the highest Faradaic efficiency of 2.7% is also obtained at the potential of -0.1 V for the H-TiO2/Au catalyst. The density functional theory (DFT) calculation results confirm that H-TiO2/Au with oxygen vacancies and the disordered surface layer is much preferred energetically for the NRR process. It proves that enhanced adsorption of N2 molecules on the catalyst and reduced reaction barriers due to the presence of defects play an important role in improving catalysts’ performances. The results show that the plasma hydrogenation technique can be used as an efficient method to modify catalysts for electrochemical NRR processes.
https://doi.org/10.1002/ente.202200085
The 2022 solar fuels roadmap. - In: Journal of physics, ISSN 1361-6463, Bd. 55 (2022), 32, 323003, S. 1-52
Renewable fuel generation is essential for a low carbon footprint economy. Thus, over the last five decades, a significant effort has been dedicated towards increasing the performance of solar fuels generating devices. Specifically, the solar to hydrogen efficiency of photoelectrochemical cells has progressed steadily towards its fundamental limit, and the faradaic efficiency towards valuable products in CO2 reduction systems has increased dramatically. However, there are still numerous scientific and engineering challenges that must be overcame in order to turn solar fuels into a viable technology. At the electrode and device level, the conversion efficiency, stability and products selectivity must be increased significantly. Meanwhile, these performance metrics must be maintained when scaling up devices and systems while maintaining an acceptable cost and carbon footprint. This roadmap surveys different aspects of this endeavor: system benchmarking, device scaling, various approaches for photoelectrodes design, materials discovery, and catalysis. Each of the sections in the roadmap focuses on a single topic, discussing the state of the art, the key challenges and advancements required to meet them. The roadmap can be used as a guide for researchers and funding agencies highlighting the most pressing needs of the field.
https://doi.org/10.1088/1361-6463/ac6f97
Anisotropy of the ΔE effect in Ni-based magnetoelectric cantilevers: a finite element method analysis. - In: Sensors, ISSN 1424-8220, Bd. 22 (2022), 13, 4958, S. 1-16
In recent investigations of magnetoelectric sensors based on microelectromechanical cantilevers made of TiN/AlN/Ni, a complex eigenfrequency behavior arising from the anisotropic ΔE effect was demonstrated. Within this work, a FEM simulation model based on this material system is presented to allow an investigation of the vibrational properties of cantilever-based sensors derived from magnetocrystalline anisotropy while avoiding other anisotropic contributions. Using the magnetocrystalline ΔE effect, a magnetic hardening of Nickel is demonstrated for the (110) as well as the (111) orientation. The sensitivity is extracted from the field-dependent eigenfrequency curves. It is found, that the transitions of the individual magnetic domain states in the magnetization process are the dominant influencing factor on the sensitivity for all crystal orientations. It is shown, that Nickel layers in the sensor aligned along the medium or hard axis yield a higher sensitivity than layers along the easy axis. The peak sensitivity was determined to 41.3 T−1 for (110) in-plane-oriented Nickel at a magnetic bias flux of 1.78 mT. The results achieved by FEM simulations are compared to the results calculated by the Euler-Bernoulli theory.
https://doi.org/10.3390/s22134958
Perturbed angular correlation technique at ISOLDE/CERN applied for studies of hydrogenated titanium dioxide (TiO2): observation of Cd-H Pairs. - In: Crystals, ISSN 2073-4352, Bd. 12 (2022), 6, 756, S. 1-10
Profound understanding of the local electronic and defect structure in semiconductors always plays a vital role in the further developing of applications of such materials. In the present work an investigation of the electronic structure in hydrogenated TiO2 (rutile) thin films is conducted by virtue of Time-Differential γ-γ Perturbed Angular Correlation spectroscopy (TDPAC or PAC) with 111mCd/Cd isotope, produced and implanted at ISOLDE/CERN. The measurements were performed at 581 K as a function of the temperature of the samples during hydrogenation. Despite the fact, that rutile single crystals usually show the presence of two local environments, when are studies with Cd/In isotopes, the current pristine thin films sample had a single electric field gradient. Upon various degrees of hydrogenation, Cd probe atoms showed underwent alterations, resulting in up to 3 different local surroundings, generally with high electric field gradients. Broad EFG distributions are likely due to randomly distributed point defects in the neighbourhood of Cd acceptors. Observed results suggest that hydrogenations performed at RT and 423 K are not able to promote unique defect configurations, while in the range of 473-573 K the formation of such configurations is observed. Therefore, one may assume that the formation of Cd-defect complexes (Cd-H pairs) is temperature enhanced. At higher levels of hydrogenation (663 K), the samples become partly amorphous that further hinders any atomistic studies with strong damped PAC spectra. Cd-H complexes seem to be stable up to annealing up to 581 K annealing. The obtained results give a deep insight into complex hydrogen defects, their interactions and bond formations with Cd acceptor.
https://doi.org/10.3390/cryst12060756