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Surface treatment is an effective method to improve the photoelectrochemical (PEC) performance of photoelectrodes. Herein, we introduced a novel strategy of surface sulfurization to modify hematite (α-Fe2O3) nanorods grown in an aqueous solution, which triggered encouraging improvement in PEC performances. In comparison to the solution-grown pristine α-Fe2O3 nanorod photoanode that is PEC inefficient and always needs high temperature (>600 °C) activation, the surface sulfurized α-Fe2O3 nanorods show photocurrent density increased by orders of magnitude, reaching 0.46 mA cm−2 at 1.23 V vs. RHE (reversible hydrogen electrode) under simulated solar illumination. This improvement in PEC performances should be attributed to the synergy of the increased carrier density, the reduced surface charge carrier recombination and the accelerated water oxidation kinetics at the α-Fe2O3/electrolyte interface, as induced by the incorporation of S ions and the formation of multi-state S species (Fe-Sx-Oy) at the surface of α-Fe2O3 nanorods. This study paves a new and facile approach to activate α-Fe2O3 and even other metal oxides as photoelectrodes for improved PEC water splitting performances, by engineering the surface structure to relieve the bottlenecks of charge transfer dynamics and redox reaction kinetics at the electrode/electrolyte interface.

A chiral structure with a negative Poisson’s ratio containing a hollow circle with varying diameters was designed, and the finite element method was used to investigate the variation in the Poisson’s ratio when the hollow circle diameter was varied (d = 0, 1, 2, 3, and 4 mm). The simulation results showed that the Poisson’s ratio was sensitive to the hollow circle diameter, and the minimum Poisson’s ratio was −0.43. Three specimens with different hollow circle diameters (d′ = 0, 1, and 3 mm) were 3D-printed from thermoplastic polyurethane, and the Poisson’s ratio and equivalent elastic modulus were measured. In the elastic range, the Poisson’s ratio increased and the equivalent elastic modulus decreased as the hollow circle diameter increased. The simulation and experimental results showed good agreement. The proposed structure is expected to be applicable to protective sports gear owing to its high energy absorption and the fact that its properties can be modified as required by adjusting the geometric parameters of the unit cell.

The authors gratefully acknowledge the financial support from the National Natural Science Foundation of China (nos. 51961165103 and 51672210) and the National Key Research and Development Program of China (2018YFB1502003 and 2017YFE0193900). S.S. is supported by the National Program for Support of Top-notch Young Professionals and “The Youth Innovation Team of Shaanxi Universities.”

In this study, we report a simple, effective and universal approach to fabricate homojunction structural TiO2 nanorod array photoelectrodes through doping of gradient distributed oxygen vacancies introduced by annealing in high vacuum with controlled time. The homogeneous junction structure promotes the separation and transport of photoexcited charge carriers, and the photocurrent density of TiO2 nanorod arrays annealed in high vacuum for 2 h was 20 times higher than that of the pristine TiO2 nanorod arrays. The results indicate that annealing in high vacuum with controlled time could form a homojunction structure, which is an effective approach for further enhancing the performance of UV–visible light driven photocatalytic materials for water splitting.

Given the proper band gap, low cost and good stability, hematite (α-Fe2O3) has been considered as a promising candidate for photoelectrochemical (PEC) water splitting, however suffers from the sluggish surface water oxidation reaction kinetics. In this study, a simple dip-coating process was used to modify the surface of α-Fe2O3 nanorod arrays with cobalt oxide (CoOx) and carbon (C) for the improved PEC performance, with a photocurrent density at 1.6 V (vs. reversible hydrogen electrode, RHE) increased from 0.10 mA/cm2 for the pristine α-Fe2O3 to 0.37 mA/cm2 for the CoOx/C modified α-Fe2O3 nanorods. As revealed by electrochemical analysis, thanks to the synergistic effect of CoOx and C, the PEC enhancement could be attributed to the enhanced charge transfer ability, decreased surface charge recombination, and accelerated water oxidation reaction kinetics. This study serves as a good example for improving PEC water splitting performance via a simple method.

In this study, Nb-doped α-Fe2O3 nanorod photoanodes were prepared via a facile solution-based process by directly adding NbCl5 in the aqueous solution. The morphology and electronic structure of Nb-doped α-Fe2O3 films depended strongly on the dopant concentrations. Compared with the undoped sample, the optimal Nb-doped α-Fe2O3 film showed an approximately 4-fold photocurrent increase under solar light at 1.0 V versus Ag/AgCl, and the incident photon-to-current conversion efficiency was increased by 2.5 times, reaching 13.7 % at 350 nm and 1.23 V versus RHE. The enhancement in PEC activity, as induced by moderate Nb doping, was attributed to the increased charge carrier density for promoted charge transfer ability as well as the smaller nanorod diameter for shortened charge transfer distance. However, superfluous Nb dopants would destroy the nanorod structure and greatly reduce the thickness of α-Fe2O3 films, leading to poor optical absorption and thus decreased photoelectrochemical performance.

Porous photoelectrodes show high efficiency in hydrogen production by water splitting. However, fabrication of porous nanorods is usually difficult. Here, we report a simple approach to fabricate a kind of novel porous rutile titanium dioxide nanorod array by an advanced ion implantation method using multiple-energy helium ion implantation and subsequent annealing. The porous nanostructure enhances the photoelectrochemical performance of the titanium dioxide nanorod array photoelectrodes under Uv-visible light illumination, where the highest photocurrent density was relatively about 10 times higher than that of the pristine titanium dioxide nanorod array. The formation of nanocavities mainly contributes to the enhancement of the photocurrent density by trapping holes inside to separate the charge carriers. The study demonstrates that ion implantation could be an effective approach to develop novel porous nanostructural photoelectrodes for the application of hydrogen production.

Engineering the interface and surface structures of semiconductor-based photoelectrodes for improved charge transfer dynamics and promoted water redox reaction kinetics is essential to achieve efficient photoelectrochemical (PEC) water splitting. In this work, α-Fe2O3 nanorods, successively coated with TiO2 and CoOx thin layers, were reported as the photoanode for solar-driven water oxidation. The obtained α-Fe2O3/TiO2/CoOx photoanode exhibits superior PEC performance as compared to bare α-Fe2O3, with a 3.3-time improvement in photocurrent density at 1.23 V vs reversible hydrogen electrode. This significant enhancement results from the formed heterojunction between α-Fe2O3 and TiO2 for the accelerated photogenerated charge separation and transfer as well as the passivated surface defects by the TiO2 overlayer for reduced charge recombination. Additionally, the existence of CoOx as the oxygen evolution catalyst significantly facilitates the surface reaction kinetics and thus reduces the overpotential for water oxidation. This study demonstrates a collaborative strategy of interface and surface engineering to design novel structures of α-Fe2O3 based photoanodes for highly efficient solar water oxidation.

Novel hybrid tetra-nitro-phthalocyanine Copper(II) (TNCuPc)/TiO2 films were successfully synthesized using a simple hydrothermal and solvothermal method. The successful deposition of TNCuPc on the TiO2 nanorods was confirmed by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The precursor concentration for hydrothermal deposition of TiO2 was optimized for light absorption and photoelectrochemical (PEC) water splitting. The hierarchical nanostructure exhibited increased light absorption ability and enhanced PEC properties. Moreover, the concentration of the precursor solution for TNCuPc deposition was also optimized for the performance of the TNCuPc/TiO2 hybrid nanostructure. The optimal sample achieved the highest photocurrent of 1.1 mA cm−2 and the highest IPCE of 51% at 610 nm.

In this study, a ternary nanostructured α-Fe2O3/Au/TiO2 film with integrating a crystalline α-Fe2O3 core, metallic Au nanoparticles (NPs), and an amorphous TiO2 overlayer is fabricated and examined as a photoanode for photoelectrocatalytic water splitting. Under simulated solar illumination, the as-prepared photoanode exhibits a four-fold increase (1.05 mA cm−2) in photocurrent density at 1.23 V versus reversible hydrogen electrode (RHE) relative to bare α-Fe2O3. Based on systematic investigations, it is proposed that Au NPs extract photoholes from the bulk of α-Fe2O3 core and then shuttle them to the outer TiO2 overlayer, and meanwhile, TiO2 overlayer efficiently captures and stores the photoholes and facilitates the hole injection into electrolyte. Thus, the remarkably improved photoelectrocatalytic water splitting performance of α-Fe2O3/Au/TiO2 photoanode is attributed to the significantly suppressed bulk and surface charge recombination due to the relayed pumping of the photogenerated charge carriers through the photoanode/electrolyte interfaces reconstructed by Au NPs and TiO2 overlayer.

This paper proposes a complete parametric approach for eigenstructure assignment in second-order system Mq+Dq+kq=cu using the displacement-plus-acceleration feedback controller. The expressions of closed-loop eigenvector matrix and feedback gains are in direct closed forms in terms of the closed-loop eigenvalues and a group parameter vectors, which represents the degree of design freedom. The main advantage of the proposed method is solved directly in matrix second-order framework, without transformation into the first-order form, and the numerical stability is better because it used only right coprime factorization and simple matrix transformation. The proposed algorithm is simple and does not contain ‘go back’ procedures. Finally, computational results show its effect and simplicity.

Ta-doped hematite (α-Fe2O3) nanorod array films were successfully prepared on fluorine-doped tin dioxide (FTO) coated glass substrates via a facile solution growth process with TaCl5 as a Ta doping precursor. Under 1 sun illumination and at an applied potential of 1.0 V vs. Ag/AgCl, the Ta-doped α-Fe2O3 photoanode with optimized dopant concentration showed a photocurrent density as high as 0.53 mA cm(-2), which was about 3.5 times higher than that of the undoped sample. As demonstrated by Mott-Schottky and X-ray absorption spectroscopy measurements, considerable increase in photoelectrochemical (PEC) performance achieved for Ta-doped α-Fe2O3 nanorod films should be mainly attributed to the increased electron donor density induced by Ta doping. However, with superfluous Ta doping, the [110]-oriented nanorod structure was destroyed, which caused greatly restrained photoinduced holes transferring to the surface and retarded surface water oxidation reaction, leading to decreased PEC water splitting activity. This study clearly demonstrated that doping could be effective to enhance the PEC activity of α-Fe2O3 nanorods as photoanodes, while it is of great necessity to balance the trade-off between the electronic structure and nanostructure evolution by optimizing the dopant concentration, for increased donor density and meanwhile with the nanorod nanostructure well preserved for directed charge transfer.

The photoelectrochemical (PEC) water splitting activity of Nb and Ta-doped hematite (α-Fe2O3) nanorods was investigated with reference to electronic structures by in situ synchrotron x-ray absorption spectroscopy (XAS). Current density-potential measurements demonstrate that the PEC activity of α-Fe2O3 nanorods depends strongly on the species and concentrations of dopants. The doping of α-Fe2O3 nanorods with a low level of Nb or Ta can improve their electrical conductivity and thereby facilitate charge transport and reduced electron-hole recombination therein. The photoconversion effects of Nb and Ta-doped α-Fe2O3 by in situ XAS in the dark and under illumination revealed opposite evolutions of the spectral intensities of the Fe L-edge and Nb/Ta L-edge, indicating that charge transfer and a conduction pathway are involved in the photoconversion. Analytic in situ XAS results reveal that the α-Fe2O3 that is doped with a low level of Nb has a greater photoconversion efficiency than that doped with Ta because Nb sites are more active than Ta sites in α-Fe2O3. The correlation between PEC activity and the electronic structure of Nb/Ta-doped α-Fe2O3 is examined in detail using in situ XAS and helps to elucidate the mechanism of PEC water splitting in terms of the electronic structure.