Solidophobic Surface for Electrochemical Extraction of High-Valued Mg(OH)2 Coupled with H2 Production from Seawater.

A significant challenge in direct seawater electrolysis is the rapid deactivation of the cathode due to the large scaling of Mg(OH)2. Herein, we synthesized a Pt-coated highly disordered NiCu alloy (Pt-NiCu alloy) electrode with superior solidophobic behavior, enabling stable hydrogen generation (100 mA cm-2, >1000 h durability) and simultaneous production of Mg(OH)2 (>99.0% purity) in electrolyte enriched with Mg2+ and Ca2+. The unconventional solidophobic property primarily stems from the high surface energy of the NiCu alloy substrate, which facilitates the adsorption of surface water and thereby compels the bulk formation of Mg(OH)2 via homogeneous nucleation. The discovery of this solidophobic electrode will revolutionarily simplify the existing techniques for seawater electrolysis and increase the economic viability for seawater electrolysis.

Self-Supported WO3@RuO2 Nanowires for Electrocatalytic Acidic Water Oxidation.

Developing catalysts with high catalytic activity and stability in acidic media is crucial for advancing hydrogen production in proton exchange membrane water electrolyzers (PEMWEs). To this end, a self-supported WO3@RuO2 nanowire structure was grown in situ on a titanium mesh using hydrothermal and ion-exchange methods. Despite a Ru loading of only 0.098 wt %, it achieves an overpotential of 246 mV for the oxygen evolution reaction (OER) at a current density of 10 mA·cm-2 in acidic 0.5 M H2SO4 while maintaining excellent stability over 50 h, much better than that of the commercial RuO2. After the establishment of the WO3@RuO2 heterostructure, a reduced overpotential of the rate-determining step from M-O* to M-OOH* is confirmed by the DFT calculation. Meanwhile, its enhanced OER kinetics are also greatly improved by this self-supported system in the absence of the organic binder, leading to a reduced interface resistance between active sites and electrolytes. This work presents a promising approach to minimize the use of noble metals for large-scale PEMWE applications.

Ligand Defect Density Regulation in Metal-Organic Frameworks by Functional Group Engineering on Linkers.

Defects in solid materials vitally determine their physicochemical properties; however, facile regulation of the defect density is still a challenge. Herein, we demonstrate that the ligand defect density of metal-organic frameworks (MOFs) with a UiO-66 structural prototype is precisely regulated by tuning the linker groups (X = OMe, Me, H, F). Detailed analyses reveal that the ligand defect concentration is positively correlated with the electronegativity of linker groups, and Ce-UiO-66-F, constructed by F-containing ligands and Ce-oxo nodes, possesses the superior ligand defect density (>25%) and identifiable irregular periodicity. The increase in ligand defect density results in the reduction of the valence state and the coordination number of Ce sites in Ce-UiO-66-X, and this merit further validates the relationship between the defective structure and catalytic performance of CO2 cycloaddition reaction. This facile, efficient, and reliable strategy may also be applicable to precisely constructing the defect density of porous materials in the future.

Atomically Dispersed Dual Metal Sites Boost the Efficiency of Olefins Epoxidation in Tandem with CO2 Cycloaddition.

Tandem catalysis provides an economical and energy-efficient process for the production of fine chemicals. In this work, we demonstrate that a rationally synthesized carbon-based catalyst with atomically dispersed dual Fe-Al sites (ADD-Fe-Al) achieves superior catalytic activity for the one-pot oxidative carboxylation of olefins (conversion ∼97%, selectivity ∼91%), where the yield of target product over ADD-Fe-Al is at least 62% higher than that of monometallic counterparts. The kinetic results reveal that the excellent catalytic performance arises from the synergistic effect between Fe (oxidation site) and Al sites (cycloaddition site), where the efficient CO2 cycloaddition with epoxides in the presence of Al sites (3.91 wt %) positively shifts the oxidation equilibrium to olefin epoxidation over Fe sites (0.89 wt %). This work not only offers an advanced catalyst for oxidative carboxylation of olefins but also opens up an avenue for the rational design of multifunctional catalysts for tandem catalytic reactions in the future.

Self-Supporting Mn-RuO2 Nanoarrays for Stable Oxygen Evolution Reaction in Acid.

Currently, the process of an acidic oxygen evolution reaction (OER) necessitates the use of Iridium dioxygen (IrO2), which is both expensive and incredibly scarce on Earth. Ruthenium dioxygen (RuO2) offers high activity for acidic OERs and presents a potential substitution for IrO2. Nevertheless, its practical application is hindered by its relatively poor stability. In this study, we have developed Mn-doped RuO2 (Mn-RuO2) nanoarrays that are anchored on a titanium (Ti) mesh utilizing a two-step methodology involving the preparation of MnO2 nanoarrays followed by a subsequent Ru exchange and annealing process. By precisely optimizing the annealing temperature, we have managed to attain a remarkably low overpotential of 217 mV at 10 mA cm-2 in a 0.5 M H2SO4 solution. The enhanced catalytic activity of our Mn-RuO2 nanoarrays can be attributed to the electronic modification brought about by the high exposure of active sites, Mn dopant, efficient mass transfer, as well as the efficient transfer of electrons between the Ti mesh and the catalyst arrays. Furthermore, these self-supported Mn-RuO2 nanoarrays demonstrated excellent long-term stability throughout a chronoamperometry test lasting for 100 h, with no discernible changes observed in the Ru chemical states.

Concerns on the Effects of Electrode Positions in Electrolyte Container for the Oxygen Evolution Reaction.

Water electrolysis is currently a major technique to produce clean hydrogen, which is regarded as a promising and sustainable energy carrier. The efficiency of water electrolysis is highly dependent on the oxygen evolution reaction (OER) on the anode. The evaluation of an OER electrocatalyst is frequently carried out on a three-electrode system in a container of electrolyte. Herein, we found that the electrode positions in the electrolyte container could significantly affect the data acquisition of OER performance. After a detailed investigation, we reveal that the difference of the OER activity of an electrocatalyst at a different position is originated from their different iRu drop and the gas diffusion resistance. For the first time, this work evokes concerns on the accurate evaluation of electrocatalysts regarding the electrode position. For fair comparisons and reliable results, it is strongly suggested to keep the electrode position unchanged in the electrochemical measurements. In addition, the establishment of a standard electrolyzer setup for electrocatalysis evaluation in the electrochemical community is also called for.

The Critical Role of Additive Sulfate for Stable Alkaline Seawater Oxidation on Nickel-Based Electrodes.

Seawater electrolysis to produce hydrogen is a critical technology in marine energy projects; however, the severe anode corrosion caused by the highly concentrated chloride is a key issue should be addressed. In this work, we discover that the addition of sulfate in electrolyte can effectively retard the corrosion of chloride ions to the anode. We take nickel foam as the example and observe that the addition of sulfate can greatly improve the corrosion resistance, resulting in prolonged operating stability. Theoretical simulations and in situ experiments both demonstrate that sulfate anions can be preferentially adsorbed on anode surface to form a negative charge layer, which repulses the chloride ions away from the anode by electrostatic repulsion. The repulsive effect of the adsorbed sulfate is also applicable in highly-active catalyst (nickel iron layered double hydroxide) on nickel foam, which shows ca. 5 times stability of that in traditional electrolyte.

Investigation of speckle suppression beyond human eye sensitivity by using a passive multimode fiber and a multimode fiber bundle.

A method of speckle suppression without any active device is expected for pico-projectors. The effectiveness of the passive method of speckle reduction using a single multimode fiber and a multimode fiber bundle was actually measured and theoretically analyzed. The dependences of the speckle contrast and speckle suppression coefficient on the parameters of multimode fiber and projection systems were investigated. Our results shown that the efficiency of speckle suppression was limited because only the radial direction of the objective lens aperture was used. An improvement using both of the radial and azimuthal directions of the objective lens aperture is required.

Superwetting Electrodes for Gas-Involving Electrocatalysis.

Gas-involving electrochemical reactions, including gas evolution reactions and gas consumption reactions, are essential components of the energy conversion processes and gathering elevating attention from researchers. Besides the development of highly active catalysts, gas management during gas-involving electrochemical reactions is equally critical for industrial applications to achieve high reaction rates (hundreds of milliamperes per square centimeter) under practical operation voltages. Biomimetic surfaces, which generally show regular micro/nanostructures, offer new insights to address this issue because of their special wetting capabilities. Although a series of nanoarray-based structured electrodes have been constructed and demonstrated with excellent performances for gas-involving electrochemical reactions, understanding of bubble wetting behavior remains elusive. In this Account, our recent works including understanding the way to achieve the superwetting properties of solid electrode surfaces, and our advanced design and fabrication of superwetting electrodes for different types of electrochemical gas-involving electrochemical reactions are summarized. To begin, we first put forward several criteria of superwetting surfaces, including superaerophobic surfaces and superaerophilic surfaces. Then, we discuss how the nanoarray-based surface engineering technology can achieve the superwetting properties, in which high roughness of the nanoarray architecture is discovered to be a critical factor for constructing superaerophobic and superaerophilic surfaces. Finally, the feasibility of superwetting electrodes for enhancing the performances of gas-involving electrochemical reactions is also analyzed. Based on theoretical guidance, a series of superaerophobic and superaerophilic electrodes with various methods, such as hydrothermal reactions, electrodeposition technology and high-temperature vapor phase growth, have been built for practice. By comparing with the traditional planar electrodes fabricated by drop-casting method, the superaerophobic electrodes afford a low adhesion force to gas products and accelerate gas bubbles evolution, resulting in fast current increase and stable current for gas evolution reactions. This phenomenon is confirmed by operating different gas evolution reactions (hydrogen evolution, oxygen evolution and hydrazine oxidation) using superaerophobic electrodes with different catalysts (e.g., MoS2, Pt and Cu). On the other side, the superaerophilic electrodes can improve the catalytic performance of gas consumption reaction (e.g., oxygen reduction reaction) by facilitating gas diffusion and electron transport. Following theoretical analyses and experimental demonstrations, we assemble several energy conversion systems (e.g., electrochemical water splitting and direct hydrazine fuel cells) based on superwetting electrodes and test their performances. By virtue of the structural advantages of electrodes, these energy conversion systems show much higher energy efficiencies than their counterparts. In the last section, we put forward several future fields which are worthy for further exploration as rational extensions of the superwetting electrodes.

Shell-Protective Secondary Silicon Nanostructures as Pressure-Resistant High-Volumetric-Capacity Anodes for Lithium-Ion Batteries.

The nanostructure design of a prereserved hollow space to accommodate 300% volume change of silicon anodes has created exciting promises for high-energy batteries. However, challenges with weak mechanical stability during the calendering process of electrode fabrication and poor volumetric energy density remain to be solved. Here we fabricated a pressure-resistant silicon structure by designing a dense silicon shell coating on secondary micrometer particles, each consisting of many silicon nanoparticles. The silicon skin layer significantly improves mechanical stability, while the inner porous structure efficiently accommodates the volume expansion. Such a structure can resist a high pressure of over 100 MPa and is well-maintained after the calendering process, demonstrating a high volumetric capacity of 2041 mAh cm-3. In addition, the dense silicon shell decreases the surface area and thus increases the initial Coulombic efficiency. With further encapsulation with a graphene cage, which allows the silicon core to expand within the cage while retaining electrical contact, the silicon hollow structure exhibits a high initial Coulombic efficiency and fast rise of later Coulombic efficiencies to >99.5% and superior stability in a full-cell battery.

Experimental demonstration of a flexible DOE loop with wideband speckle suppression for laser pico-projectors.

The compact and straightforward construction of a pico-projector using an original method for speckle suppression via a simple 1D diffractive optical element (DOE) structure on a loop of flexible film with tracked motion is demonstrated. The 1D-DOE structure is based on binary pseudorandom sequences. The method requires very little energy and space and can decrease speckle noise to levels below the detection sensitivity of the human eye. Large speckle suppression coefficients and low speckle contrasts are obtained for blue, green, and red lasers. Speckle suppression efficiency will be further significantly improved by optimization of the DOE structure and film material.

Identifying the Active Surfaces of Electrochemically Tuned LiCoO2 for Oxygen Evolution Reaction.

Identification of active sites for catalytic processes has both fundamental and technological implications for rational design of future catalysts. Herein, we study the active surfaces of layered lithium cobalt oxide (LCO) for the oxygen evolution reaction (OER) using the enhancement effect of electrochemical delithiation (De-LCO). Our theoretical results indicate that the most stable (0001) surface has a very large overpotential for OER independent of lithium content. In contrast, edge sites such as the nonpolar (112̅0) and polar (011̅2) surfaces are predicted to be highly active and dependent on (de)lithiation. The effect of lithium extraction from LCO on the surfaces and their OER activities can be understood by the increase of Co4+ sites relative to Co3+ and by the shift of active oxygen 2p states. Experimentally, it is demonstrated that LCO nanosheets, which dominantly expose the (0001) surface show negligible OER enhancement upon delithiation. However, a noticeable increase in OER activity (∼0.1 V in overpotential shift at 10 mA cm-2) is observed for the LCO nanoparticles, where the basal plane is greatly diminished to expose the edge sites, consistent with the theoretical simulations. Additionally, we find that the OER activity of De-LCO nanosheets can be improved if we adopt an acid etching method on LCO to create more active edge sites, which in turn provides a strong evidence for the theoretical indication.

Superaerophobic RuO2 -Based Nanostructured Electrode for High-Performance Chlorine Evolution Reaction.

Constructing a nanostructured electrode with superaerophobic surface property (i.e., superlow adhesion to gas bubbles) has been strikingly highlighted as an advanced technology to minimize the energy loss during various electrochemical gas evolution reactions. Herein, aiming at enhancing the performance of chlorine evolution reaction (ClER), which holds the key for chlor-alkali industry as well as water treatment, a nanostructured RuO2 @TiO2 electrode is demonstrated to overcome the bubble shielding effect, thereby maximizing the working area and offering a robust working condition. Benefitting from the direct growing architecture and the superaerophobic surface property, this nanostructured RuO2 @TiO2 electrode exhibits an excellent ClER performance, reaching 50 mA cm-2 at a low potential of 1.10 V (vs SCE) with a Faradaic efficiency over ≈90%. Moreover, a prominent stability (250 mA cm-2 for 10 h) is observed for this nanostructured electrode, probably due to the small vibrations and scratching forces from gas product.

Cramér-Rao lower bound analysis of phase diversity for sparse aperture optical systems.

Aberration detection of subapertures is critical to the resolution of a sparse aperture optical system. In this work, the Cramér-Rao lower bound (CRLB) expression of aberrations was first derived for the subapertures of a sparse aperture optical system. The aberrations were estimated by phase diversity, assuming that the photons follow the Poisson distribution. The derived formula has been applied to the Golay3 sparse aperture system to calculate the CRLB of the subapertures' aberrations with different defocus distances, fill factors, and ratios of photon numbers between the focal and defocal images. According to the CRLB criterion, the results indicate that the accuracy of aberration estimation increases as the fill factor of the sparse aperture system increases. The results also demonstrate that the optimal defocus distance of phase diversity is achieved when the CRLB reaches its minimum. The optimal ratio of photon numbers between the focal and defocal images is around 3∶7. However, for the piston error, more photons in the defocal image yield more accurate estimation results. This method can also be applied to the sparse aperture optical systems with other different configurations.

High-Performance Water Electrolysis System with Double Nanostructured Superaerophobic Electrodes.

Catalysts screening and structural optimization are both essential for pursuing a high-efficient water electrolysis system (WES) with reduced energy supply. This study demonstrates an advanced WES with double superaerophobic electrodes, which are achieved by constructing a nanostructured NiMo alloy and NiFe layered double hydroxide (NiFe-LDH) films for hydrogen evolution and oxygen evolution reactions, respectively. The superaerophobic property gives rise to significantly reduced adhesion forces to gas bubbles and thereby accelerates the hydrogen and oxygen bubble releasing behaviors. Benefited from these metrics and the high intrinsic activities of catalysts, this WES affords an early onset potential (≈1.5 V) for water splitting and ultrafast catalytic current density increase (≈0.83 mA mV(-1) ), resulting in ≈2.69 times higher performance compared to the commercial Pt/C and IrO2 /C catalysts based counterpart under 1.9 V. Moreover, enhanced performance at high temperature as well as prominent stability further demonstrate the practical application of this WES.

Electrochemical tuning of vertically aligned MoS2 nanofilms and its application in improving hydrogen evolution reaction.

The ability to intercalate guest species into the van der Waals gap of 2D layered materials affords the opportunity to engineer the electronic structures for a variety of applications. Here we demonstrate the continuous tuning of layer vertically aligned MoS2 nanofilms through electrochemical intercalation of Li(+) ions. By scanning the Li intercalation potential from high to low, we have gained control of multiple important material properties in a continuous manner, including tuning the oxidation state of Mo, the transition of semiconducting 2H to metallic 1T phase, and expanding the van der Waals gap until exfoliation. Using such nanofilms after different degree of Li intercalation, we show the significant improvement of the hydrogen evolution reaction activity. A strong correlation between such tunable material properties and hydrogen evolution reaction activity is established. This work provides an intriguing and effective approach on tuning electronic structures for optimizing the catalytic activity.

CoSe2 nanoparticles grown on carbon fiber paper: an efficient and stable electrocatalyst for hydrogen evolution reaction.

Development of a non-noble-metal hydrogen-producing catalyst is essential to the development of solar water-splitting devices. Improving both the activity and the stability of the catalyst remains a key challenge. In this Communication, we describe a two-step reaction for preparing three-dimensional electrodes composed of CoSe2 nanoparticles grown on carbon fiber paper. The electrode exhibits excellent catalytic activity for a hydrogen evolution reaction in an acidic electrolyte (100 mA/cm(2) at an overpotential of ∼180 mV). Stability tests though long-term potential cycles and extended electrolysis confirm the exceptional durability of the catalyst. This development offers an attractive catalyst material for large-scale water-splitting technology.

A hierarchical Ni-Co-O@Ni-Co-S nanoarray as an advanced oxygen evolution reaction electrode.

Developing an efficient electro-catalyst for water oxidation is essential for improving the performance, which holds the key for a number of energy conversion and storage devices. Here we report an effective method for fabricating a Ni-Co-O@Ni-Co-S hierarchical nanoarray, which showed a significantly improved activity relative to Ni-Co-O nanowire arrays for oxygen evolution reactions. The enhanced performance was attributed to the secondary formed Ni-Co-S nanoplatelets which not only acted as efficient electrocatalysts, but also facilitated the electrolyte penetration and increased the surface area.

Sulfur-regulated CoSe2 nanowires with high-charge active centers for electrochemical nitrate reduction to ammonium.

Developing high-efficiency electrocatalysts for nitrate-to-ammonia transformation holds significant promise for the production of ammonia, a crucial component in agricultural fertilizers and as a carbon-free energy carrier. In this study, we propose a viable strategy involving sulfur doping to modulate both the microstructure and electronic properties of CoSe2 for nitrate reduction. This approach remarkably enhances the conversion of nitrate to ammonia by effectively regulating the adsorption capability of nitrogenous intermediates. Specifically, sulfur-doped CoSe2 nanowires (S-CoSe2 NWs) exhibit a peak faradaic efficiency of 93.1% at -0.6 V vs. RHE and achieve the highest NH3 yield rate of 11.6 mg h-1 cm-2. Mechanistic investigations reveal that sulfur doping facilitates the creation of highly charged active sites, which enhance the adsorption of nitrite and subsequent hydrogenation, leading to improved selectivity towards ammonia production.

The construction of a nomogram to predict the prognosis and recurrence risks of UPJO.

Objective: This study was conducted to explore the risk factors for the prognosis and recurrence of ureteropelvic junction obstruction (UPJO). Methods: The correlation of these variables with the prognosis and recurrence risks was analyzed by binary and multivariate logistic regression. Besides, a nomogram was constructed based on the multivariate logistic regression calculation. After the model was verified by the C-statistic, the ROC curve was plotted to evaluate the sensitivity of the model. Finally, the decision curve analysis (DCA) was conducted to estimate the clinical benefits and losses of intervention measures under a series of risk thresholds. Results: Preoperative automated peritoneal dialysis (APD), preoperative urinary tract infection (UTI), preoperative renal parenchymal thickness (RPT), Mayo adhesive probability (MAP) score, and surgeon proficiency were the high-risk factors for the prognosis and recurrence of UPJO. In addition, a nomogram was constructed based on the above 5 variables. The area under the curve (AUC) was 0.8831 after self cross-validation, which validated that the specificity of the model was favorable. Conclusion: The column chart constructed by five factors has good predictive ability for the prognosis and recurrence of UPJO, which may provide more reasonable guidance for the clinical diagnosis and treatment of this disease.