Enhanced Solar Fuel Production over In2 O3 @Co2 VO4 Hierarchical Nanofibers with S-Scheme Charge Separation Mechanism.

The conversion of CO2 into valuable solar fuels via photocatalysis is a promising strategy for addressing energy shortages and environmental crises. Here, novel In2 O3 @Co2 VO4 hierarchical heterostructures are fabricated by in situ growing Co2 VO4 nanorods onto In2 O3 nanofibers. First-principle calculations and X-ray photoelectron spectroscopy (XPS) measurements reveal the electron transfer between In2 O3 and Co2 VO4 driven by the difference in work functions, thus creating an interfacial electric field and bending the bands at the interfaces. In this case, the photogenerated electrons in In2 O3 transport to Co2 VO4 and recombine with its holes, indicating the formation of In2 O3 @Co2 VO4 S-scheme heterojunctions and resulting in effective separation of charge carriers, as confirmed by in situ irradiation XPS. The unique S-scheme mechanism, along with the enhanced optical absorption and the lower Gibbs free energy change for the production of * CHO, significantly contributes to the efficient CO2 photoreduction into CO and CH4 in the absence of any molecule cocatalyst or scavenger. Density functional theory simulation and in situ diffuse reflectance infrared Fourier transform spectroscopy are employed to elucidate the reaction mechanism in detail.

Enhancing Hole Transport Uniformity for Efficient Inverted Perovskite Solar Cells through Optimizing Buried Interface Contacts and Suppressing Interface Recombination.

[4-(3,6-dimethyl-9H-carbazol-9yl)butyl]phosphonic acid (Me-4PACz) self-assembly material has been recognized as a highly effective approach for mitigating nickel oxide (NiOx) surface-related challenges in inverted perovskite solar cells (IPSCs). However, its uneven film generation and failure to effectively passivate the buried interface defects limit the device's performance improvement potential. Herein, p-xylylenediphosphonic acid (p-XPA) containing bilateral phosphate groups (-PO3H2) is introduced as an interface layer between the NiOx/Me-4PACz and the perovskite layer. P-XPA can flatten the surface of hole transport layer and optimize interface contact. Meanwhile, p-XPA achieves better energy level alignment and promotes interfacial hole transport. In addition, the bilateral -PO3H2 of p-XPA can chelate with Pb2+ and form hydrogen bond with FA+ (formamidinium cation), thereby suppressing buried interface non-radiative recombination loss. Consequently, the IPSC with p-XPA buried interface modification achieves champion power conversion efficiency of 25.87 % (certified at 25.45 %) at laboratory scale (0.0448 cm2). The encapsulated target device exhibits better operational stability. Even after 1100 hours of maximum power point tracking at 50 °C, its efficiency remains at an impressive 82.7 % of the initial efficiency. Molecules featuring bilateral passivation groups optimize interfacial contact and inhibit interfacial recombination, providing an effective approach to enhancing the stability and efficiency of devices.

Single-Atom Iridium on Hematite Photoanodes for Solar Water Splitting: Catalyst or Spectator?

Single-atom catalysts (SACs) on hematite photoanodes are efficient cocatalysts to boost photoelectrochemical performance. They feature high atom utilization, remarkable activity, and distinct active sites. However, the specific role of SACs on hematite photoanodes is not fully understood yet: Do SACs behave as a catalytic site or as a spectator? By combining spectroscopic experiments and computer simulations, we demonstrate that single-atom iridium (sIr) catalysts on hematite (α-Fe2O3/sIr) photoanodes act as a true catalyst by trapping holes from hematite and providing active sites for the water oxidation reaction. In situ transient absorption spectroscopy showed a reduced number of holes and shortened hole lifetime in the presence of sIr. This was particularly evident on the second timescale, indicative of fast hole transfer and depletion toward water oxidation. Intensity-modulated photocurrent spectroscopy evidenced a faster hole transfer at the α-Fe2O3/sIr/electrolyte interface compared to that at bare α-Fe2O3. Density functional theory calculations revealed the mechanism for water oxidation using sIr as a catalytic center to be the preferred pathway as it displayed a lower onset potential than the Fe sites. X-ray photoelectron spectroscopy demonstrated that sIr introduced a mid-gap of 4d state, key to the fast hole transfer and hole depletion. These combined results provide new insights into the processes controlling solar water oxidation and the role of SACs in enhancing the catalytic performance of semiconductors in photo-assisted reactions.

Realizing Nanolime Aqueous Dispersion via Ionic Liquid Surface Modification to Consolidate Stone Relics.

After decades of research in the conservation of cultural heritage, nanolime (NL) has emerged as a potential alternative inorganic material to the frequently used organic materials. However, its poor kinetic stability in water has been a major challenge that restricted its penetration depth through cultural relics and resulted in unsatisfactory conservation outcomes. Here, for the first time, we realize NL water dispersion by modification of ionic liquid (1-butyl-3-methylimidazolium tetrafluoroborate) via a sample aqueous solution deposit method. Our findings indicate that the cation of the ionic liquid (IL) binds strongly to the surface of NL particles (IL-NL) by forming hydrogen bonds with Ca(OH)2 facets. The absorption of IL causes an unexpected significant alteration in the morphology of NL particles and results in a drastic reduction in NL's size. More importantly, this absorption endows NL excellent kinetic stability dispersed into water and implements NL water dispersion, which makes a breakthrough in terms of extreme poor kinetic stability of as-synthesized NL and commercial NL in water. The mechanism driving IL-NL water dispersion is explained by Stern theory. In the context of consolidating weathered stone, the presence of IL may delay carbonation of NL but the penetration depth of IL-NL through stone samples is three times deeper than that of as-synthesized and commercial NLs. Additionally, the consolidation strength of IL-NL is similar to that of as-synthesized NL and commercial NL. Moreover, IL-NL has no significant impact on the permeability, pore size, and microstructure of consolidated stone relics. Our research contributes to the field of NL-related materials and will enhance the dissemination and utilization of NL-based materials in the preservation of water-insensitive cultural heritage.

The mediating effects of self-directed learning ability and critical thinking ability on the relationship between learning engagement and problem-solving ability among nursing students in Southern China: a cross-sectional study.

BACKGROUND: Problem-solving ability has been identified as a core competence that nursing students should develop, and it plays a vital role in career development. Therefore, it is necessary to investigate factors related to problem-solving ability and the path relationships among those factors in the context of nursing students. OBJECTIVE: This study aims to identify the factors that affect problem-solving ability, and to investigate path relationships of self-directed learning ability, critical thinking ability, learning engagement, and problem-solving ability among nursing students. DESIGN: A cross-sectional study. SETTINGS: The Department of Nursing at a university located in Shanghai, China. SAMPLE: A total of 540 nursing students with a three-year education program were enrolled in the current study. METHODS: Data were collected by using a structured questionnaire, including general information, learning engagement, self-directed learning ability, critical thinking ability, and problem-solving ability of nursing students. Pearson's correlations were used to explore the relationships between learning engagement, self-directed learning ability, critical thinking ability, and problem-solving ability. The path relationships were analyzed by constructing a structural equation model using AMOS software. RESULTS: Our results showed that learning engagement, self-directed learning ability, and critical thinking ability were positively associated with problem-solving ability. Furthermore, learning engagement did not influence problem-solving ability directly, but it affected problem-solving ability indirectly via self-directed learning ability and critical thinking ability among nursing students. Additionally, the total effects of self-directed learning (0.442) and critical thinking ability (0.581) were more prominent than learning engagement (0.361) on problem-solving ability. CONCLUSIONS: To improve the problem-solving ability of nursing students, nursing educators should develop targeted strategies to enhance learning engagement, self-directed learning ability, and critical thinking ability.

Association between ageing knowledge and willingness to care for older adults among nursing students in China: the mediating role of attitude towards older adults.

Little is known about the mediating effect of attitude toward older adults on the relationship between aging knowledge and willingness to care for older adults. We applied the theory of planned behavior (TPB) and the knowledge-attitude-behavior (KAB) model as theoretical frameworks to examine the mediation effect of attitude toward older adults. Data from 388 Chinese nursing students were analyzed. The Willingness to Care for Older People (WCOP) scale, Kogan's Attitude toward Older People scale (KAOP) and Facts on Aging Quiz (FAQ) were utilized to assess willingness, attitude and aging knowledge, respectively. Data were analyzed using SPSS 22. 0 with the PROCESS macro. Bootstrap methods were used to obtain the significance of mediating effects. The study showed that aging knowledge was significantly associated with willingness to care for older adults and that attitude toward older adults mediated the association. Bootstrapping method confirmed the significance of the indirect effect of aging knowledge through attitude, accounting for 18.9% of the total willingness variance. Overall, based on the TPB and the KAB theoretical framework, our data support the notion that improving aging knowledge and attitude may contribute to improve the willingness to aged care among nursing students.

Gradient Heating Epitaxial Growth Gives Well Lattice-Matched Mo2 C-Mo2 N Heterointerfaces that Boost Both Electrocatalytic Hydrogen Evolution and Water Vapor Splitting.

An optimized approach to producing lattice-matched heterointerfaces for electrocatalytic hydrogen evolution has not yet been reported. Herein, we present the synthesis of lattice-matched Mo2 C-Mo2 N heterostructures using a gradient heating epitaxial growth method. The well lattice-matched heterointerface of Mo2 C-Mo2 N generates near-zero hydrogen-adsorption free energy and facilitates water dissociation in acid and alkaline media. The lattice-matched Mo2 C-Mo2 N heterostructures have low overpotentials of 73 mV and 80 mV at 10 mA cm-2 in acid and alkaline solutions, respectively, comparable to commercial Pt/C. A novel photothermal-electrocatalytic water vapor splitting device using the lattice-matched Mo2 C-Mo2 N heterostructure as a hydrogen evolution electrocatalyst displays a competitive cell voltage for electrocatalytic water splitting.

Critical Role of Removing Impurities in Nickel Oxide on High-Efficiency and Long-Term Stability of Inverted Perovskite Solar Cells.

The performance enhancement of inverted perovskite solar cells applying nickel oxide (NiOx ) as the hole transport layer (HTL) has been limited by impurity ions (such as nitrate ions). Herein, we have proposed a strategy to obtain high-quality NiOx nanoparticles via an ionic liquid-assisted synthesis method (NiOx -IL). Experimental and theoretical results illustrate that the cation of the ionic liquid can inhibit the adsorption of impurity ions on nickel hydroxide through a strong hydrogen bond and low adsorption energy, thereby obtaining NiOx -IL HTL with high conductivity and strong hole-extraction ability. Importantly, the removal of impurity ions can effectively suppress the redox reaction between the NiOx film and the perovskite film, thus slowing down the deterioration of device performance. Consequently, the modified inverted device shows a striking efficiency exceeding 22.62 %, and superior stability maintaining 92 % efficiency at a maximum power point tracking under one sun illumination for 1000 h.

Hybrid nanostructures of metal/two-dimensional nanomaterials for plasmon-enhanced applications.

Hybrid nanostructures composed of graphene or other two-dimensional (2D) nanomaterials and plasmonic metal components have been extensively studied. The unusual properties of 2D materials are associated with their atomically thin thickness and 2D morphology, and many impressive structures enable the metal nanomaterials to establish various interesting hybrid nanostructures with outstanding plasmonic properties. In addition, the hybrid nanostructures display unique optical characteristics that are derived from the close conjunction of plasmonic optical effects and the unique physicochemical properties of 2D materials. More importantly, the hybrid nanostructures show several plasmonic electrical effects including an improved photogeneration rate, efficient carrier transfer, and a plasmon-induced "hot carrier", playing a significant role in enhancing device performance. They have been widely studied for plasmon-enhanced optical signals, photocatalysis, photodetectors (PDs), and solar cells. In this review, the developments in the field of metal/2D hybrid nanostructures are comprehensively described. Preparation of hybrid nanostructures is first presented according to the 2D material type, as well as the metal nanomaterial morphology. The plasmonic properties and the enabled applications of the hybrid nanostructures are then described. Lastly, possible future research in this promising field is discussed.

Correction: Hybrid nanostructures of metal/two-dimensional nanomaterials for plasmon-enhanced applications.

Correction for 'Hybrid nanostructures of metal/two-dimensional nanomaterials for plasmon-enhanced applications' by Xuanhua Li et al., Chem. Soc. Rev., 2016, 45, 3145-3187.

Au NPs@MoS2 Sub-Micrometer Sphere-ZnO Nanorod Hybrid Structures for Efficient Photocatalytic Hydrogen Evolution with Excellent Stability.

MoS2 shows promising applications in photocatalytic water splitting, owing to its uniquely optical and electric properties. However, the insufficient light absorption and lack of performance stability are two crucial issues for efficient application of MoS2 nanomaterials. Here, Au nanoparticles (NPs)@MoS2 sub-micrometer sphere-ZnO nanorod (Au NPs@MoS2 -ZnO) hybrid photocatalysts have been successfully synthesized by a facile process combining the hydrothermal method and seed-growth method. Such photocatalysts exhibit high efficiency and excellent stability for hydrogen production via multiple optical-electrical effects. The introduction of Au NPs to MoS2 sub-micrometer spheres forming a core-shell structure demonstrates strong plasmonic absorption enhancement and facilitates exciton separation. The incorporation of ZnO nanorods to the Au NPs@MoS2 hybrids further extends the light absorption to a broader wavelength region and enhances the exciton dissociation. In addition, mutual contacts between Au NPs (or ZnO nanorods) and the MoS2 spheres effectively protect the MoS2 nanosheets from peeling off from the spheres. More importantly, efficiently multiple exciton separations help to restrain the MoS2 nanomaterials from photocorrosion. As a result, the Au@MoS2 -ZnO hybrid structures exhibit an excellent hydrogen gas evolution (3737.4 µmol g-1 ) with improved stability (91.9% of activity remaining) after a long-time test (32 h), which is one of the highest photocatalytic activities to date among the MoS2 based photocatalysts.

Designing and fabricating double resonance substrate with metallic nanoparticles-metallic grating coupling system for highly intensified surface-enhanced Raman spectroscopy.

Recently, nanoparticle-film coupling systems in which metal nanoparticles (supported localized surface plasmons, LSPs) are separated from a flat metal film (supported surface plasmon polaritons, SPPs) by a spacer have been widely reported due to its strong local enhancement field. However, there is are limited studies, which employ the design of combing metal grating into the nanoparticle-film gap system. Here, we propose and fabricate a novel double-resonance SERS system by strategically assembling Au NPs separated by a MoO3 nanospacer from an Ag grating film. The Ag grating with clear SPP effect is used for the first time in a double-resonance system, and the monolayer Au NPs array is well assembled onto the top of the Ag grating with a compact and uniform distribution (inter-particles gap of about 5 nm). As a result, we experimentally and theoretically demonstrate a significant near-field enhancement. The very strong near-field produced in the proposed SERS substrates is due to multiple couplings, including the Au NPs-Ag grating film coupling and Au NPs-Au NPs coupling. In addition, the as-proposed SERS substrates show good reproducibility of SERS, which have potential applications in plasmonic sensing and analytical science.

Heterojunction-Induced Rapid Transformation of Ni3+/Ni2+ Sites which Mediates Urea Oxidation for Energy-Efficient Hydrogen Production.

Water electrolysis is an environmentally-friendly strategy for hydrogen production but suffers from significant energy consumption. Substituting urea oxidation reaction (UOR) with lower theoretical voltage for water oxidation reaction adopting nickel-based electrocatalysts engenders reduced energy consumption for hydrogen production. The main obstacle remains strong interaction between accumulated Ni3+ and *COO in the conventional Ni3+-catalyzing pathway. Herein, a novel Ni3+/Ni2+ mediated pathway for UOR via constructing a heterojunction of nickel metaphosphate and nickel telluride (Ni2P4O12/NiTe), which efficiently lowers the energy barrier of UOR and avoids the accumulation of Ni3+ and excessive adsorption of *COO on the electrocatalysts, is developed. As a result, Ni2P4O12/NiTe demonstrates an exceptionally low potential of 1.313 V to achieve a current density of 10 mA cm-2 toward efficient urea oxidation reaction while simultaneously showcases an overpotential of merely 24 mV at 10 mA cm-2 for hydrogen evolution reaction. Constructing urea electrolysis electrolyzer using Ni2P4O12/NiTe at both sides attains 100 mA cm-2 at a low cell voltage of 1.475 V along with excellent stability over 500 h accompanied with nearly 100% Faradic efficiency.

Co-Self-Assembled Monolayers Modified NiOx for Stable Inverted Perovskite Solar Cells.

[4-(3,6-dimethyl-9H-carbazol-9yl)butyl]phosphonic acid (Me-4PACz) self-assembled molecules (SAM) are an effective method to solve the problem of the buried interface of NiOx in inverted perovskite solar cells (PSCs). However, the Me-4PACz end group (carbazole core) cannot forcefully passivate defects at the bottom of the perovskite film. Here, a Co-SAM strategy is employed to modify the buried interface of PSCs. Me-4PACz is doped with phosphorylcholine chloride (PC) to form a Co-SAM to improve the monolayer coverage and reduce leakage current. The phosphate group and chloride ions (Cl-) in PC can inhibit NiOx surface defects. Meantime, the quaternary ammonium ions and Cl- in PC can fill organic cations and halogen vacancies in the perovskite film to enable defects passivation. Moreover, Co-SAM can promote the growth of perovskite crystals, collaboratively solve the problem of buried defects, suppress nonradiative recombination, accelerate carrier transmission, and relieve the residual stress of the perovskite film. Consequently, the Co-SAM modified devices show power conversion efficiencies as high as 25.09% as well as excellent device stability with 93% initial efficiency after 1000 h of operation under one-sun illumination. This work demonstrates the novel approach for enhancing the performance and stability of PSCs by modifying Co-SAM on NiOx.

Large electronegativity differences between adjacent atomic sites activate and stabilize ZnIn2S4 for efficient photocatalytic overall water splitting.

Photocatalytic overall water splitting into hydrogen and oxygen is desirable for long-term renewable, sustainable and clean fuel production on earth. Metal sulfides are considered as ideal hydrogen-evolved photocatalysts, but their component homogeneity and typical sulfur instability cause an inert oxygen production, which remains a huge obstacle to overall water-splitting. Here, a distortion-evoked cation-site oxygen doping of ZnIn2S4 (D-O-ZIS) creates significant electronegativity differences between adjacent atomic sites, with S1 sites being electron-rich and S2 sites being electron-deficient in the local structure of S1-S2-O sites. The strong charge redistribution character activates stable oxygen reactions at S2 sites and avoids the common issue of sulfur instability in metal sulfide photocatalysis, while S1 sites favor the adsorption/desorption of hydrogen. Consequently, an overall water-splitting reaction has been realized in D-O-ZIS with a remarkable solar-to-hydrogen conversion efficiency of 0.57%, accompanying a ~ 91% retention rate after 120 h photocatalytic test. In this work, we inspire an universal design from electronegativity differences perspective to activate and stabilize metal sulfide photocatalysts for efficient overall water-splitting.

Hydrovoltaic effect-enhanced photocatalysis by polyacrylic acid/cobaltous oxide-nitrogen doped carbon system for efficient photocatalytic water splitting.

Severe carrier recombination and the slow kinetics of water splitting for photocatalysts hamper their efficient application. Herein, we propose a hydrovoltaic effect-enhanced photocatalytic system in which polyacrylic acid (PAA) and cobaltous oxide (CoO)-nitrogen doped carbon (NC) achieve an enhanced hydrovoltaic effect and CoO-NC acts as a photocatalyst to generate H2 and H2O2 products simultaneously. In this system, called PAA/CoO-NC, the Schottky barrier height between CoO and the NC interface decreases by 33% due to the hydrovoltaic effect. Moreover, the hydrovoltaic effect induced by H+ carrier diffusion in the system generates a strong interaction between H+ ions and the reaction centers of PAA/CoO-NC, improving the kinetics of water splitting in electron transport and species reaction. PAA/CoO-NC exhibits excellent photocatalytic performance, with H2 and H2O2 production rates of 48.4 and 20.4 mmol g-1 h-1, respectively, paving a new way for efficient photocatalyst system construction.

In situ photocatalytically enhanced thermogalvanic cells for electricity and hydrogen production.

High-performance thermogalvanic cells have the potential to convert thermal energy into electricity, but their effectiveness is limited by the low concentration difference of redox ions. We report an in situ photocatalytically enhanced redox reaction that generates hydrogen and oxygen to realize a continuous concentration gradient of redox ions in thermogalvanic devices. A linear relation between thermopower and hydrogen production rate was established as an essential design principle for devices. The system exhibited a thermopower of 8.2 millivolts per kelvin and a solar-to-hydrogen efficiency of up to 0.4%. A large-area generator (112 square centimeters) consisting of 36 units yielded an open-circuit voltage of 4.4 volts and a power of 20.1 milliwatts, as well 0.5 millimoles of hydrogen and 0.2 millimoles of oxygen after 6 hours of outdoor operation.

Room temperature nondestructive encapsulation via self-crosslinked fluorosilicone polymer enables damp heat-stable sustainable perovskite solar cells.

Encapsulation engineering is an effective strategy to improve the stability of perovskite solar cells. However, current encapsulation materials are not suitable for lead-based devices because of their complex encapsulation processes, poor thermal management, and inefficient lead leakage suppression. In this work, we design a self-crosslinked fluorosilicone polymer gel, achieving nondestructive encapsulation at room temperature. Moreover, the proposed encapsulation strategy effectively promotes heat transfer and mitigates the potential impact of heat accumulation. As a result, the encapsulated devices maintain 98% of the normalized power conversion efficiency after 1000 h in the damp heat test and retain 95% of the normalized efficiency after 220 cycles in the thermal cycling test, satisfying the requirements of the International Electrotechnical Commission 61215 standard. The encapsulated devices also exhibit excellent lead leakage inhibition rates, 99% in the rain test and 98% in the immersion test, owing to excellent glass protection and strong coordination interaction. Our strategy provides a universal and integrated solution for achieving efficient, stable, and sustainable perovskite photovoltaics.

Polydopamine-Modified Nanolime with High Kinetic Stability in Water for the Consolidation of Stone Relics.

As a promising inorganic nanomaterial for the conservation of arenaceous sandstone-based relics such as wall painting, ancient building, stone heritage etc., nanolime (NL) has drawn increasing attention in recent years. Usually, NL needs to be dispersed into an alcoholic solution when applied. Nevertheless, a back-migration phenomenon of NL to the surface of the stone and delayed carbonation of NL enabled by alcohol do not guarantee good preservation effects. Dispersing NL into water can avoid the above issues. However, NL water suspension shows extremely poor kinetic stability, greatly restricting the penetration of NL into stone relics as well as bringing unfavorable impacts to the treated stone heritage. Here, we develop a facile method to synthesize polydopamine (PDA)-modified NL (PDA@NL). Characterizations demonstrate that PDA is uniformly distributed on the surface of NL particles though hydrogen bonds. In addition, the presence of PDA reduces the size of NL particles and achieves the highest specific surface area of NL reported to date. More importantly, water suspension of PDA@NL is far more stable than that of pure NL. The kinetic stability mechanism of PDA@NL in water is attributed to the lessened spatial interactions between NL particles, which is realized by the coverage of PDA on the surface of NL particles. Furthermore, the coverage of PDA does not inhibit carbonation. Within 105 h, NL in PDA@NL completes carbonation and obtains 93.7% calcite, which is comparable to that of NL suspension. Permeability tests prove that the PDA@NL suspension penetrates far deeper through stone specimens compared with the NL suspension. Additionally, PDA@NL presents good consolidation performances for stone samples. Our work opens a new direction for the modification of NL that will boost the studies of NL-modified materials as well as the conservation of cultural heritage.

Boosting photocatalytic hydrogen production from water by photothermally induced biphase systems.

Solar-driven hydrogen production from water using particulate photocatalysts is considered the most economical and effective approach to produce hydrogen fuel with little environmental concern. However, the efficiency of hydrogen production from water in particulate photocatalysis systems is still low. Here, we propose an efficient biphase photocatalytic system composed of integrated photothermal-photocatalytic materials that use charred wood substrates to convert liquid water to water steam, simultaneously splitting hydrogen under light illumination without additional energy. The photothermal-photocatalytic system exhibits biphase interfaces of photothermally-generated steam/photocatalyst/hydrogen, which significantly reduce the interface barrier and drastically lower the transport resistance of the hydrogen gas by nearly two orders of magnitude. In this work, an impressive hydrogen production rate up to 220.74 µmol h-1 cm-2 in the particulate photocatalytic systems has been achieved based on the wood/CoO system, demonstrating that the photothermal-photocatalytic biphase system is cost-effective and greatly advantageous for practical applications.