Achieving Long-Lived Charge Separated State through Ultrafast Interfacial Hole Transfer in Redox Sites-Isolated CdS Nanorods for Enhanced Photocatalysis.

As opposed to natural photosynthesis, a significant challenge in a semiconductor-based photocatalyst is the limited hole extraction efficiency, which adversely affects solar-to-fuel efficiency. Recent studies have demonstrated that photocatalysts featuring spatially isolated dual catalytic oxidation/reduction sites can yield enhanced hole extraction efficiencies. However, the decay dynamics of excited states in such photocatalysts have not been explored. Here a ternary barbell-shaped CdS/MoS2/Cu2S heterostructure is prepared, comprising CdS nanorods (NRs) interfaced with MoS2 nanosheets at both ends and Cu2S nanoparticles on the sidewall. By using transient absorption (TA) spectra, highly efficient charge separation within the CdS/MoS2/Cu2S heterostructure are identified. This is achieved through directed electron transfer to the MoS2 tips at a rate constant of >8.3 × 109 s-1 and rapid hole transfer to the Cu2S nanoparticles on the sidewall at a rate of >6.1 × 1010 s-1, leading to an exceptional overall charge transfer constant of 2.3 × 1011 s-1 in CdS/MoS2/Cu2S. The enhanced hole transfer efficiency results in a remarkably prolonged charge-separated state, facilitating efficient electron accumulation within the MoS2 tips. Consequently, the ternary CdS/MoS2/Cu2S heterostructure demonstrates a 22-fold enhancement in visible-light-driven H2 generation compare to pure CdS nanorods. This work highlights the significance of efficient hole extraction in enhancing the solar-to-H2 performance of semiconductor-based heterostructure.

Strong Interfacial Chemical Bonding in Regulating Electron Transfer and Stabilizing Catalytic Sites in a Metal-Semiconductor Schottky Junction for Enhanced Photocatalysis.

The weak electronic interaction at metal-photocatalyst heterointerfaces often compromises solar-to-fuel performance. Here, a trifunctional Schottky junction, involving chemically stabilized ultrafine platinum nanoparticles (Pt NPs, ≈3 nm in diameter) on graphitic carbon nitride nanosheets (CNs) is proposed. The Pt-CN electronic interaction induces a 1.5% lattice compressive strain in Pt NPs and maintains their ultrafine size, effectively preventing their aggregation during photocatalytic reactions. Density functional theory calculations further demonstrate a significant reduction in the Schottky barrier at the chemically bonded CN-Pt heterointerface, facilitating efficient interfacial electron transfer, as supported by femtosecond transient absorption spectra (fs-TAS) measurements. The combined effects of lattice strain, stabilized Pt NPs, and efficient interfacial charge transport collaboratively enhance the photocatalytic performance, leading to over an 11-fold enhancement in visible light H2 production (8.52 mmol g-1 h-1) compared to the CN nanosheets with the in situ photo-deposited Pt NPs (0.76 mmol g-1 h-1). This study highlights the effectiveness of strong metal-semiconductor electronic interactions and underscores the potential for developing high-efficiency photocatalysts.

A 3d-4d-5d High Entropy Alloy as a Bifunctional Oxygen Catalyst for Robust Aqueous Zinc-Air Batteries.

High entropy alloys (HEAs) are highly suitable candidate catalysts for oxygen evolution and reduction reactions (OER/ORR) as they offer numerous parameters for optimizing the electronic structure and catalytic sites. Herein, FeCoNiMoW HEA nanoparticles are synthesized using a solution-based low-temperature approach. Such FeCoNiMoW nanoparticles show high entropy properties, subtle lattice distortions, and modulated electronic structure, leading to superior OER performance with an overpotential of 233 mV at 10 mA cm-2 and 276 mV at 100 mA cm-2 . Density functional theory calculations reveal the electronic structures of the FeCoNiMoW active sites with an optimized d-band center position that enables suitable adsorption of OOH* intermediates and reduces the Gibbs free energy barrier in the OER process. Aqueous zinc-air batteries (ZABs) based on this HEA demonstrate a high open circuit potential of 1.59 V, a peak power density of 116.9 mW cm-2 , a specific capacity of 857 mAh gZn -1 , and excellent stability for over 660 h of continuous charge-discharge cycles. Flexible and solid ZABs are also assembled and tested, displaying excellent charge-discharge performance at different bending angles. This work shows the significance of 4d/5d metal-modulated electronic structure and optimized adsorption ability to improve the performance of OER/ORR, ZABs, and beyond.

A π-Conjugated Van der Waals Heterostructure Between Single-Atom Ni-Anchored Salphen-Based Covalent Organic Framework and Polymeric Carbon Nitride for High-Efficiency Interfacial Charge Separation.

Semiconductor-based heterostructures have exhibited great promise as a photocatalyst to convert solar energy into sustainable chemical fuels, however, their solar-to-fuel efficiency is largely restricted by insufficient interfacial charge separation and limited catalytically active sites. Here the integration of high-efficiency interfacial charge separation and sufficient single-atom metal active sites in a 2D van der Waals (vdW) heterostructure between ultrathin polymeric carbon nitride (p-CN) and Ni-containing Salphen-based covalent organic framework (Ni-COF) nanosheets is illustrated. The results reveal a NiN2 O2 chemical bonding in NiCOF nanosheets, leading to a highly separated single-atom Ni sites, which will function as the catalytically active sites to boost solar fuel production, as confirmed by X-ray absorption spectra and density functional theory calculations. Using ultrafast femtosecond transient adsorption (fs-TA) spectra, it shows that the vdW p-CN/Ni-COF heterostructure exhibits a faster decay lifetime of the exciton annihilation (τ = 18.3 ps) compared to that of neat p-CN (32.6 ps), illustrating an efficiently accelerated electron transfer across the vdW heterointerface from p-CN to Ni-COF, which thus allows more active electrons available to participate in the subsequent reduction reactions. The photocatalytic results offer a chemical fuel generation rate of 2.29 mmol g-1 h-1 for H2 and 6.2 µmol g-1 h-1 for CO, ≈127 and three times higher than that of neat p-CN, respectively. This work provides new insights into the construction of a π-conjugated vdW heterostructure on promoting interfacial charge separation for high-efficiency photocatalysis.

π-Conjugated In-Plane Heterostructure Enables Long-Lived Shallow Trapping in Graphitic Carbon Nitride for Increased Photocatalytic Hydrogen Generation.

The relatively short-lived excited states, such as the nascent electron-hole pairs (excitons) and the shallow trapping states, in semiconductor-based photocatalysts produce an exceptionally high charge carrier recombination rate, dominating a low solar-to-fuel performance. Here, a π-conjugated in-plane heterostructure between graphitic carbon nitride (g-CN) and carbon rings (Crings ) (labeling g-CN/Crings ) is effectively synthesized from the thermolysis of melamine-citric acid aggregates via a microwave-assisted heating process. The g-CN/Crings in-plane heterostructure shows remarkably suppressed excited-state decay and increased charge carrier population in photocatalysis. Kinetics analysis from the femtosecond time-resolved transient absorption spectroscopy illustrates that the g-CN/Crings π-conjugated heterostructure produces slower exciton annihilation (τ1  = 7.9 ps) and longer shallow electron trapping (τ2  = 407.1 ps) than pristine g-CN (τ1  = 3.6 ps, τ2  = 264.1 ps) owing to Crings incorporation, both of which enable more photoinduced electrons to participate in the photocatalytic reactions, thereby realizing photoactivity enhancement. As a result, the photocatalytic activity exhibits an eightfold enhancement in visible-light-driven H2 generation. This work provides a viable route of constructing π-conjugated in-plane heterostructures to suppress the excited-state decay and improve the photocatalytic performance.

Negating Na‖Na3Zr2Si2PO12 interfacial resistance for dendrite-free and "Na-less" solid-state batteries.

Solid electrolytes hold promise in safely enabling high-energy metallic sodium (Na) anodes. However, the poor Na‖solid electrolyte interfacial contact can induce Na dendrite growth and limit Na utilization, plaguing the rate performance and energy density of current solid-state Na-metal batteries (SSSMBs). Herein, a simple and scalable Pb/C interlayer strategy is introduced to regulate the surface chemistry and improve Na wettability of Na3Zr2Si2PO12 (NZSP) solid electrolyte. The resulting NZSP exhibits a perfect Na wettability (0° contact angle) at a record-low temperature of 120 °C, a negligible room-temperature Na‖NZSP interfacial resistance of 1.5 Ω cm2, along with an ultralong cycle life of over 1800 h under 0.5 mA cm-2/0.5 mA h cm-2 symmetric cell cycling at 55 °C. Furthermore, we unprecedentedly demonstrate in situ fabrication of weight-controlled Na anodes and explore the effect of the negative/positive capacity (N/P) ratio on the cyclability of SSSMBs. Both solid-state Na3V2(PO4)3 and S full cells show superior electrochemical performance at an optimal N/P ratio of 40.0. The Pb/C interlayer modification demonstrates dual functions of stabilizing the anode interface and improving Na utilization, making it a general strategy for implementing Na metal anodes in practical SSSMBs.

Three-dimensional surface-enhanced Raman scattering substrates constructed by integrating template-assisted electrodeposition and post-growth of silver nanoparticles.

Three-dimensional (3D) plasmonic nano-arrays can provide high surface-enhanced Raman scattering (SERS) sensitivity, good spectral uniformity and excellent reproducibility. However, it is still a challenge to develop a simple and efficient method for fabrication of 3D plasmonic nano-arrays with high SERS performance. Here we report a facile approach to construct ordered arrays of silver (Ag) nanoparticles-assembled spherical micro-cavities using polystyrene (PS) sphere template-assisted electrodeposition and post-growth. The electrodeposited small Ag nanoparticles grow into bigger stable nanoparticles during the post-growth process, which could significantly improve the SERS sensitivity. The Ag nanoparticles-assembled 3D micro-cavity array provides much more hotspots in the excitation laser beam-covered volume than the two-dimensional counterpart. The relative standard deviation (RSD) of 612 cm-1 peak of rhodamine 6G (R6G) was calculated to be 8%, and the RSD of the characteristic peak taken from substrates of different batches was less than 10%. The detectable lower concentration as low as 1 fM was achieved for an aqueous solution of R6G. Such SERS substrate also showed high sensitivity to thiram (fungicide) and paraquat (herbicide) in water with limits of detection of 0.067 nM and 2.5 nM respectively. Furthermore, it also demonstrated that SERS detection of pesticide residues on fruits can be realized, showing a potential application in rapid monitoring food safety.

CdS Nanorods Anchored with Crystalline FeP Nanoparticles for Efficient Photocatalytic Formic Acid Dehydrogenation.

Photocatalytic dehydrogenation of formic acid is a promising strategy for H2 generation. In this work, we report the use of crystalline iron phosphide (FeP) nanoparticles as an efficient and robust cocatalyst on CdS nanorods (FeP@CdS) for highly efficient photocatalytic formic acid dehydrogenation. The optimal H2 evolution rate can reach ∼556 µmol·h-1 at pH 3.5, which is more than 37 times higher than that of bare CdS. Moreover, the photocatalyst demonstrates excellent stability; no significant decrease of the catalytic activity was observed during continuous testing for more than four days. The apparent quantum yield is ∼54% at 420 nm, which is among the highest values obtained using noble-metal-free photocatalysts for formic acid dehydrogenation. This work provides a novel strategy for designing highly efficient and economically viable photocatalysts for formic acid dehydrogenation.

Homogeneous Molecular Iron Catalysts for Direct Photocatalytic Conversion of Formic Acid to Syngas (CO+H2 ).

The catalytic decomposition of formic acid to generate syngas (a mixture of H2 and CO) is a highly valuable strategy for energy conversion. Syngas can be used directly in internal combustion engines or can be converted to liquid fuels, meeting future energy challenges in a sustainable manner. Herein, we report the use of homogeneous molecular iron catalysts combined with a CdS nanorods (NRs) semiconductor to construct a highly efficient photocatalytic system for direct conversion of formic acid to syngas at room temperature and atmospheric pressure. Under optimal conditions, the photocatalytic system presents an activity of 150 mmol gcatalyst -1 h-1 towards H2 , and an apparent quantum yield (AQY) of 16.8 %, making it among the most active noble-metal-free photocatalytic systems for H2 evolution from formic acid under visible light. Meanwhile, these iron-based molecular catalysts also demonstrate remarkable enhancement in CO evolution with robust stability. The mechanistic role of the molecular catalyst is further investigated by using cyclic voltammetry, which suggests the formation of FeI species as the key step in the catalytic conversion of formic acid to syngas.

Stabilizing black phosphorus nanosheets via edge-selective bonding of sacrificial C60 molecules.

Few-layer black phosphorus (BP) with an anisotropic two-dimensional (2D)-layered structure shows potential applications in photoelectric conversion and photocatalysis, but is easily oxidized under ambient condition preferentially at its edge sites. Improving the ambient stability of BP nanosheets has been fulfilled by chemical functionalization, however this functionalization is typically non-selective. Here we show that edge-selective functionalization of BP nanosheets by covalently bonding stable C60 molecules leads to its significant stability improvement. Owing to the high stability of the hydrophobic C60 molecule, C60 functions as a sacrificial shield and effectively protects BP nanosheets from oxidation under ambient condition. C60 bonding leads to a rapid photoinduced electron transfer from BP to C60, affording enhanced photoelectrochemical and photocatalytic activities. The selective passivation of the reactive edge sites of BP nanosheets by sacrificial C60 molecules paves the way toward ambient processing and applications of BP.

Highly Efficient and Stable Water-Oxidation Electrocatalysis with a Very Low Overpotential using FeNiP Substitutional-Solid-Solution Nanoplate Arrays.

The development of efficient water-oxidation electrocatalysts based on inexpensive and earth-abundant materials is significant to enable water splitting as a future renewable energy source. Herein, the synthesis of novel FeNiP solid-solution nanoplate (FeNiP-NP) arrays and their use as an active catalyst for high-performance water-oxidation catalysis are reported. The as-prepared FeNiP-NP catalyst on a 3D nickel foam substrate exhibits excellent electrochemical performance with a very low overpotential of only 180 mV to reach a current density of 10 mA cm-2 and an onset overpotential of 120 mV in 1.0 m KOH for the oxygen evolution reaction (OER). The slope of the Tafel plot is as low as 76.0 mV dec-1 . Furthermore, the long-term electrochemical stability of the FeNiP-NP electrode is investigated by cyclic voltammetry (CV) at 1.10-1.55 V versus reversible hydrogen electrode (RHE), demonstrating very stable performance with negligible loss in activity after 1000 CV cycles. This present FeNiP-NP solid solution is thought to represent the best OER catalytic activity among the non-noble metal catalysts reported so far.

Synergistic Effect of a Molecular Cocatalyst and a Heterojunction in a 1 D Semiconductor Photocatalyst for Robust and Highly Efficient Solar Hydrogen Production.

Photocatalytic production of hydrogen by water splitting is a promising pathway for the conversion of solar energy into chemical energy. However, the photocatalytic conversion efficiency is often limited by the sluggish transfer of the photogenerated charge carriers, charge recombination, and subsequent slow catalytic reactions. Herein, we report a highly active noble-metal-free photocatalytic system for hydrogen production in water. The system contains a water-soluble nickel complex as a molecular cocatalyst and zinc sulfide on 1D cadmium sulfide as the heterojunction photocatalyst. The complex can efficiently transport photogenerated electrons and holes over a heterojunction photocatalyst to hamper charge recombination, leading to highly improved catalytic efficiency and durability of a heterojunction photocatalyst- molecular cocatalyst system. The results show that under optimal conditions, the average apparent quantum yield was approximately 58.3 % after 7 h of irradiation with monochromatic 420 nm light. In contrast, the value is only 16.8 % if the molecular cocatalyst is absent. Such a remarkable performance in a molecular cocatalyst-based photocatalytic system without any noble metal loading has, to the best of our knowledge, not been reported to date.

Enhanced photocatalytic H2 production on CdS nanorods with simple molecular bidentate cobalt complexes as cocatalysts under visible light.

Photocatalytic hydrogen production via water splitting has attracted much attention for future clean energy application. Herein we report a noble-metal-free photocatalytic hydrogen production system containing a simple bidentate cobalt Schiff base complex as the molecular cocatalyst, CdS nanorods as the photosensitizer, and ascorbic acid as the electron donor. The system shows highly enhanced photocatalytic activity compared to pure CdS NRs under visible light (λ > 420 nm). Under optimal conditions, the turnover numbers (TONs) for hydrogen production reached ∼15 200 after 12 hours of irradiation, and an apparent quantum yield of ∼27% was achieved at 420 nm monochromatic light. Steady-state photoluminescence (PL) spectra indicated efficient charge transfer between the excited CdS NRs and the cobalt cocatalyst for improved hydrogen production. Spectroscopic studies of the photocatalytic reaction revealed the reduction of the Co(ii) complex to Co(i) species, which are probably active intermediates for hydrogen evolution. On the basis of the spectroscopic studies, we propose a reaction mechanism for hydrogen production in the present photocatalytic system.