Exploiting highly active noble-metal-free cocatalysts is pivotal for practical solar-to-hydrogen conversion via photocatalytic water splitting. Herein, a hierarchical nickel phosphide nanosheet array-graphene (Ni2P-GR) composite cocatalyst was fabricated by low-temperature phosphorization of a Ni(OH)2-GR precursor. Using eosin Y as the visible-light photosensitizer, Ni2P-GR exhibits exceptional H2-evolution activity with a rate of 20 035 & micro;mol g-1 h-1, significantly outperforming pristine Ni2P, the Ni(OH)2-GR precursor, and most reported noble-metal-free hybrid systems. Combined experimental and density functional theory studies reveal that Ni2P-GR achieves optimized hydrogen adsorption free energy (Delta G*), lowers the hydrogen evolution reaction kinetic barrier, and establishes a favorable intermediate adsorption-desorption equilibrium. Moreover, its hierarchical architecture maximizes active-site exposure, while graphene accelerates charge separation. These merits endow Ni2P-GR with outstanding activity and durability. This work provides a rational strategy for optimizing noble-metal-free cocatalyst composition and microstructure to boost photocatalytic H2 production.

Electrochemical water splitting for hydrogen production is an important path for the preparation of green hydrogen. However, the sluggish kinetics and high energy consumption of the anode oxygen evolution reaction (OER) have restricted its development. The hydrazine oxidation reaction (HzOR), with its low theoretical potential, fast kinetics, clean products, and the ability to simultaneously treat hydrazine-containing wastewater, has emerged as an ideal anode reaction to replace OER. Transition metal phosphides (TMPs) have shown noble-metal-like activity in HzOR catalysis due to their tunable d-band electronic structure, abundant active sites, high conductivity, and structural stability, making them highly promising non-noble metal catalysts. However, most existing reviews focus on the catalytic performance of TMPs in general hydrogen evolution reaction (HER)/OER systems or merely briefly mention HzOR as one of many anode reactions. Therefore, this review aims to comprehensively and systematically elaborate on the design strategies of TMPs catalysts for hydrazine-assisted electrolytic water splitting for hydrogen production and their applications in HzOR, deeply discuss the current progress, challenges, and future directions, and provide references for the development and industrial application of low-cost, high-efficiency, and high-stability hydrazine-assisted hydrogen production catalysts.

Efficient and durable oxygen evolution reaction electrocatalysts are essential for sustainable production of hydrogen via water electrolysis. Here, we present a lattice–interface synergy strategy to construct a heterostructured catalyst by electrodepositing ultrathin NiFe-LDH nanosheets onto Co, La codoped CeO₂ supported on copper foam. The hydrothermally synthesized Co,La-CeO₂ introduces controllable lattice strain and abundant oxygen vacancies, thereby enhancing conductivity and structural stability. The presence of robust interfacial interaction between NiFe-LDH and Co,La-CeO₂ promotes charge transfer and optimizes the adsorption of oxygen intermediates. Consequently, the NiFe-LDH/Co,La-CeO₂/CF electrode achieves an overpotential of only 230 mV at 50 mA cm⁻² with a Tafel slope of 74.65 mV dec⁻¹, and maintains 97.14% of its original current density after 50 h of continuous testing. This work underscores the importance of lattice doping and interface engineering in catalyst design and offers a general framework for developing high-performance non-precious-metal OER catalysts.

Electrocatalytic nitrate reduction reaction (NO3RR) offers a bright pathway for ammonia (NH3) production and protection of the environment. Most NO3RR catalysts still suffer from insufficient surface active hydrogen (Hads). In the research, a Cu/Co4N heterostructure is constructed in which the Cu acts as the adsorption for NO3 - while the Co4N enhances the water dissociation to supply Hads for the consecutive NO2 --to-NH3 pathway. Due to the synergistic effect, the Cu/Co4N heterostructure exhibits excellent performance for NO3RR in neutral electrolyte. At a potential of -0.6 V vs RHE (reversible hydrogen electrode), the Cu/Co4N heterostructure attained a Faradaic efficiency (FE) of 93% with an NH3 production of 27.64 mg h-1 cm-2. Benefiting from its outstanding NO3RR activity, a Zn-NO3 - battery employing the Cu/Co4N heterostructure as the cathode achieved a maximum power density of 10.1 mW cm-2. The study supplies valuable opinions in the tandem catalysis of heterostructure catalysts and offers an aspect for devising high-performance NO3RR catalysts, aiming to achieve effectual selectivity, sustainable NH3 yield, and environmental contamination control.

Regulating electronic structure via a uniform magnetic field effectively optimizes catalytic performance, yet rationally utilizing external magnetic fields to tune catalyst structure, promote small-molecule oxidation, and clarify mechanisms remains a key challenge. Here, a 0.7 T magnetic field was introduced during Fe-Ni2P@NF electrochemical activation to construct a Ni & horbar;O & horbar;Fe heterogeneous oxygen bridge, boosting urea oxidation (UOR) and hydrogen evolution (HER). In situ Raman revealed the magnetic field-induced Ni & horbar;O & horbar;Fe formation on 0 T and 0.7 T Fe-Ni2P@NF surfaces-this structure is more stable than NiOOH and functions as an electron transfer channel from Fe to Ni. Infrared spectroscopy revealed synergistic dual-site behavior: Ni sites enhance urea adsorption, while Fe sites in the Ni & horbar;O & horbar;Fe bridge stabilize *OH species; electron donation from Fe to Ni through the oxygen bridge promotes Ni-2(+) oxidation to higher-valent states (Ni-3(+)/Ni-4(+)), activating Ni centers for UOR. DFT calculations supported this electronic modulation mechanism-Fe-mediated electron transfer upshifts the Ni d-band center, strengthening urea adsorption and lowering the *NH & horbar;O ->*N & horbar;O rate-determining step barrier. Notably, at 100 mA cm(-)(2), 0.7 T-Fe-Ni2P@NF powers the HER//UOR electrolyze at only 1.54 V, outperforming water electrolyzes (1.62 V).

Constructing S-scheme heterojunctions preserves the intrinsic redox capabilities of both semiconductors while promoting the separation of photogenerated electrons and holes, making it a promising approach for enhancing the properties of semiconductors. In this study, an S-scheme Cd0.8Zn0.2S-CeO2 (CZS-CeO2) heterojunction was successfully fabricated via the in-situ growth of CZS nanowires on CeO2 nanocubes. The S-scheme charge-transfer mechanism of the CZS-CeO2 composites during photocatalytic reactions was confirmed through in-situ X-ray photoelectron spectroscopy and density functional theory calculations. These results demonstrate that the interfacial electric field (IEF) significantly facilitates charge separation and transport within the heterojunction. Consequently, the CZS-CeO2 composites exhibited excellent photocatalytic hydrogen production performance under simulated sunlight irradiation, surpassing that of blank CZS. Particularly, the optimal photocatalytic hydrogen generation rate for CZS-15%CeO2 reached 58 mmolg-1h-1, approximately 8.8 times higher than that of blank CZS. After five consecutive cycles of testing, CZS-15%CeO2 retained a relatively high level of activity. This enhanced stability can be attributed to the fabrication of S-scheme heterojunctions, which effectively suppressed hole-induced photocorrosion of CZS. This investigation provides a beneficial reference for the rational design of S-scheme heterojunction photocatalysts for efficient and stable photocatalytic hydrogen production. Published by Elsevier B.V. All rights reserved.

Constructing efficient cocatalyst-supported semiconductors to promote charge separation has been recognized as a promising strategy for enhancing photocatalytic hydrogen evolution. Herein, we successfully synthesized a Cd0.8Zn0.2S-Co(OH)2 (CZS-Co(OH)2) composite by loading Co(OH)2 cocatalysts onto CZS nanowires via a lowtemperature reflux method. Photocatalytic activity tests demonstrate that the CZS-Co(OH)2 composite exhibits significantly improved photocatalytic properties in contrast to pristine CZS. Especially, CZS-10%Co(OH)2 (CZS10C) achieves the maximum hydrogen generation rate upon simulated sunlight illumination, reaching 18.44 mmol g- 1 h- 1, approximately 3.8 times that of the original CZS. Subsequent cyclic experiments further reveal that the photocatalytic activity of CZS10C remains nearly unchanged after five consecutive cycles. Moreover, a series of characterization results confirm that CZS10C exhibits elevated separation efficiency of photogenerated electron-hole pairs and increased active area. This research proposes a viable strategy for utilizing earth-abundant cocatalysts in metal sulfide-based photocatalytic systems, offering a reference for the construction of low-cost and efficient photocatalytic materials.

Nitric oxide (NO)-based gas therapy represents an emerging strategy for cancer treatment, which, however, still suffers from insufficient intracellular NO production for compromised therapeutic efficiency due to limited endogenous hydrogen peroxide (H2O2) concentration and relatively slow NO generation rate. The use of metal-organic framework (MOF) with highly ordered porous structure and functional adjustability to design a multienzyme-like nanozyme provides a simple yet reliable approach for efficient and sustainable NO generation. Herein, a MOF-based nanozyme with multienzyme-like properties is constructed by depositing ultrasmall gold nanoparticles (Au NPs) and subsequently loading a NO donor, l-arginine (l-Arg) on an iron porphyrin integrated MOF, which enables efficient and sustainable NO generation for synergistic tumor therapy. Two notable merits of this design are (i) incorporation of Au NPs with glucose oxidase (GOx)-like property for effectively depleting intratumoral glucose, and simultaneously generating large amounts of H2O2, which is further utilized to initiate the effective production of NO and reactive oxygen species (ROS) by taking advantage of the peroxidase (POD)/NO synthase (NOS)-like activities of iron porphyrin, and (ii) deposition of ultrasmall Au NPs on the MOF for remarkably improving the structural stability of nanocomposites to circumvent the low catalytic efficiency associated with serious aggregation. This nanozyme achieves a high tumor inhibitory rate of 87.3 % with negligible systemic effects in a 4T1-tumor-bearing mice model by integrating NO, and ROS generation and starvation therapy with synergistic efficiency. Such an ingenious integration of multienzyme-like nanozyme and MOF paves a new way for NO-based gas therapy.

In this work, MoS2/FeS2 nanocomposites were synthesized by a green and simple one-step hydrothermal method to improve the poor Fenton-like activity of MoS2. A series of characterization techniques demonstrated that the MoS2 and FeS2 were chemically and firmly bonded through the Mo-S-Fe bonding. Optimization experiments confirmed that MoS2/FeS2-7-12 h provided the best Fenton-active degradation of sulfamethazine (SMZ), with almost all of the SMZ being degraded within 5 min. Mechanistic studies and Density functional theory results indicated that FeS2 coordinated on the MoS2 surface of MoS2/FeS2-7-12 h can enhance the adsorption and activation for H2O2, with an enhanced Bader charge transfer of 0.44 e(-) and an improved H2O2 adsorption energy of -0.72 eV compared with MoS2 and FeS2. In addition, The formed Mo-S-Fe bonding during the synthesis process can accelerate the redox cycles of Mo(IV)/Mo(V) and Fe(III)/Fe(II), and thus achieving the efficient generation of center dot OH and center dot O-2(-). Cycling tests showed that MoS2/FeS2-7-12 h could still maintain relatively good degradation activity after five cycles, indicating its excellent recyclability. The satisfactory universality, recyclability and performance enabled MoS2/FeS2-7-12 h to serve as a promising candidate for H2O2 activation.

Flexible sensors exhibit transformative potential across diverse applications ranging from continuous health monitoring to advanced human-machine interaction. However, conventional unimodal sensors are limited in their ability to capture multidimensional signals in complex scenarios. To address this issue, this study synthesized a polymerizable deep eutectic solvent (pDES) from choline chloride (Chcl) and acrylic acid (AA). Subsequently, phytic acid (PA), hollow polyaniline microspheres (HPS), and graphene oxide (GO) were incorporated into the pDES, resulting in a composite eutectogel (PAAGH gel) via photoinitiated free radical polymerization. Benefiting from the synergistic effects of multiple hydrogen bonding interactions and a dual conductive network, the PAAGH gel exhibited excellent mechanical properties and electrical conductivity, with a tensile strength of up to 195 kPa, strain at break of 1768 %, conductivity of 0.8 × 10-2 S/m, and a self-healing efficiency of 94.5 % within 48 h. Notably, its extensive hydrogen bonding network provided robust adhesion to various substrates, including plastics, rubbers, and metals. Furthermore, the integration of the dual conductive network (HPS/GO) into the gels enabled a strain sensitivity of 9.7, a response time to pressure of 46 ms, a wide temperature monitoring range of 0-100 °C, along with long-term stability. Capitalizing on the exceptional sensing characteristics, the assembled sensor array exhibited strong capabilities in human health monitoring, hand motion recognition, and the spatial distribution of temperature and pressure signals. These features collectively open up promising applications for the sensor in areas such as electronic skin and intelligent prosthetics.

Nitrate (NO 3 ‒ ) pollution poses significant threats to water quality and global nitrogen cycles. Alkaline electrocatalytic NO 3 ‒ reduction reaction (NO 3 RR) emerges as an attractive route for enabling NO 3 ‒ removal and sustainable ammonia (NH 3 ) synthesis. However, it suffers from insufficient proton (H + ) supply in high pH conditions, restricting NO 3 ‒ -to-NH 3 activity. Herein, we propose a halogen-mediated H + feeding strategy to enhance the alkaline NO 3 RR performance. Our platform achieves near-100% NH 3 Faradaic efficiency (pH = 14) with a current density of 2 A cm –2 and enables an over 99% NO 3 – -to-NH 3 conversion efficiency. We also convert NO 3 ‒ to high-purity NH 4 Cl with near-unity efficiency, suggesting a practical approach to valorizing pollutants into valuable ammonia products. Theoretical simulations and in situ experiments reveal that Cl-coordination endows a shifted d -band center of Pd atoms to construct local H + -abundant environments, through arousing dangling O-H water dissociation and fast *H desorption, for *NO intermediate hydrogenation and finally effective NO 3 ‒ -to-NH 3 conversion.

Systematic and in-depth explorations of the effects of side-chain modulation on the molecular assembly, optoelectronic properties, and photocatalytic properties of supramolecular systems, as well as the kinetics of charge separation and migration in these systems, are rare. In this study, a novel supramolecular photocatalyst with an alkoxy side chain (S-EPDI) was successfully developed through subtle design of the short and linear alkoxyl side chains, affording a phenol degradation efficiency approximately four times that of the counterpart with an alkyl side chain (S-APDI). Notably, combined density functional theory (DFT) calculations, absorption spectroscopy, and other characterizations revealed that the perylene diimide (PDI) molecular units, through π-π stacking, formed a unique rotationally offset stacked supramolecular structure, exhibiting a significant dipole moment. This gave rise to the formation of a larger inherent electric field within S-EPDI compared to S-APDI. Moreover, the study quantitatively demonstrated that a stronger inherent electric field and lower rate of surface charge recombination facilitate efficient separation of the photogenerated carriers. Therefore, the side-chain molecular engineering method employed in this study offers an effective approach for modulating the kinetics of charge migration.

The first-generation semiconductor materials represented by silicon (Si) and germanium (Ge) still hold a dominant position in many fields, including micro-electromechanical systems (MEMS) and integrated circuits (ICs). The processing of these materials continues to attract significant research attention for improvements in quality and efficiency. This study proposes a novel hybrid laser-enhanced particle-laden electrochemical machining (LEPL-ECM) process, whereby pulsed laser irradiation is utilized to selectively and locally enhance the electrical conductivity of Ge at specific locations. A neutral electrolyte jet, containing abrasive diamond particles, is applied to the location on the wafer surface opposite the laser irradiation, facilitating a localized and enhanced electrochemical dissolution. The effect of micro-particle erosion effectively removes the generated oxides and potential passivation layers, ensuring continuous and efficient electrochemical reactions. Consequently, high-quality micro-dimples with an entrance diameter of about 380-800 μm, a depth of around 138-300 μm, and a quasi-mirror surface with the roughness (Sa) of as low as 59.8 nm can be achieved within 90 seconds. Furthermore, the effects of the applied voltage, laser power and processing time on the resulting dimple characteristics and surface quality are discussed, along with a detailed morphology characterization. Dense micro-pits, radial streamlined micro-grooves and a special transitional region have been observed on dimple center, sidewall and near the edge, respectively, and the formation mechanism have been analyzed. Finally, a simulation of the electrolyte jet induced fluid pressure and velocity as well as the particle trajectory and distributions within and surrounding the dimple structure was conducted, which reveals that the synergistic mechanism associated with the hybrid material removal process involves both electrochemical corrosion and abrasive erosion.

The construction and application of metal-organic cages with accessible internal cavities have witnessed rapid development, however, the precise synthesis of complex metal-organic capsules with multiple cavities and achievement of multi-guest encapsulation, and further in-depth comprehension of host-multi-guest recognition remain a great challenge. Just like building LEGO blocks, herein, we have constructed a series of high-order layered metal-organic architectures of generation n (n = 1/2/3/4 is also the number of cavities) by multi-component coordination-driven self-assembly using porphyrin-containing tetrapodal ligands (like plates), multiple parallel-podal ligands (like clamps) and metal ions (like nodes). Importantly, these high-order assembled structures possessed different numbers of rigid and separate cavities formed by overlapped porphyrin planes with specific gaps. The host-guest experiments and convincing characterization proved that these capsules G2-G4 could serve as host structures to achieve multi-guest recognition and unprecedentedly encapsulate up to four C60 molecules. More interestingly, these capsules revealed negative cooperation behavior in the process of multi-guest recognition, which provides a new platform to further study complicated host-multi-guest interaction in the field of supramolecular chemistry. Complex metal-organic capsules with large cavities (1-4 pockets) have been prepared and used as host structures for multi-guest recognition, displaying intriguing negative cooperation behavior within separate rigid cavities in the binding of C60.

The exploitation of electrocatalysts with high activity and durability for HER is desirable for future energy systems, but it is still a challenge.NMPs have attracted increasing attentions, but the preparation process often needs toxic regents or dangerous reaction conditions. Herein, we develop a general green method to fabricate metal-rich NMPs anchored on NPG through pyrolyzing DNA cross-linked complexes. The obtained Ru 2 P-NPG exhibits an ultrasmall overpotential of 7 mV at 10 m A cm -2 and ultralow Tafel slope of 33 mV dec -1 in 1.0 mol L -1 KOH, even better than that of commercial Pt/C. In addition, Ru 2 P-NPG also shows low overpotentials of 29 and 78 mV in 0.5 mol L -1 H 2 SO 4 and 1.0 mol L -1 PBS, respectively. The superior activity can be attributed to the ultrafine dispersion of Ru 2 P nanoparticles for more accessible sites,more defects formed for abundant active sites, the two-dimensional plane structure for accelerated electron transfer and mass transport, as well as the regulation of electron distribution of the catalyst. Moreover, the synthetic method can also be applied to prepare other metal-rich noble metal phosphides（Pd 3 P-NPG and Rh 2 P-NPG）, which also exhibits high activity for HER. This work provides an effective strategy for designing NMP-based electrocatalysts.

Interface engineering is an effective strategy for the design of electrochemical catalysts with attractive performance for hydrogen evolution reaction. Herein, the Molybdenum carbide/molybdenum phosphide (Mo2C/MoP) heterostructure deposited on nitrogen (N), phosphorous (P) co-doped carbon substrate (Mo2C/MoP-NPC) is fabricated by one-step carbonization. The electronic structure of Mo2C/MoP-NPC is changed by optimizing the ratio of phytic acid and aniline. The calculation and experimental results also show that there is an electron interaction on the Mo2C/MoP interface, which optimizes the adsorption free energy of hydrogen (H) and improves the performance of hydrogen evolution reaction. Mo2C/MoP-NPC exhibits significant low overpotentials at 10 mA.cm(-2) current density, 90 mV in 1 M KOH and 110 mV in 0.5 M H2SO4, respectively. In addition, it shows superior stability over a broad pH range. This research provides an effective method for the construction of novel heterogeneous electrocatalysts and is conducive to the development of green energy.

The exploitation of electrocatalysts with high activity and durability for the hydrogen evolution reaction is significant but also challenging for future energy systems. Transition metal phosphides (TMPs) have attracted a lot of attention due to their effective activity for the hydrogen evolution reaction, but the complicated preparation of metal phosphides remains a bottleneck. In this study, a green fabrication method is designed and proposed to construct N, P co-doped graphene (NPG)-supported cobalt phosphide (Co2P) nanoparticles by using DNA as both N and P sources. Thanks to the synergistic effect of NPG and Co2P, the Co2P/NPG shows effective activity with a small overpotential of 144 mV and a low Tafel slope of 72 mV dec−1 for the hydrogen evolution reaction. This study describes a successful green synthesis strategy for the preparation of high-performance TMPs.

碱性电解水具有操作易实现、设备费用低和寿命长的特点,是目前应用最广泛的将可再生资源转化为氢能的技术.但电解水存在能耗高的问题,因此需要高效催化剂提高能量转化效率.钌具有与铂相近的金属-氢键强度,是极具前景的制氢催化剂.综述了近年来钌基催化剂的制备及其碱性电解水制氢反应的最新研究进展.与廉价过渡金属材料相比,钌基催化剂具有优异的电化学活性和稳定性,是一种很有前景的析氢材料.以目前主要研究的钌金属及其合金、钌基磷化物、钌基硫化物、钌基硒化物为代表,分别进行了简要的介绍和评价,最后提出了钌基电催化剂在制氢应用中存在的问题和未来的发展方向.

The unique structure and property of K+-modified graphitic carbon nitride (K-CN) nanosheets would be beneficial for developing advanced epoxy nanocomposites. However, the compatibility between K-CN nanosheets and epoxy matrix is a big challenge. In this study, we demonstrate a new and effective method to improve the compatibility of K-CN nanosheets and epoxy by using 1-(oxiran-2-ylmethyl)-1H-indole (IN) as surface modifier through the cation-p interaction between K+ on the surface of K-CN nanosheets and indole group of IN. In addition, the covalent bond between epoxy group of IN and amino group of curing agent could be used to participate in the formation of the epoxy network. When the content of K-CN nanosheets is 0.5 wt%, the tensile strength of prepared epoxy nanocomposites increases by 60.7% and extensibility of prepared epoxy nanocomposites increases by 53.4% compared to neat epoxy resin. In addition, the prepared epoxy nanocomposites are used as efficient reusable photocatalysts for degradation of methylene blue (MB). The efficiency of MB degradation is 98% within 60 min. This work opens up a new avenue to fabricate high-performance epoxy nanocomposites with multifunctional properties for advanced engineering applications.