Conventional catalytic ammonia decomposition is inherently limited by competitive adsorption constraints, as reactant activation and product recombination compete for the identical active metal sites, necessitating high operating temperatures. Herein, we report a spatial site-differentiation strategy to circumvent this constraint by engineering Y-N-Y motifs within a Y2O3 support. This targeted nitridation preserves the sub-nanometer dispersion of an ultralow-loading (0.1 wt%) ruthenium phase. Combined spectroscopic and density functional theory analyses reveal that nitrogen substitution modulates the electron density of adjacent yttrium atoms, creating localized Lewis acid centers. This electronic restructuring shifts the primary ammonia binding locus from the metallic ruthenium to the modified support, yielding an adsorption energy of -3.05 eV. Under non-thermal plasma excitation, this dual-site architecture physically uncouples the reaction pathway: the nitrided support selectively anchors and activates ammonia, liberating the adjacent ruthenium clusters strictly for rapid hydrogen recombination. Consequently, the catalyst achieves >90% ammonia conversion at a measured bed temperature of 400 °C. This surface-engineering approach provides a practical framework for overcoming competitive adsorbate crowding, offering a highly viable strategy for the design of advanced plasma-catalytic systems for energy conversion.

Cocatalyst structure during photodeposition is shaped not only by precursor chemistry but also by the semiconductor surface properties. However, the role of dopant-induced band edge shifts in governing cocatalyst nucleation remains elusive. In Al-doped SrTiO3, Al-substitution upshifts the surface conduction band minimum by similar to 0.43 eV, placing O2-driven reoxidation and Rh3+ reduction in direct kinetic competition, a condition absent in undoped SrTiO3. Consequently, photodeposition under ambient conditions stabilizes Rh in a mixed-valence Rh0/Rh3+ state, yielding ultrafine nanoparticles that anchor CrO x into a well-defined Rh@RhCrO x core-shell structure. In contrast, under evacuated conditions, Rh3+ reduction proceeds more completely, forming aggregated metallic Rh0 particles with poor interfacial contact. Time-resolved photoluminescence measurements confirm that the core-shell catalyst exhibits a dominant monoexponential decay with a lifetime of 1.26 ns, signifying suppressed trap-mediated carrier loss, whereas the sample prepared under evacuated conditions shows a multicomponent decay with a prominent slow component attributable to trap-mediated relaxation. The core-shell catalyst achieves H2 and O2 evolution rates of 2.98 and 1.47 mmol & centerdot;g-1 & centerdot;h-1, approximately 2-fold higher than those of the sample prepared under evacuated conditions, with an apparent quantum efficiency of 77.9% at 365 nm. These results demonstrate that dopant-controlled band tuning determines the atmosphere sensitivity of cocatalyst nucleation, providing a practical strategy to tailor the oxidation state and interfacial structure of cocatalysts for highly efficient photocatalytic water splitting.

Carbon capture technologies generally face the challenge of high energy consumption, which stems from the need to overcome strong chemical bond energy during the regeneration of CO2 adsorbents. Electrochemical carbon capture technology achieves adsorption/desorption cycles through potential regulation and theoretically has the potential to couple with renewable energy electricity and significantly reduce net energy consumption. Carbon capture technologies generally face the challenge of high energy consumption, which stems from the need to overcome strong chemical bond energy during the regeneration of CO2 adsorbents. Electrochemical carbon capture technology achieves adsorption/desorption cycles through potential regulation and theoretically has the potential to couple with renewable energy electricity and significantly reduce net energy consumption. Under this context, this Review systematically summarized recent progress in electrochemical capture, CO2 reduction, and their integrated systems. Initially, it elucidated the reduction pathways of captured carbon species and highlighted their mechanistic differences from free CO2 reduction. Furthermore, the microenvironment regulation strategies at the reaction interface are discussed, including pulsed-potential reconstruction, cation/anion effects, and interfacial water design, aiming to reconcile the incompatibility between capture and conversion. Besides, the catalyst design strategies were also analyzed to conclude the possible mechanism of the high-value multicarbon production. Critically, to address the highly corrosive of amine-rich media, it highlighted the co-design of both the catalytic interface and the capture media. Finally, this review evaluated the long-term system stability, mapping the degradation mechanisms of capture media, membranes, and catalysts, and envisioned macroscopic system-level optimizations, aiming to provide a decisive path toward industrial decarbonization.

Facet-engineered semiconductor single crystals hold considerable promise for applications ranging from solar fuels to photovoltaics. However, solid-state syntheses, though operationally simpler, typically fail at facet control due to limited atomic mobility, whereas solution/flux-based methods rely heavily on additives. Herein, we report a straightforward, self-directing solid-state ion doping strategy for synthesizing well-defined cuboidal rhodiumdoped SrTiO3 (SrTiO3:Rh) single-crystalline particles with predominant (1 0 0)/(0 1 0) facet exposure. This strategy is based on the identification of a previously unrecognized dual role of ionic Rh precursors as intrinsic structure-directing agents and visible-light sensitizers, facilitating concurrent crystal growth, facet stabilization and controlled doping incorporation during a single calcination step. Compared to Rh2O3-derived SrTiO3:Rh, a milestone photocatalyst historically suffered from poor facet control, these cuboidal crystals with anisotropic electronic surface structures exhibited enhanced crystallinity, superior charge separation efficiency and accelerated surface reaction kinetics, resulting in an order-of-magnitude improvement in visible-light-driven hydrogen evolution. Notably, when integrated into a liquid-phase Z-scheme system with BiVO4 and Fe3+/Fe2+ redox mediators, the SrTiO3:Rh single crystals exhibited a remarkable apparent quantum yield of 3.2 % at 420 nm for overall water splitting. This facile, self-directing synthetic approach addresses key challenges in traditional solid-state routes, providing valuable guidance for rational facet and doping engineering in diverse functional semiconductors for energy conversion.

Microwave-assisted catalysis is a promising technique for the efficient degradation of volatile organic compounds, but its practical application is limited by the challenge of designing catalysts that possess both superior catalytic activity and exceptional microwave absorption capabilities. In this study, a series of cobalt oxide (Co3O4)/carbon nanotube (CNT) composite catalysts with varying CNT contents were synthesized to investigate their microwave-catalytic performance. Quantitative analysis revealed that the introduction of CNTs significantly enhanced the dielectric loss of the composites primarily through conduction loss and interfacial polarization from the conductive network, complementing the intrinsic magnetic loss of Co3O4. The composite containing 10 wt% CNT (Co3O4/CNT-10) exhibited the best microwave absorption, with a minimum reflection loss of-40 dB. This sample achieved an optimal balance between efficient microwave energy conversion and catalytic performance, reaching nearly 100 % benzene removal under microwave irradiation. However, excessive CNT loading led to thermal decomposition and catalyst deactivation due to overpowering heating. This work clarifies that while utilizing conductive loss is a highly effective pathway for enhancing a catalyst's microwave response, the success of the design ultimately depends on balancing the powerful absorption capability with the material's intrinsic thermal stability.

The Cu2O-based photocathode has been widely applied in photoelectrocatalytic hydrogen evolution and carbon dioxide reduction systems. However, the poor stability of Cu2O caused by photocorrosion highly restricts the application. In this work, a multilayer configuration is designed as Cu2O/ZnO/SnO2 via sequential depositions of electrodeposition and spin-coating. The liquid-phase epitaxial growths of the Cu2O and ZnO layers are achieved by sequential electrodepositions on a FTO/Au substrate. The decoration of a uniform SnO2 layer onto Cu2O/ZnO is realized by a SnO2 QDs coating and provides dual functions for boosted electron transfer and surface reaction. The protection of the SnO2 layer is fulfilled by the inhibition of Cu+ transformation, resulted from the compact covering of SnO2 QDs onto the exposed surface of the Cu2O and ZnO layers. Consequently, the enhanced photocurrent density and improved stability are obtained for Cu2O/ZnO/SnO2 compared to bare Cu2O and Cu2O/ZnO sample photocathodes. The necessary role of SnO2 QDs serving as electron transfer and protection layers studied in this work reveals the remarkable potential in the modification of other vulnerable electrode materials.

The development of efficient and stable visible-light-driven Z-scheme systems for overall water splitting was crucial for solar hydrogen production. However, performance was often limited by photocorrosion of sulfide-based hydrogen evolution photocatalysts and competing, deactivating side reactions involving the redox shuttle. Herein, we construct a robust Z-scheme system by employing a CoP-modified Ni-doped Zn0.5Cd0.5S heterojunction with strong interfacial interaction as the HEP, coupled with BiVO4 as the oxygen evolution photocatalyst. The optimized system exhibited an apparent quantum yield of 4.06% at 420 nm and enabled sustained co-evolution of hydrogen and oxygen at a near-stoichiometric ratio. It also demonstrated outstanding cycling stability. Crucially, it had been demonstrated that the regulation of the internal polarizability of HEP effectively suppressed the competitive reduction of the redox medium and the formation of passivated Prussian blue derivatives on the catalyst surface. This work provides fundamental insights into mitigating the side effects caused by fusion through polarizability regulation.

Solid solution strategy could improve the photocatalytic performance thermodynamically, yet the study focusing on the carrier dynamics of the solid solution catalysts was equally important. Herein, a series of ZnxCd1-xS solid solutions were successfully synthesized based on band structure regulation, and the carrier dynamics were investigated by femtosecond transient absorption spectroscopy (TAS) and DFT, which unveiled a variation of the mixed direct-to-indirect bandgap transition mechanism in ZnxCd1-xS solid solution. The indirect bandgap exhibited a lower photocarrier recombination rate and, more importantly, could also serve as a trapping center for photocarrier, thus promoting the efficiency of charge separation. Consequently, ZnxCd1-xS solid solutions achieved an approximately eleven-fold enhancement in the hydrogen evolution rate (1426.66 mu mol h(-1)) relative to that of bare CdS (129.83 mu mol h(-1)) under visible light (>420 nm). This work proposed that the enhanced photocatalytic performance could originate from both thermodynamic and kinetic aspects simultaneously, and that the alteration of the photocarrier transition mechanism is one of the main factors affecting the kinetics.

Although the "Solar Fuels" represented a highly promising strategy for establishing a circular carbon economy, however, the photocatalytic, photoelectrocatalytic, and even photovoltaic-electrocatalytic technologies are inherently constrained by the efficiency and intermittency of solar irradiation energy, limiting their operation to daylight hours when solar energy is insufficient. In response to this challenge, this Perspective proposed a novel concept of integrated CO2 capture and artificial photosynthesis, which aims to enable efficient solar fuel production through the temporal and spatial integration of carbon capture technologies with solar energy conversion processes, simultaneously decreasing the energy consumption of the carbon capture during the CO2 release period. Furthermore, the challenges, as well as opportunities, associated with the development of such coupled systems, were also summarized, further to foster a more synergistic relationship between academia and industry to accelerate commercial viability.

The oxygen evolution reaction represents the primary kinetic bottleneck in photoelectrochemical water splitting and typically necessitates an external bias. The fundamental impact of charge accumulation induced by applied overpotential remains insufficiently understood. This work identified that the excess accumulation of surface-positive charges on BiVO4 photoanodes acts as a detrimental kinetic barrier that impedes water oxidation. The construction of a NiO-BiVO4 p-n junction could facilitate electron migration toward the photoanode surface to effectively neutralize excess positive charge and modulate the polarizability of V-O bonds. In situ Raman spectra reveal the formation of high-valent Ni4+ species within NiOOH+ stabilized the V-O bond polarizability. Consequently, the photoanode achieved a photocurrent density of 6.48 mA cm-2 at 1.23 VRHE. This work revealed that rational regulation of interfacial charge density via p-n junction engineering was critical for stabilizing key bond polarizabilities, providing a general strategy to overcome kinetic limitations in solar energy conversion.

In this context, a Al2O3 doped SrTiO3 (Al:SrTiO3) was synthesized via the molten salt method. The spatial separation active sites of the hydrogen evolution and the CO2 reduction in photocatalysis were revealed by using absorbed H2 as a probe, which indicated that CoOOH could be the photocatalytic CO2 reduction active site while RhCrOx could serve as the main site for hydrogen species activation and generation. The photocatalytic CO2 reduction could be determined by the spatial-temporal transfer of active hydrogen species coupled with carriers, from the interface of RhCrOx-Al:SrTiO3 to CoOOH-Al:SrTiO3 probably. More importantly, the competitive relationship between liquid water molecules, active hydrogen species, and CO2 was proved, indicating that the water film may hinder the spatial-scale migration of active hydrogen species and CO2 absorption. This work explored photocatalytic CO2 reduction from overall water splitting systems and emphasized the importance of the spatial shielding effect of interfacial water molecules.

Particulate photocatalytic systems using nanoscale photocatalysts have been developed as an attractive promising route for solar energy utilization to achieve resource sustainability and environmental harmony. Dynamic obstacles are considered as the dominant inhibition for attaining satisfactory energy-conversion efficiency. The complexity in light absorption and carrier transfer behaviors has remained to be further clearly illuminated. It is challenging to trace the fast evolution of charge carriers involved in transfer migration and interfacial reactions within a micro–nano-single-particle photocatalyst, which requires spatiotemporal high resolution. In this review, comprehensive dynamic descriptions including irradiation field, carrier separation and transfer, and interfacial reaction processes have been elucidated and discussed. The corresponding mechanisms for revealing dynamic behaviors have been explained. In addition, numerical simulation and modeling methods have been illustrated for the description of the irradiation field. Experimental measurements and spatiotemporal characterizations have been clarified for the reflection of carrier behavior and probing detection of interfacial reactions. The representative applications have been introduced according to the reported advanced research works, and the relationships between mechanistic conclusions from variable spatiotemporal measurements and photocatalytic performance results in the specific photocatalytic reactions have been concluded. This review provides a collective perspective for the full understanding and thorough evaluation of the primary dynamic processes, which would be inspired for the improvement in designing solar-driven energy-conversion systems based on nanoscale particulate photocatalysts.

Photocatalytic CO2 reduction technology offers a promising pathway for the resource utilization of CO2. Copper (I)-based cocatalysts have been attracting significant attention due to their exceptional CO2 activation capability and ability to suppress the hydrogen evolution reaction. In this study, we employ a solid-phase sulfidation method to in-situ anchor Cu2S nanoclusters on Ti3+-enriched TiO2 nanorods, constructing an intimately coupled Cu2S/TiO2 heterostructure. The loading of Cu2S significantly enhances both the CO2 reduction activity and CH4 selectivity of TiO2. The optimized 1 % Cu2S/TiO2 photocatalyst achieves CO and CH4 production rates of 6.71 mu mol g- 1 h- 1 and 1.20 mu mol g- 1 h- 1, representing 1.41-fold and 5.71-fold improvements over pristine TiO2, respectively. Density Functional Theory (DFT) calculations reveal that the Schottky junction between metallic Cu2S and TiO2 provided a strong driving force for photogenerated charge redistribution, promoting charge separation efficiency. In-situ Diffuse Reflectance Infrared Fourier Transform (DRIFT) spectroscopy and CO2 Temperature-Programmed Desorption (CO2-TPD) results demonstrate that Cu2S loading strengthened C--O bond activation, making CO2 reduction more favorable. More importantly, combined in-situ DRIFTS and DFT calculations indicate that Cu2S not only reduces the energy barrier for *COOH formation (0.39 eV vs.0.16 eV) but also dramatically decrease the hydrogenation barrier for *CHO (0.83 eV vs. 0.17 eV), thereby establishing a more energetically favorable pathway for CH4 generation and achieving simultaneous improvements in both activity and selectivity. This study not only develops an efficient photocatalytic CO2 reduction photocatalyst, but also provides crucial theoretical insights into the mechanistic regulation of activity and selectivity in CO2 reduction processes.

Rapid, nonequilibrium heating drives mesoscale structural evolution in heterogeneous composite materials under extreme thermal conditions, critically influencing performance in aerospace propulsion and advanced structural applications. However, existing experimental techniques lack the capability to directly observe heterogeneous structural evolution and intercomponent interactions under controlled conditions that closely mimic realistic nonequilibrium thermal fronts. Consequently, theoretical models, which assume equilibrium conditions or neglect dynamic structural evolution, remain insufficiently validated and cannot accurately predict these critical transformation pathways. Here, we developed a gradiated fast-heating system (>20 °C/s) enabling precise control of heating rate gradients within submillimeter transition regions in a single specimen, seamlessly integrated with sequential synchrotron X-ray tomography and radiography to directly visualize internal structural evolution. This approach allowed capture of diverse structural transformation pathways spanning microsecond-to-millisecond timescales under distinct nonequilibrium thermal conditions, revealing the complete sequence from initial pyrolysis through ignition to final burnout. We found that local heating rates, rather than bulk temperatures, dictate void formation dynamics and fragmentation pathways. In regions with high local heating rates, rapid void nucleation within the binder phase created reticulated porous networks, evolving four times faster than curved interfacial voids observed in adjacent regions experiencing lower heating rates. Furthermore, a cascade of heterogeneous component interactions subsequently fragmented the metallic network into isolated clusters, seeding critical ignition hotspots that governed combustion initiation and propagation mechanisms. These findings indicate that kinetic processes, influenced notably by heating rate, play an important role in mesostructural evolution under nonequilibrium conditions.

The study focuses on improving the removal efficiency of submicron particles using negative air ions (NAIs), which are challenging to remove. To enhance this efficiency, cascaded carbon fiber tubular (CFT) chargers were designed to boost particle charging. Through experiments and numerical simulations, the chargers' enhancement mechanisms, cooperation effects, and overall performance were evaluated. The optimal configuration for the CFT charger was identified as a gap distance (d =2.0 r(0))and grounded electrode length (L0/ =4 pi r(0)/3)that ensures high collection efficiency (96.7 % for 0.5 mu m particles at 4 m/s) and ultra-low ozone generation (7.25 ppb). The study found that while the average electric field strength (E) and ion density significantly influence charging, an un-usual improvement in collection efficiency was observed the charger with d =2.0 r(0) at u =3 m/s, likely due to the potential predominance of the maximum electric field strength (Emax) at relative higher velocity. Besides, the CFT charger demonstrated balanced performance compared to other reported works, although higher relative humidity (80 +/- 5 % RH) inhibits removal efficiency, which can be mitigated by reducing gas velocity.

Crystal facet-dependent photogenerated charge separation and surface reactions are crucial for efficient photoelectrochemical (PEC) water splitting. However, the kinetic mismatch between photogenerated hole transfer and the water oxidation reaction (WOR) can impede the PEC performance of photoanodes. Herein, uniform octadecahedral BiVO4 (O-BiVO4) single crystal photoanodes with exposed {040}, {011}, and high-reactivity {121} facets are synthesized to reveal the significance of synchronizing photogenerated hole transfer with WOR activity. The results show that the photogenerated holes preferentially accumulate on the {121} facets with excellent WOR activity. Consequently, the O-BiVO4 photoanode exhibits an impressive photocurrent density of 2.05mA/cm2 at 1.23V versus the reversible hydrogen electrode (VRHE), which is 4.4 times higher than that of decahedral BiVO4 surrounded by {040} and {011} facets. Furthermore, the PEC performance of O-BiVO4 outperforms most state-of-the-art unmodified BiVO4, attributed to the well-matched kinetic process between photogenerated holes transfer and the WOR. After loading NiFeOOH as an oxygen evolution cocatalyst, a stable photocurrent density of 4.63mA/cm2 at 1.23 VRHE is achieved. This work offers valuable insight into the relationship between semiconductor photoanode performance and the crystal facets, guiding the rational design of high-reactivity crystal facets for efficient solar energy conversion.

CO 2 emissions and increased concentration will be harmful to the environment. Electrochemical carbon capture, including flue gas carbon capture, ship exhaust carbon capture, and direct air carbon capture, provides a promising alternative method for thermochemical techniques due to its remarkable characteristic of low energy consumption. This review aims to summarize the recent progress via electrochemical carbon dioxide capture, including the thermodynamics and kinetics, inorganic and organic capture systems, and direct air carbon capture. Especially, recent progress on the related key materials of electrochemical carbon capture, including redox-active absorbents, Amine-based absorbents, Ion-selective membrane materials, Inorganic molten salt as media materials, and Electrode materials, is summarized. It is anticipated that this review will stimulate scholarly interest in the electrochemical capture of CO 2 and provide valuable insights for future research works concentrated on the coupling CO 2 capture and in situ conversion into solar fuels, which will not only further decrease the energy consumption, but also broaden the research area of photo(electro)catalysis, photovoltaic electrocatalysis.

N-type sulfide semiconductors are promising photocatalysts due to their broad visible-light absorption, facile synthesis and chemical diversity. However, photocorrosion and limited electron transport in one-step excitation and solid-state Z-scheme systems hinder efficient overall water splitting. Liquid-phase Z-schemes offer a viable alternative, but sluggish mediator kinetics and interfacial side reactions impede their construction. Here we report a stable Z-scheme system integrating n-type CdS and BiVO₄ with a [Fe(CN)₆]³⁻/[Fe(CN)₆]⁴⁻ mediator, achieving 10.2% apparent quantum yield at 450 nm with stoichiometric H₂/O₂ evolution. High activity reflects synergies between Pt@CrOx and Co3O4 cocatalysts on CdS, and cobalt-directed facet asymmetry in BiVO₄, resulting in matched kinetics for hydrogen and oxygen evolution in a reversible mediator solution. Stability is dramatically improved through coating CdS and BiVO4 with different oxides to inhibit Fe4[Fe(CN)6]3 precipitation and deactivation by a hitherto unrecognized mechanism. Separate hydrogen and oxygen production is also demonstrated in a two-compartment reactor under visible light and ambient conditions. This work unlocks the long-sought potential of n-type sulfides for efficient, durable and safe solar-driven hydrogen production.

The intrinsic driving force of semiconductor-based photocatalysts for separation and transfer of photoexcited charge carriers is still insufficient kinetically. The establishment and enhancement of an internal electric field within single particles are effective approaches to accelerate carrier migration with the introduction of symmetric breaking. In our work, a facet-selective doping strategy is proposed as the synergetic combination of the asymmetric facet effect and doping effect on truncated {100} and {110} SrTiO3 single nanoparticles as the model, which is realized via facet-selective photodeposition and facet-domain doping methods. For {100} facets, Rh doping with aliovalent Rh3+ substituted for Ti4+ after Rh valence regulation leads to p-type transformation compared to pristine n-type {110} facets without doping, resulting in the opposite shift of the surface band bending direction within the space charge region. Due to facet-selective p-type transformation, surface electric fields contributed by anisotropic band bendings are aligned between the doped p-type {100} facet with downward bending and the undoped n-type {110} facet with upward bending. Therefore, the directional migration of electrons to {100} facets is boosted by the intensified facet-oriented electric field and the photocatalytic performance is improved (2-fold) for hydrogen evolution with similar to 1.75% AQY at 400 nm consequently.

Effective charge separation and transfer at the semiconductor-cocatalyst interface are essential for efficient photoelectrochemical (PEC) water splitting. However, identifying an appropriate interlayer to promote interfacial charge transfer remains a substantial challenge. Herein, a hole transport layer (HTL) composed of NiFe layered double hydroxide (NiFe-LDH) was introduced onto a nanoporous BiVO4 photoanode to suppress interfacial charge recombination. Spectroscopic analyses reveal that the incorporation of the NiFe-LDH HTL facilitates the formation of a favorable energy band alignment, enabling efficient extraction of photogenerated holes from BiVO4 and significantly reducing both interfacial and bulk recombination losses. The subsequent deposition of Co3Ge2O5(OH)(4) as the oxygen evolution catalyst (OEC) further enhances the charge transfer kinetics and surface oxygen evolution reaction (OER) activity, as verified by photoelectrochemical experiments and theoretical calculations. Consequently, the BiVO4/NiFe-LDH/Co3Ge2O5(OH)(4) photoanode achieves a photocurrent density of 5.15 mA/cm(2) at 1.23 V versus the reversible hydrogen electrode (V-RHE), along with excellent operational stability. Additionally, charge separation and injection efficiencies of 92.6% and 87.2% are achieved at 1.23 V-RHE, respectively. These findings underscore the critical role of the HTL in tailoring interfacial energetics to advance efficient solar water oxidation.