Photocatalytic molecular oxygen (O2) activation provides a sustainable approach to produce singlet oxygen (1O2) for organic contaminants detoxification. However, the charge carriers-involved pathway usually suffers from unsatisfactory 1O2 production efficiency owing to energy loss caused by photogenerated hole-mediated superoxide species () oxidation. If the photoinduced species could be directly extracted onto photocatalysts surface rather than completely separated into electron and holes, traditional built-in electric field-triggering charge-carriers extraction process might be circumvented, promoting the electroneutral excitons-mediated 1O2 production. Herein, we demonstrate that introducing sulfate ions on bismuth oxybromide surface ([SO4]-BiOBr) using a facile photoetching-coordination strategy can regulate its steric hindrance and surface excitonic states. Benefiting from the energy gradient from the bulk to surface excitonic states, [SO4]-BiOBr exhibits extremely high-efficiency bulk exciton extraction performance. Different from the counterparts favoring the O2 chemisorption via a side-on mode, [SO4]-BiOBr with larger steric hindrance preferentially transfers the energy of long-lived excitons to physically absorbed O2, resulting in the photocatalytically generated reactive oxygen species (ROS) switching from to 1O2 and thereby boosting the dechlorination and degradation of 4-chlorophenol (4-CP). This study reveals the pivotal effect of surface modification on regulating the excitonic processes of semiconductors for efficient 1O2 photosynthesis and subsequent wastewater purification. (sic)(sic)(sic)(sic)(sic)(sic)(O2)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(1O2)(sic)(sic).(sic)(sic),(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic))(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic),(sic)(sic)(sic)1O2(sic)(sic)(sic)(sic).(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)-(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic),(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic),(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)1O2(sic)(sic).(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)-(sic)(sic)(sic)(sic),(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(BiOBr)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)([SO4]-BiOBr),(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic).(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic),[SO4]-BiOBr(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic).(sic)(sic)(sic)(sic)(sic)(sic)(sic)BiOBr(sic)(sic)"side-on"(sic)(sic)(sic)(sic)(sic)(sic)(sic)O2(sic)(sic),(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)[SO4]-BiOBr(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)O2,(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)& centerdot;O2 -(sic)(sic)(sic)1O2,(sic)(sic)(sic)(sic)(sic)(sic)4-(sic)(sic)(sic)(4-CP)(sic)(sic)(sic)(sic)(sic)(sic)(sic).(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic),(sic)(sic)(sic)1O2(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic).

Scalable synthesis of ductile nanoscale metals is pivotal for modern industry, strongly depending on energy-intensive manufacturing processes and extensive use of chemical agents along with pronounced carbon fingerprints. Herein, we introduce a mechanochemical three-dimensional dynamic shearing approach that reduces the mean particle size of conventional ductile metals (Al, Fe, Cu, and Zn) from tens of micrometers to below 500 nm. Central to this approach is the use of silicic acid (H2SiO3), which, with its moderate Mohs hardness and irregular, sharp structure, exerts intense vertical local shear forces on compressed metal sheets, thereby overcoming the spatial limitations of quasi-two-dimensional uniform mechanical surface load and effectively fragmenting ductile metals into nanoparticles. Simultaneously, H2SiO3 can form a protective silica gel layer for in situ stabilization of the nanoparticles. As a proof-of-concept, we establish large-scale production of nanoscale Fe with over 70% Fe0 content at a low cost of $3730 per ton, offering excellent storage stability and enhanced heavy metal removal performances for environmental remediation. Life cycle assessments reveal that this dynamic shearing approach reduces environmental impacts by 70%–88% and decreases carbon emissions by 62%–78% compared to conventional liquid or gas-phase reduction methods, advancing sustainable manufacturing practices in the realm of nanotechnology.

The electrochemical upgrading of methanol to formate is constrained by CO poisoning from *CHO intermediate dehydrogenation, hindering its industrial application. Herein, we report that engineering atomically polarized Ptδ+-Ptδ- dipoles on Ti felt achieves a formate Faradaic efficiency of 99% at +0.9 V vs. RHE, which is better than that of commercial Pt/C (62%). Moreover, a formate production rate of 945 mmol gPt-1 h-1 is achieved with stable performance for more than 5 days at 100 mA cm-2. These dipoles comprise spatially adjacent electron-deficient Ptδ+ bonded to lattice O and electron-rich Ptδ- coordinated to unsaturated Ti atoms working synergistically. The Ptδ+ site dehydrogenates CH3OH to *CHO, which adsorbs across the dipole in a side-on Ptδ+-OHC-Ptδ- bridging configuration. Within this configuration, Ptδ- donates electrons via d→π* backdonation to the π* antibonding orbital of *CHO, steering its direct hydroxylation and generating electrostatic repulsion for rapid HCOOH desorption. This strategy reduces environmental impact by 88% and carbon emissions by 11% relative to conventional thermal routes, demonstrating the potential of dipole engineering for C1 electrochemistry.

The utilization of hydrazine (N2H4) as a liquid-phase carrier offers a promising approach for on-demand H2 production. However, its splitting is challenged by parasitic cleavage of the N-N bond, which generates ammonia byproducts and wastes energy. Here, we designed a single-atomic catalyst comprising Ru(IV) coordinated by four oxygen atoms on a Ti felt, achieving near-quantitative selectivity (99.9%) for N2 and H2 at an ultralow cell voltage of 35 mV with a current density of 100 mA cm-2, significantly outperforming conventional Ru-based catalysts with N2 selectivity below 66%. Mechanistic investigations reveal that O-coordination stabilizes the high-valent Ru(IV) in a low-spin d4 electronic state. This electronic state promotes a monodentate end-on adsorption configuration of N2H4, enhancing electron donation from the terminal adsorbed N2H4 while minimizing the Ru→N back-donation into the N-N σ* orbital. Consequently, N-N cleavage is effectively suppressed, promoting successive N-H bond cleavage for clean H2 release. Impressively, this catalyst enabled direct conversion of aerospace wastewater containing 1,780 ppm of N2H4 to pure H2 (99.99%) with a net-negative carbon footprint of -2.25 kg CO2/t, offering an innovative and sustainable approach for waste-to-energy in the environmental and energy fields.

Regulating the H2O2 activation pathway is a remarkable way for the adjustment of active oxygen species. Regarding the lack of the tunability of the reductive activation and oxidative activation of H2O2 over BiOCl, herein we first demonstrated the tensile-strained Cu doped (0 0 1) facets exposed BiOCl nanoplates should boost the OVs governed cooperative reductive and oxidative activation of H2O2. The tunability of the reductive activation and oxidative activation of H2O2 was mainly governed by its adjustable O and H adsorption modes and the regulation of photogenerated carriers transfer. The doped Cu in BiOCl rather than OVs as the adsorption center of H2O2 by O promoted its reductive activation to center dot OH, largely enhanced the center dot OH dominated degradation of sodium salicylic acid (SANa) to 6.0 times of that of BiOCl. On the contrary, the repair of partial OVs favored the adsorption of H2O2 by H-bond structure, which steered the oxidative activation of H2O2 to center dot O2- and 1O2 for degrading sodium pentachlorophenate (PCPNa) more efficiently. This work reveals a new way for adjusting the active oxygen species via the cooperative reductive activation and oxidative activation of H2O2 for selective degradation of aromatic compounds in water solution.

Electrochemical CO2 reduction to multicarbon (C2+) hydrocarbons offers a promising route for value-added fuels and chemical feedstocks, yet its selectivity is usually limited by the sluggish symmetric C-C coupling. Herein, we demonstrate the synthesis of phosphidated Cu-Ni-Cu triangular single-atom cones (Ni1PCu2) by decorating Cu nanowires with Ni single atoms and P. These Ni1PCu2 can deliver an impressive CO2-to-C2+ hydrocarbon (C2H4 43%, C2H6 48%) Faradaic efficiency of 91% under solar light at an ultralow bias of -0.3 VRHE, and a stable C2+ hydrocarbon production rate of 370 μmol h-1 cm-2 for 4 days at 100 mA cm-2, where the Cu nanowires harness solar light to generate plasmonic electrons for the CO2 activation and its subsequent conversion to *CO, while electronegative phosphidation induces the formation of Cu+ sites to well stabilize *CO across high coverages. Strategically positioned Ni single atoms generate and confine active hydrogen (•H) for efficient hydrogenation of adjacent Cu+-*CO into Cu+-*CHO. The resulting Cu+-*CHO displays a weakened C-O bond and enhanced C nucleophilicity, allowing for solar-powered asymmetric C-C coupling with neighboring *CO toward efficient and selective C2+ hydrocarbon synthesis.

Ambient activation of molecular oxygen (O2) into hydroxyl radicals (•OH) constitutes an elementary stage in green oxidation chemistry. However, conventional strategies that heavily rely on H2O2 represent great bottlenecks in sluggish O-O bond cleavage and poor •OH selectivity. Herein, we report an H2O2-independent O2 activation pathway for robust •OH formation, though a transient iron-peroxo intermediate (surface-bound Fe-•OOH) on zero-valent iron (ZVI). This critical Fe-•OOH intermediate is formed from the oxalic acid (OA)-mediated proton-coupled electron transfer (PCET) of O2, where OA, dual-functioning as electron acceptor and proton donor, can alter O2 adsorption on Fe sites from a bridging mode into an end-on one, facilitating its direct mono-hydrogenation into Fe-•OOH. The asymmetric Fe-•OOH then undergoes facile O-O bond heterolysis, generating •OH with a high yield rate of 155.3 µmol L⁻¹ h⁻¹ and selectivity of 85.6%. In a structure-activity relationship investigation, the surface-coordinated organic carboxylic acids with available α-hydrogen atoms are determined as ideal reagents to initiate PCET for Fe-•OOH formation. This work provides a proof-of-concept scenario for efficient H2O2-independent O2 activation and offers a sustainable alternative for green oxidation.

Nitroaromatic and halogenated compounds are typical persistent organic pollutants (POPs) with high toxicity, poor biodegradability, and long-distance mobility. Traditional advanced oxidation processes (AOPs) cannot accomplish efficient mineralization of POPs because their strong electron-withdrawing groups decrease the electron cloud density of the benzene ring or adjacent carbon atoms, thereby enhancing the structures' stability. Although advanced reduction processes (ARPs) can effectively weaken the stubborn bonds of POPs and lower the ring-opening barriers of aromatic structures and halogenated aliphatic carbon skeletons, the generated high-toxicity intermediates in comparison to parent POPs might bring greater environmental risk. In this regard, the reduction-oxidation coupling (ROC) process might synchronously utilize the dual advantages of AOPs and ARPs to degrade POPs. However, the inherent mechanism of ROC-mediated POPs' decontamination and detoxification is still not fully understood. This review introduces the inherent mechanisms of AOPs, ARPs, and ROC process, summarizes the evidence of reactive species generation, and demonstrates that the ROC process can effectively eliminate and mineralize POPs via a barrier-decreasing and toxicity-attenuating pathway. We also discuss the challenges and perspectives of the ROC process for POP elimination in aspects of fundamental research and industrial application. We believe that a critical understanding of the ROC process can offer new perspectives and guidelines for POP elimination.

Green methanol production via solar-driven redox cycles integrated with next-generation carbon capture represents a commercially compelling but financially underexplored pathway to hard-to-abate industrial decarbonization. Carbon-rich flue gas (FG) from industrial point sources is a readily available but underutilized feedstock for thermochemical co-production of syngas and value-added chemical intermediates when coupled with concentrated solar power (CSP)-driven redox systems. Using a techno-economic and financial risk assessment framework, this study evaluated a two-stage carbon capture–solar redox process capable of producing H₂ + CO-rich syngas at high selectivity and green methanol at commercially viable yields. Monte Carlo simulation was employed to select the optimal technology readiness level (TRL) transition pathway, and the effects of carbon credit pricing, renewable energy tariff volatility, capital expenditure (CAPEX) uncertainty, and feedstock-to-solar-input mass ratio were rigorously assessed. At an optimized solar-to-fuel efficiency threshold, a 10 wt% Fe-ZnO/Char redox-active sorbent-catalyst with a 2:1 feedstock-to-catalyst mass ratio delivered 65.3% methanol selectivity and 79.9 vol% H₂ + CO syngas concentration. The catalyst system improved CO₂ capture, syngas upgrading, and deoxygenation, with ZnO incorporation modifying surface acid-site distribution and promoting hydrogen transfer, dehydration, demethoxylation, and cracking. Apparent coke concentration decreased by approximately 29.3%, from 6.42% (Fe/Char) to 4.54% (Fe-ZnO/Char), confirming superior coke resistance. Price-risk hedging analysis employing Value-at-Risk (VaR) and real-options valuation demonstrates that this integrated system achieves investment readiness at carbon prices above USD 65/tonne CO₂, with an internal rate of return (IRR) exceeding 12% under base-case methanol price scenarios. Fe-ZnO/Char is established as a promising catalyst architecture for the long-term, financially robust transformation of industrial CO₂ into green methanol via solar redox integration.

In the operational diagnosis of air-source heat pumps,the conventional coefficient of performance has limitations in distinguishing environmental effects from equipment performance degradation because of its dependency on the operating conditions.To address this issue,this study proposes a performance consistency index based on the second law of thermodynamics.By normalizing the second law efficiency under actual operating conditions against its value under rated conditions,a diagnostic method is established for energy efficiency based on this index,with operational robustness and design benchmarking capabilities.The study demonstrates that the performance consistency index inherits the stability and comparability of second-law efficiency,effectively decoupling the effects of environmental parameter fluctuations and equipment performance degradation.It is independent of the operating conditions and accurately characterizes the equipment status.With a design benchmark based on performance consistency index PCI=1,the deviations between the actual performance and design objectives were quantified.Validation through operational diagnosis of four units confirmed that the performance consistency index successfully identified the degradations in partial-load energy efficiency and low-temperature performance.The performance consistency index provides a theoretical tool for the long-term energy efficiency monitoring of air-source heat pumps,enabling the precise identification of inefficient units through threshold settings and supporting scientific decision-making for equipment renewal in"coal-to-electricity"projects.

Water is not a passive solvent but an actively tunable participant in aqueous-phase redox processes, whose reactivity can be regulated by modulating its molecular states and dynamics. Here, we introduce a multi-scale water modulation strategy using a hydrophilic polysaccharide network to reorganize the aqueous environment and suppress the corrosion of nanoscale zero-valent iron (nZVI). At the molecular scale, the polysaccharides tune free water (FW) into bound and intermediate water (BW/IW), which together account for ∼45% of total water. This water-state redistribution elevates the reaction barrier for H2O-Fe(0) interactions from 8.2 eV (FW) to 10.5 eV (BW), and the observed reaction rate constant (kobs) shows a strong linear dependence on the BW+IW fraction (R2 ≈ 0.99). At the nanoscale, the network imposes hydrophilic confinement (mesh size ≈ 1.1 nm) that restricts water access to reactive Fe(0) sites, causing a rapid attenuation of early-stage reactions (<12 days). At the macroscale, the modulated water forms a viscoelastic matrix (G' > G″) that retains in situ-generated H2 microdomains, creating interfacial shielding that suppresses prolonged reactions (>12 days). By linking water's molecular organization to macroscopic redox behavior, this work provides a framework for using the water modulation to stabilize corrosion-sensitive nanoparticles.

Building heating decarbonization in cold climates depends on air-source heat pumps (ASHPs) delivering their nameplate seasonal performance, yet field audits keep recording a rated-vs-realized COP gap that is largest at the cold extreme. The gap is operational rather than material: hardware is sized correctly, but the control strategy is suboptimal. Commercial defrost control has been diagnosed almost exclusively through single-sided indicators of over-defrost — defrost frequency or the defrost-phase energy fraction — which are silent on the converse failure: a controller that fails to dispatch needed defrosts and runs with a frost-blocked coil. Using a 26-unit parallel field test of mass-produced enhanced vapor injection ASHPs in Mohe, China (ambient down to −42 °C), we expose a U-shape control-failure geometry that the single-sided view masks. We introduce a paired metric framework: Defrost Energy Burden (DEB), the fraction of electrical input consumed by the defrost phase, captures over-defrost; Frost Energy Burden (FEB), the shortfall of observed COP relative to each unit's frost-free laboratory baseline at the same ambient, captures under-defrost. The 124 Brand×T-RH bins partition into four quadrants (cutoffs 19.17% DEB/7.80% FEB), with median combined waste rising 9.8%→44.5%. The 28 frost-blocked bins span 11 brands and hide a median 12.8% COP shortfall invisible to DEB-only diagnostics. Five brands swing between branches across temperature zones in the same factory-new unit — most consistent with control-coupled rather than hardware drivers. The findings motivate a U-shape Strategy Robustness Test in extreme-cold certification protocols (e.g., GB/T 25127, EN 14511) probing both branches.

High-temperature creep resistance and microstructural stability are important issues for gradient Cu–Ni alloys considered for severe thermomechanical environments. Dual-gradient Cu–Ni alloys, characterized by coupled gradients in grain size and composition, are promising candidates for such applications, but remain vulnerable to microstructural degradation under combined thermal and mechanical loading. The high density of GBs renders the fine-grained region prone to GB sliding, thereby promoting strain localization and premature failure. A hybrid MC and MD approach is employed to investigate the role of GB segregation in high-temperature creep and deformation mechanisms of dual-gradient Cu–Ni alloys. The results show that spontaneous segregation of Zr atoms at GBs significantly reduces the average GB energy and induces a pronounced solute drag effect. By contrast, the model with gradient Zr segregation exhibits distinct creep kinetics, with the steady-state stress exponent distribution evolving into a broader two-stage regime. At low and intermediate stress levels, the pronounced solute drag effect retards GB migration, shifting the deformation mode from unaccommodated GB sliding to a constrained, slip-accommodated interfacial mechanism. This transition in deformation mechanism suppresses strain localization at GBs in the fine-grained region, thereby reducing creep deformation. The synergy between the dual-gradient structure and GB segregation contributes to improved creep resistance and high-temperature structural stability, providing atomistic insight into the design of creep-resistant gradient alloys.

Advanced oxidation processes (AOPs) have caught considerable attention in environmental remediation with reactive oxygen species (ROS) generation from dioxygen, water, or low-cost peroxidants. However, the reported non-selective ROS generation techniques cannot meet more stringent regulatory requirements due to low efficacy and toxic by-products generation. Therefore, the comprehensive influence of ROS generation on degradation efficiency and toxicity variation of environmental pollutants should be explored. This review deconstructs the generation of superoxide radicals, hydroxyl radicals, and singlet oxygen in different systems at the electronic level, clarifying the dependence of various ROS generation pathways to electronic structure, surface properties, and interfacial microenvironment of catalysts. Furthermore, we systematically refine the universal principles for targeted ROS generation by precisely regulating reactants activation and intermediate transformation through defects engineering, dimension downsizing, and surface functionalization. Several cases were presented to demonstrate the superiority of selective ROS generation for efficient purification of typical air and wastewater contaminants. The challenges and perspectives of selective ROS generation of AOPs in aspects of fundamental research and industrial application were also discussed. We believe that a crucial understanding of selective ROS generation in AOPs can offer new perspectives and guidelines to accomplish deep purification and detoxification of contaminants in air and wastewater.

Iron sulfides (FexSy), a key carrier of geochemical elements cycling, have attracted much attention in investigating their environmental chemical behaviors and pollutants transformation mechanisms due to the unique redox cycles of iron and sulfur species. However, the unclear interface reaction process‌, complex environmental factors, and multi-pollutants synergism ‌bring enormous challenges to reveal the roles of iron and sulfur species in environmental pollutants abatement. This review first introduces the classification, distribution regularities, and geochemical cycle mechanisms of FexSy in nature. Subsequently, we summary the reduction and oxidation behaviors of FexSy in activating environmental dioxygen, water molecules and common peroxides, mainly focusing on the electron transfer pathways along with elemental cycles of Fe and S, and generation of reactive species (i.e., reductive reactive species (RRSs) and reactive oxygen species (ROSs)). We noted that reactive species generation of specific FexSy phases under different redox conditions is co-determined by their crystal structure and defect chemistry. Then, we demonstrate that engineering reactive sites of FexSy enables to promote the decomposition and transformation of pollutants, including the removal of heave metal ions, RRSs or ROSs-involved pollutants removal, as well as the cooperation of RRSs and ROSs in a reductive and oxidative coupling (ROC) process for the degradation of refractory organic pollutants. We also discuss the challenges and perspectives of FexSy in the detoxification and decontamination of environmental pollutants in aspects of fundamental research and industrial application.

Chiral organic-inorganic metal halide semiconductors (MHSs) have emerged as promising materials for chiroptoelectronics, spintronics and ferroelectrics. However, commonly used chiral cations with nonconductive aliphatic and aromatic structures exhibit large energy gaps between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) relative to those of the inorganic frameworks. This energy mismatch between the chiral spacer and the inorganic sublattice creates a barrier that hinders charge-carrier transport, leading to inefficient out-of-plane charge mobility and strong quantum confinement effects. To address this challenge, we design and synthesize chiral n-type naphthalenediimide (NDI)-based cations, (R)-2-(7-ethyl-1,3,6,8-tetraoxo-3,6,7,8-tetrahydrobenzo[lmn][3,8]phenanthrolin-2(1H)-yl)propan-1-aminium ((R)-NDIEPA+). We successfully tune the LUMO level of (R)-NDIEPA+ to align with that of the inorganic sublattice, and the resulting chiral one-dimensional (1D) (R-NDIEPA)PbI3 MHS demonstrates a type II band alignment that facilitates charge separation, as evidenced by quenched photoluminescence and transient absorption dynamics indicative of ultrafast charge transfer across the organic-inorganic interface. As a result, these materials demonstrate an approximately 7-fold enhancement in electron mobility compared to the chiral 1D MHS incorporating nonconductive aromatic cations. (R-NDIEPA)PbI3 also exhibits a strong circular dichroism (CD) signal, confirming effective chirality transfer from the organic cation to the inorganic framework. These findings underscore the importance of leveraging the electronic properties of chiral organic cations while preserving strong chiroptical activity, highlighting the potential of (R-NDIEPA)PbI3 for chiroptoelectronic applications such as circularly polarized light photodetectors and other spintronic devices.

ABSTRACT The selective aqueous hydrogenation of 5‐hydroxymethylfurfural (HMF) to 2,5‐bis(hydroxymethyl)furan (BHMF) is pivotal for biomass valorization. While nanoscale zero‐valent iron (nZVI) offers a sustainable H 2 ‐free alternative, its efficiency is severely suppressed by a rigid interfacial water layer that impedes substrate access and drives non‐selective pathways. Herein, we surmount this limitation by engineering atomically dispersed Ni sites on nZVI to orchestrate a surface proton‐coupled electron transfer (PCET). Mechanistically, single Ni atoms in the electron‐deficient state (Ni δ+ ) function as “electron pumps”, establishing a direct longitudinal inner‐sphere channel for electron delivery towards the −CHO group of HMF. Concurrently, the Ni δ+ sites facilitate prompt proton release by weakening hydrogen binding on adjacent lattice oxygen. Ni δ+ ‐induced electronic modulation transforms proximal lattice Fe into strong Lewis acids to polarize bulk water, creating a continuous lateral proton shuttle to the adsorbed HMF. This orthogonal PCET system drastically boosts electron selectivity from 10.6% (pristine nZVI) to 81.6%, achieving >95% HMF conversion (20–150 mM) with >95% BHMF selectivity under ambient conditions, outperforming pristine nZVI (<10% conversion) by orders of magnitude. This work demonstrates that engineering interfacial PCET pathways can reverse classical solvent inhibition, opening a general route for efficient aqueous hydrogenation.

Photocatalytic O2 activation involving charge carriers offers a sustainable approach for wastewater decontamination. However, its efficiency is often hampered by insufficient charge separation and inadequate O-O bond activation. Herein, we demonstrate that constructing monatomic manganese and oxygen vacancy dual sites (Mn1-VO) on the BiOCl surface enables homolytic O2 dissociation into atomic reactive oxygen species (•O−). The strategically introduced Mn1 site facilitates robust exciton dissociation into charge carriers. Coupled with the adjacent VO, it switches the O2 adsorption configuration from an end-on to a side-on bridging mode, stretching the O-O bond from 1.22 Å to 3.04 Å and promoting its barrierless cleavage into •O−. In the photodegradation of nitrogen-containing heterocyclic aromatic contaminants (NHACs), •O− preferentially attacks the unsaturated alkene double bonds or C-N bonds within the heterocycles, leading to deconjugated oxidation and subsequent ring-opening mineralization. Remarkably, BiOCl with Mn1-VO dual sites exhibit superior photoactivity for degrading refractory NHACs with conjugated multi-membered rings, such as carbamazepine, sulfadimidine, sulfamethoxazole, and norfloxacin, outperforming counterparts with only Mn1 or VO sites. This work highlights the crucial role of metal-oxygen vacancy dual sites in modulating O2 activation for solar-driven wastewater purification.

Chemical recycling of brominated plastic waste necessitates the concurrent mitigation of hazardous brominated compounds and the preservation of valuable hydrocarbons, which remains unachievable with conventional thermochemical methods. Here, we report that such a dilemma has been resolved by a solar-driven method using a bifunctional material comprising nanoscale zerovalent iron (nZVI) dispersed on a HZSM-5 zeolite. Under sole light irradiation, the nZVI intensively absorbs photons and raises its temperature to trigger the photothermochemically partial cleavage of C-C/C-H bonds in polyolefins and polystyrene to produce condensable hydrocarbon fragments over HZSM-5, and immobilizes dissociated C-Br as a solid, stable FeBr2 phase with >90% debromination efficiency. We demonstrate the scalability of this process with a 0.5 m × 0.5 m solar-driven apparatus that achieves a rapid plastic processing rate of 1.93 gplastic cm-2·h-1. This solar-driven one-step strategy offers a sustainable path for decontaminating and valorizing real-world additive-laden plastic waste.