Energy & Environmental Science最新文献

The generation of free carriers through extrinsic doping is essential for transforming the electronic properties of organic semiconductors (OSCs). Doped OSCs play a crucial role in the successful operation of a wide range of electrical and optoelectronic devices, but challenges remain associated with dopant design, such as processability, stability and efficacy. Herein, we introduce a class of versatile p-type dopants based on metallocenium salts with the general formula ([M(C₁₀H_10−n)(X)_n]⁺[Y]⁻) that meet these requirements. Critical to this approach is the ability to independently tune the cation via the redox-active metal cation (M) and the functionality (X) on the cyclopentadiene ring, allowing control over the oxidation strength. Simultaneously, the ability to tune the counter-anion (Y) allows control over the doping efficacy and stability of the resultant doped OSC⁺ salt. In this study, we systematically investigate the effect of cation and anion structures on the doping of OSCs and elucidate structure–property relationships for dopant design. We unravel the doping mechanism and demonstrate that such dopants can be used to enhance the hole extraction yield by 45% at perovskite/OSC heterojunctions. Perovskite/OSC photoactive layers using metallocenium dopants show significantly increased tolerance to moisture induced degradation as compared to films using conventional LiTFSI based dopants. Finally, we showcase the use of our optimised ferrocenium dopant in n–i–p configuration perovskite solar cells, demonstrating LiTFSI-free and additive-free devices with impressive solar-light to electrical power conversion efficiencies reaching 25.30%.

Dual-deposition aqueous Zn||I₂ batteries, via reversible Zn plating/stripping and four-electron (4e⁻) iodine redox, represent promising high-energy systems. However, their practical application is hindered by low areal capacity and limited cycle life, stemming from severe shuttling, hydrolysis, the insulating nature of iodine species, and Zn corrosion. Here, we introduce a coordination-escorted organo-interhalogen conversion strategy employing choline cations (Ch⁺) and 2-acetbromamide (BrAce) as coregulators to address these challenges. Ch⁺ ions coordinate strongly with key intermediates (I₃⁻, I₂, and organo-interhalogen complexes), effectively suppressing the shuttle effect and stabilizing organo-interhalogen complexes. This coordination induces a smooth semiliquid iodine deposition/dissolution process during the 4e⁻ conversion, significantly improving electrical contact and redox kinetics. Simultaneously, the interface shielding effect of Ch⁺ effectively protects the deposited Zn anode. Markedly outperforming existing systems, this battery achieves a well-balanced capacity between the I⁻/I⁰ and I⁰/I⁺ steps, a threefold increase in iodine utilization (∼70%), and a tenfold longer cycle life (exceeding 12 000 cycles) at 20 mA cm⁻² under a practical areal capacity of 2.5 mAh cm⁻². A dual-deposition configuration also delivers 800 cycles with nearly 100% retention. This approach concurrently addresses critical issues in 4e⁻ iodine redox and Zn anode chemistry, offering a universal paradigm to explore other dual-deposition high-energy systems.

Achieving efficient photocatalytic carbon dioxide (CO₂) reduction is crucial for sustainable energy and carbon neutrality. However, a fundamental challenge resides in the rational design and fine-tuning of catalyst active sites. Here, we construct edge-rich nickel–aluminum layered double hydroxide (E_D-NiAl-LDH) nanoflakes with abundant lattice O defects for effective and selective solar-driven CO₂ conversion in a pure water system. The E_D-NiAl-LDH exhibits an excellent carbon monoxide (CO) production rate of 773.4 µmol g⁻¹ h⁻¹ with a high selectivity of 98.5%, surpassing that of state-of-the-art photocatalysts reported in recent years. Outdoor tests also demonstrate an impressive CO₂-to-CO photo-conversion rate of 500 µmol g⁻¹ h⁻¹, with stable activity over an 80-hour period. In situ characterization methods and theoretical calculations confirm that the edge-rich structure provides abundant unsaturated coordination-regulated high-spin Ni active sites. The high-spin Ni active sites possess half-filled degenerate e_g orbitals in the octahedral field, which significantly accelerates the migration of photogenerated electrons from Ni to CO₂ molecules while inhibiting other competitive reactions, thereby enabling the observed exceptional performance. This work establishes edge engineering as a general strategy to unlock high-spin catalytic centers in LDHs, advancing the design of efficient solar fuel systems.

The bottleneck of overall photosynthesis of hydrogen peroxide (H₂O₂) lies in the slow kinetic water oxidation half-reaction. This inefficiency arises from the principal species of the stable quadrilateral configuration in liquid water, which obstructs the effective extraction of hydrogen from water molecules necessary for the reduction of O₂ to H₂O₂. In this study, the incorporation of sulfonic acid groups into organic polymer photocatalysts induced the adsorption of smaller water clusters with a weak hydrogen bond, leading to enhanced kinetics of the photocatalytic water oxidation reaction. Notably, the introduction of various sulfonic acid groups significantly improved the photocatalytic H₂O₂ production under alkaline conditions (1 M NaOH) without the use of sacrificial reagents. The optimal sulfonated photocatalyst achieved a H₂O₂ production rate of 45.54 µmol h⁻¹, representing a 14-fold increase compared to the pristine one. Furthermore, the solar-to-chemical conversion (SCC) efficiency reached 0.04% in a real outdoor environment, surpassing all previously reported values. Thorough investigations into the underlying mechanisms demonstrated that the incorporation of sulfonate groups enhances the separation efficiency of photogenerated charge carriers. More importantly, this modification led to enhanced adsorption of small water clusters, which mitigated the competition posed by the water oxidation process and ultimately facilitated the extraction of hydrogen from water molecules for the photosynthetic production of H₂O₂.

The oxygen evolution reaction (OER) critically governs the efficiency of proton exchange membrane water electrolysis (PEMWE), yet its kinetics remain constrained by energy-scaling relationships. This work reports on an oxyanion-modification-induced hydrogen-bond-assisted adsorbate evolution mechanism that significantly boosts the performance of the acidic OER. Single-atom Zn and lattice S are designed as cation–anion pairs to co-stabilize the SO₄²⁻ groups. The optimized Zn₁/RuS_yO_2–x–SO₄ achieves a low overpotential of 158 mV at 10 mA cm⁻² and outstanding stability during a continuous 235-h test in a 0.5 M H₂SO₄ electrolyte. Operando spectroscopy and theoretical calculations reveal that SO₄²⁻ species significantly lower the energy barrier of the rate-determining step in the adsorbate evolution mechanism by forming hydrogen bonds with key *OOH intermediates, thereby circumventing the typical scaling limitations. Concurrently, the formation of hydrogen bonds and strong electronic interactions between the SO₄²⁻ groups and water molecules promote water adsorption and accumulation on the Zn₁/RuS_yO_2–x–SO₄ surface, further enhancing the reaction kinetics. Moreover, the incorporated SO₄²⁻ groups significantly impede lattice O loss and Ru dissolution, extending the durability of Zn₁/RuS_yO_2–x–SO₄ during acidic OERs. This study provides a novel cation–anion co-anchoring oxyanion strategy to overcome existing energy-scaling constraints, enabling a more efficient Ru-based catalyst for PEMWE application.

The solvation structure of electrolytes can decide the movement of ions and regulate interfacial chemistries in rechargeable batteries. A variety of novel solvation structures have been reported with the rapid evolution of electrolyte chemistry. This review provides a comprehensive summary of the working principles of novel solvations based on ion/dipole interactions in rechargeable batteries. First, the motivation, development, and design concepts of solvation structures are introduced. Then, the electrochemical reaction mechanisms and corresponding performance of new solvation structures are discussed in depth by systematically analyzing different ion/dipole interactions. Ion–dipole interactions can balance solvation effects to improve the reduction stability of solvents. Ion–ion interactions are promising for fast charge and constructing robust alloy interphases. Dipole–dipole interactions can further shrink cluster size and expand the temperature range of electrolytes. This enables customized solvation structures to meet different application scenarios, establishing a specific design paradigm. Finally, the current issues and possible future directions are highlighted, providing theoretical guidance for innovative designs of solvation chemistry.

The sustainable production of ammonia (NH₃) via the electrochemical nitrate reduction reaction (NO₃⁻RR) presents a dual solution for environmental remediation and renewable energy storage. However, this process is hindered by the sluggish kinetics of the sequential deoxygenation and hydrogenation steps, particularly under alkaline conditions, where proton scarcity exacerbates the competing hydrogen evolution reaction (HER). In this study, heterostructured Cu₃Mo₂O₉/Cu is purposely designed so that it can be reductively formed during the NO₃⁻RR to incorporate the advantages of dual-function active sites in the processes of water dissociation and nitrate reduction. Experimental and theoretical results indicate that the in situ generated Cu₃Mo₂O₉ is proposed to facilitate H₂O dissociation and likely contribute to proton (H⁺) supply, while metallic Cu enhances nitrate adsorption and facilitates subsequent deoxygenation. The Cu₃Mo₂O₉/Cu catalyst achieves an excellent NH₃ faradaic efficiency (FE) of 97.5% at −0.5 V vs. RHE with an NH₃ yield rate of 19.3 mg h⁻¹ mg_cat⁻¹ in 0.05 M KNO₃. This performance is among the highest under neutral/alkaline H-cell conditions. The Cu₃Mo₂O₉/Cu-based Zn–nitrate battery delivers a peak power density of 20.24 mW cm⁻² and maintains an FE_NH3 of 93.8% at 60 mA cm⁻². This study elucidates the dynamic synergy of heterostructured catalysts for multi-step reactions and establishes a general framework for coupling catalytic nitrate conversion with energy storage applications.

Hydrogen-based fuels are expected to support maritime shipping in reaching net-zero climate targets. However, the complexity of hydrogen-based fuel supply, propulsion system deployment, and fleet composition make their full life cycle decarbonization potential unclear. A comprehensive fleet-level assessment of their decarbonization potential is thus essential. Here, we evaluate the life cycle climate change impact of global container shipping using hydrogen-based fuels from 2020 to 2050, considering fuel mix, propulsion system, ship size and transport demand. By integrating energy scenarios from the International Energy Agency with socio-economic scenarios from the Shared Socioeconomic Pathways and the Organization for Economic Co-operation and Development, we explore three scenarios that represent different levels of ambition for the future hydrogen production transition, hydrogen-based fuel use, and corresponding transport demand: the Less Ambitious, Ambitious and Very Ambitious scenarios. Our findings indicate that container shipping's greenhouse gas (GHG) emissions per tonne-nautical mile could decrease from 22 g CO₂-eq in 2020 to 21 g, 9 g, and 3 g CO₂-eq by 2050 under the Less Ambitious, Ambitious, and Very Ambitious scenarios, respectively. Cumulative GHG emissions from global container shipping could reach 9–12 Gt, 7–10 Gt, and 4–5 Gt CO₂-eq between 2020 and 2050 across these scenarios, accounting for 1–3% of the global carbon budget required to achieve the worldwide net-zero target. The substitution of heavy fuel oil with hydrogen-based fuels does not always lead to a reduction in GHG emissions: in the Less Ambitious scenario, cumulative emissions increase by 0.4–0.6 Gt CO₂-eq due to the slow decarbonization in hydrogen production, whereas in the Ambitious and Very Ambitious scenarios, they decline by 1–2 Gt and 3–5 Gt CO₂-eq, respectively. Deep decarbonization of maritime shipping requires overcoming key bottlenecks in renovating the fleet, scaling up ammonia production and electrolyzer capacity, and ensuring sufficient renewable electricity supply. This highlights the need for coherent policies to foster multi-sectoral coordination among maritime shipping, hydrogen-based fuel production, and power generation to maximize their decarbonizing potential.

Inefficiencies in the slurry mixing stage are a major factor in high scrap rates in battery manufacturing, thus hindering sustainable production. Current offline characterisation techniques for slurry microstructure and rheology are slow and inadequate for closed-loop quality control or process optimisation. This review evaluates ultrasound as a promising inline, non-invasive characterisation tool to address this crucial need. We critically examine decades of developments and applications in ultrasonic evaluation techniques, assessing their relevance and identifying challenges specific to the high-concentration, non-Newtonian battery slurries. Key wave-slurry interaction mechanisms, including attenuation, wave speed, scattering, and guided wave propagation, are discussed in the context of characterising microstructural features (e.g. particle dispersion and agglomeration) and macroscopic rheological properties (e.g. viscosity and viscoelasticity). To make full use of the crucial yet limited information accessible via ultrasound, we propose a hybrid framework marrying ultrasonic and other offline data through physics-informed machine learning for accurate and comprehensive property estimation. With the analyses and framework, this review points to a clear path towards achieving robust inline monitoring and efficient optimisation of battery slurry mixing.