Carbon Energy最新文献

Lithium-sulfur (Li-S) batteries are promising for high-energy-density storage, but their performance is limited by sluggish lithium polysulfide (LiPS) conversion kinetics. Here, we tackle this issue by synthesizing ultrafine truncated octahedral TiO₂ nanocrystals (P-O_v-TiO₂), featuring specific {101} facets and dual defects—phosphorus doping and oxygen vacancies. Acting as an efficient electrocatalyst in the separator, P-O_v-TiO₂ exhibits superior catalytic properties, where oxygen vacancies modulate the electronic structure, enhancing electron enrichment and charge transfer; phosphorus doping tailors the d-band center of the catalyst, strengthening Ti-S interactions between the {101} facets and LiPSs. As a result, Li-S coin cells modified with P-O_v-TiO₂ achieve a high specific capacity of 895 mAh g⁻¹ at 5 C and exhibit a minimal decay rate of 0.14% per cycle over 200 cycles. Furthermore, Li-S pouch cells deliver a high capacity of 1004 mAh g⁻¹ at 0.1 C under lean electrolyte conditions. This study elucidates the mechanisms of charge states on specific crystal planes and deepens our understanding of dual-defect engineering in Li-S electrochemistry, offering a promising approach for developing efficient and cost-effective catalysts for Li-S battery applications.

Functionalization has emerged as a pivotal endeavor to tailor the surface properties of photocatalysts. We propose a facile amine functionalization strategy to establish a Cu−In−Zn−S (CIZS)/NiS_x hybrid with covalent bonds using individual ethylenediamine (EDA) molecules. Our approach witnesses a remarkable photocatalytic hydrogen evolution (PHE) competence of 65.93 mmol g⁻¹ h⁻¹ driven by visible light, the highest value yielded by CIZS to date. X-ray absorption spectra of CIZS and density functional theory (DFT) calculations confirm the crucial amine N→Cu coordination after amine functionalization. The new emerging coordination via lone-pair electron donation profitably accesses the regulation of the coordination environment, electronic structures, and carrier behavior. Moreover, individual EDA molecule with two-terminal −NH₂ group serves as a molecular bridge to hybrid CIZS and NiS_x cocatalyst via N→Cu and N→Ni coordination, favorably promoting efficient charge transport. This study provides advances in practical functionalizing photocatalysts.

Developing electrocatalysts to inhibit polysulfide shuttling and expedite sulfur species conversion is vital for the evolution of Lithium-sulfur (Li-S) batteries. This work provides a facile strategy to design an intimate heterostructure of MIL-88A@CdS as a sulfur electrocatalyst combining high sulfur adsorption and accelerated polysulfide conversion. The MIL-88A can give a region of high-ordered polysulfide adsorption, whereas the CdS is an effective nanoreactor for the sulfur reduction reaction (SRR). Notedly, the significant size difference between MIL-88A and CdS enables the unique heterostructure interactions. The large-size MIL-88A ensures a uniform distribution of CdS nanoparticles as a substrate. This configuration facilitates control of the initial polysulfide adsorption position relative to its final deposition site as lithium sulfide. The heterostructure also demonstrates rapid transport and efficient conversion of lithium polysulfides. Consequently, the Li-S battery with MIL-88A@CdS heterostructure modified separator delivers exceptional performance, achieving an areal capacity exceeding 6 mAh cm⁻², an excellent rate capability of 980 mAh g⁻¹ at 5 C, and notable cycling stability in a 2 Ah pouch cell over 100 cycles. This work is significant for elucidating the relationship between heterostructure and electrocatalytic performance, providing great insights for material design aimed at highly efficient future electrocatalysts in practical applications.

Photoreforming of formic acid (FA) represents a compelling technology for green hydrogen (H₂) production, but the application is limited by the relatively low activity and selectivity. Recent advancements have introduced transition-metal nitrides (TMNs) as a new class of co-catalysts for photocatalytic FA reforming, showing impressive performance but still having the disadvantage of suboptimal H₂ selectivity. Here, we present a novel Cu–W₂N₃ cocatalyst with abundant Cu single-atom sites. On combining with a CdS photocatalyst, the CdS/Cu–W₂N₃ system demonstrated an elevated H₂ generation rate of 172.69 μmol·h⁻¹ and superior H₂ selectivity in comparison to CdS/W₂N₃. Comprehensive experimental and theoretical investigations indicate that the introduction of Cu single-atom sites in Cu–W₂N₃ leads to a robust interaction with CdS, which optimizes the charge transfer. More significantly, the Cu single-atom sites modify the inert surface of the W₂N₃ cocatalyst, creating conducive electron transfer channels and leading to an abundance of active sites favorable for hydrogen evolution reaction (HER), consequently resulting in higher H₂ selectivity than pristine W₂N₃. This study provides a promising approach to achieving an efficient photoreforming reaction with specific selectivity via the design of novel cocatalysts with specialized active sites.

Demand for fast-charging lithium-ion batteries (LIBs) has escalated incredibly in the past few years. A conventional method to improve the performance is to chemically partly substitute the transition metal with another to increase its conductivity. In this study, we have chosen to investigate the lithium diffusion in doped anatase (TiO₂) anodes for high-rate LIBs. Substitutional doping of TiO₂ with the pentavalent Nb has previously been shown to increase the high-rate performances of this anode material dramatically. Despite the conventional belief, we explicitly show that Nb is mobile and diffusing at room temperature, and different diffusion mechanisms are discussed. Diffusing Nb in TiO₂ has staggering implications concerning most chemically substituted LIBs and their performance. While the only mobile ion is typically asserted to be Li, this study clearly shows that the transition metals are also diffusing, together with the Li. This implies that a method that can hinder the diffusion of transition metals will increase the performance of our current LIBs even further.

Photothermal catalysis utilizing the full solar spectrum to convert CO₂ and H₂O into valuable products holds promise for sustainable energy solutions. However, a major challenge remains in enhancing the photothermal conversion efficiency and carrier mobility of semiconductors like Bi₂MoO₆, which restricts their catalytic performance. Here, we developed a facile strategy to synthesize vertically grown Bi₂MoO₆ (BMO) nanosheets that mimic a bionic butterfly wing scale structure on a biomass-derived carbon framework (BCF). BCF/BMO exhibits high catalytic activity, achieving a CO yield of 165 μmol/(g·h), which is an increase of eight times compared to pristine BMO. The wing scale structured BCF/BMO minimizes sunlight reflection and increases the photothermal conversion temperature. BCF consists of crystalline carbon (sp²-C region) dispersed within amorphous carbon (sp³-C hybridized regions), where the crystalline carbon forms “nano-islands”. The N–C–O–Bi covalent bonds at the S-scheme heterojunction interface of BCF/BMO function as electron bridges, connecting the sp²-C nano-islands and enhancing the multilevel built-in electric field and directional trans-interface transport of carriers. As evidenced by DFT calculation, the rich pyridinic-N on the carbon nano-island can establish strong electron coupling with CO₂, thereby accelerating the cleavage of *COOH and facilitating the formation of CO. Biomass waste-derived carbon nano-islands represent advanced amorphous/crystalline phase materials and offer a simple and low-cost strategy to facilitate carrier migration. This study provides deep insights into carrier migration in photocatalysis and offers guidance for designing efficient heterojunctions inspired by biological systems.

Hard carbon is the most commercially viable anode material for sodium-ion batteries (SIBs), and yet, its practical implementation remains constrained by insufficient low-voltage plateau capacity, a critical parameter governing storage capacity. This study introduces a targeted component removal and chemical etching strategy to precisely tailor the porous structure of hard carbon and thus remarkably enhance the plateau capacity. In this strategy, alkaline-dissolved components are removed to form a closed-pore core with tunable size. Subsequently, the in situ occupied alkaline engineers the pore structure through chemical etching. The optimized hard carbon material not only has short-range disordered graphite domains to facilitate Na⁺ ions' intercalation and deintercalation but also has abundant micropores and closed-pore structures with appropriate pore sizes and an ultrathin carbon layer (1−3 layers) to significantly increase the sodium storage sites. The resulting hard carbon delivers a high reversible specific capacity of 389.6 mAh g⁻¹ with a low-voltage plateau capacity as high as up to 261.5 mAh g⁻¹ and an initial Coulombic efficiency of 90.7%. Crucially, this cost-effective methodology shows broad precursor adaptability across lignocellulosic biomass, establishing a universal paradigm for designing high-performance carbonaceous anodes for SIBs.

Back cover image: Regulating the freedom and distribution of H₂O molecules is crucial for enlarging the electrochemical window of aqueous electrolytes. Hao and Qiu et al. fabricated a heterogel electrolyte by utilizing the bicontinuous microemulsion as template. In this image, the brown pipelike passage represents the interpenetrating oil phase, while the green “tadpole-shaped” objects are actually the surfactant Tween 20. The hydrophobic tail of the surfactant tends to orderly assemble at the electrode surface and enrich the oil phase to create a hydrophobic interfacial microenvironment, thus preventing the proximity of H₂O molecules, resulting in an expanded electrochemical window. Article number: 10.1002/cey2.697

Front cover image: Heterointerfaces are promising candidates for anode materials of aqueous rocking-chair Zn-ion batteries. However, it suffers from interfacial problems between solvation sheath and desolvation processes of solvated Zn²⁺, and in article number 10.1002/cey2.691, Peng Cai, Kangli Wang, and Kai Jiang, et al. firstly propose that the built-in electric field (BEF) effects at the heterointerfaces can promote the desolvation processes of solvated zinc ions, inhibiting the hydrogen evolution reactions (HERs), and improving the cycling stabilities in the deep discharge states.

Cd-based Cs₇Cd₃Br₁₃ perovskites, featuring both tetrahedral and octahedral polyhedral structures, have garnered significant acclaim for their efficient luminescent performance achieved through multi-exciton state regulation by doping. However, it remains controversial whether the doping sites are in the octahedra or tetrahedra of Cs₇Cd₃Br₁₃. To address this, we introduced Pb²⁺ and Sb³⁺ ions and, supported by experimental and theoretical evidence, demonstrated that these ions preferentially occupy the octahedra. Among them, Pb²⁺ ions single doping achieves a near-unity photoluminescence quantum yield of 93.7%, which results in excellent X-ray scintillation performance, high light yield of 41,772 photon MeV⁻¹, and a low detection limit of 29.78 nGy_air s^–1. Moreover, this incorporation of Pb²⁺ and Sb³⁺ enabled an exciton state regulation strategy, resulting in standard white light emission with CIE chromaticity coordinates of (0.33, 0.33). Additionally, a multifaceted optical anticounterfeiting and information encryption scheme was designed based on the differences in optical properties caused by the different sensitivities of [PbBr₆]⁴⁻ octahedron and [SbBr₆]³⁻ octahedron to temperature and excitation wavelengths. These diverse photoluminescence characteristics provide new insights and practical demonstrations for advanced X-ray imaging, lighting, optical encryption, and anticounterfeiting technologies.