RESUMEN

Phase engineering is an effective strategy for modulating the electronic structure and electron transfer mobility of cobalt selenide (CoSe2) with remarkable sodium storage. Nevertheless, it remains challenging to improve fast-charging and cycling performance. Herein, a heterointerface coupling induces phase transformation from cubic CoSe2 to orthorhombic CoSe2 accompanied by the formation of MoSe2 to construct a CoSe2/MoSe2 heterostructure decorated with N-doped carbon layer on a 3D graphene foam (CoSe2/MoSe2@NC/GF). The incorporated Mo cations in the bridged o-CoSe2/MoSe2 not only act an electron donor to regulate charge-spin configurations with more active electronic states but also trigger the upshift of d/p band centers and a decreased ∆d-p band center gap, which greatly enhances ion adsorption capability and lowers the ion diffusion barrier. As expected, the CoSe2/MoSe2@NC/GF anode demonstrates a high-rate capability of 447 mAh g-1 at 2 A g-1 and an excellent cyclability of 298 mAh g-1 at 1 A g-1 over 1000 cycles. The work deepens the understanding of the elaborate construction of heterostructured electrodes for high-performance SIBs.

RESUMEN

The pursuit of anode materials capable of rapid and reversible potassium storage performance is a challenging yet fascinating target. Herein, a heterointerface engineering strategy is proposed to prepare a novel superstructure composed of amorphous/crystalline Re2Te5 anchored on MXene substrate (A/C-Re2Te5/MXene) as an advanced anode for potassium-ion batteries (KIBs). The A/C-Re2Te5/MXene anode exhibits outstanding reversible capacity (350.4 mAh g-1 after 200 cycles at 0.2 A g-1), excellent rate capability (162.5 mAh g-1 at 20 A g-1), remarkable long-term cycling capability (186.1 mAh g-1 at 5 A g-1 over 5000 cycles), and reliable operation in flexible full KIBs, outperforming state-of-the-art metal chalcogenides-based devices. Experimental and theoretical investigations attribute this high performance to the synergistic effect of the A/C-Re2Te5 with a built-in electric field and the elastic MXene, enabling improved pseudocapacitive contribution, accelerated charge transfer behavior, and high K+ ion adsorption/diffusion ability. Meanwhile, a combination of intercalation and conversion reactions mechanism is observed within A/C-Re2Te5/MXene. This work offers a new approach for developing metal tellurides- and MXene-based anodes for achieving stable cyclability and fast-charging KIBs.

RESUMEN

Visible-light responsive, stable, and abundant absorbers are required for the rapid integration of green, clean, and renewable technologies in a circular economy. Photoactive solid-solid heterojunctions enable multiple charge pathways, inhibiting recombination through efficient charge transfer across the interface. This study spotlights the physico-chemical synergy between titanium dioxide (TiO2) anatase and carbon nitride (CN) to form a hybrid material. The CN(10%)-TiO2(90%) hybrid outperforms TiO2 and CN references and literature homologs in four photo and photoelectrocatalytic reactions. CN-TiO2 achieved a four-fold increase in benzylamine conversion, with photooxidation conversion rates of 51, 97, and 100 % at 625, 535, and 465 nm, respectively. The associated energy transfer mechanism was elucidated. In photoelectrochemistry, CN-TiO2 exhibited 23 % photoactivity of the full-spectrum measurement when using a 410 nm filter. Our findings demonstrate that CN-TiO2 displayed a band gap of 2.9 eV, evidencing TiO2 photosensitization attributed to enhanced charge transfer at the heterointerface boundaries via staggered heterojunction type II.

RESUMEN

Vacancy engineering and heterostructure construction are regarded as potent approaches for synergistically boosting hydrogen production in renewable energy conversion. Herein, a selective phosphorization strategy was implemented to fabricate coral-like ZnO/FeCoP@N-doped carbon hierarchical microspheres (ZnO/FeCoP@NCHMS) via only controllably phosphorizing the Co and Fe atoms in a precursor, which was formed by generating ZnCoFe LDH on the surface of a zinc cobalt coordination polymer microsphere. Then, by adopting a reduction treatment for ZnO/FeCoP@NCHMS, the innovative ZnO/FeCoPv@NCHMS with abundant phosphorus vacancies (Pv) was realized. The introduction of phosphorus vacancy could optimize the electronic structures of metal phosphides and accelerate the reconstruction of active species, thus speeding up the reaction kinetic. Likewise, the plentiful heterointerfaces greatly expedite the transfer of electrons and protons, exposing ultra-high active sites. By virtue of these fascinating characters and the unique coral-like hierarchical architecture, the as-prepared ZnO/FeCoPv@NCHMS reveal preeminent electrocatalytic activities, and the overpotentials for the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER) are as low as 177 and 173 mV at 10 mA cm-2 in alkaline medium, respectively. Impressively, the water electrolysis device assembled by ZnO/FeCoPv@NCHMS requires a mere cell voltage of 1.508 V to attain a current density of 10 mA cm-2. Furthermore, the ZnO/FeCoPv@NCHMS also demonstrate extraordinary durability, sustaining operation for at least 28 h (at 100 mA cm-2) during the water splitting process. This study provides novel insights into defect regulation and heterointerface construction for overall water splitting.

RESUMEN

Integrating electrochemical upcycling of polyethylene-terephthalate (PET) and the hydrogen evolution reaction (HER) is an energy-saving approach for electrolytic hydrogen (H2) production, along with the coproduction of formate. Herein, a novel and rapid strategy of cold plasma phosphating is employed to synthesize Co2P-Ni2P heterointerface decorated on carbon cloth (Co2P-Ni2P/CC) to catalyze H2 generation and reform PET. Notably, the obtained Co2P-Ni2P/CC exhibits eminent ethylene glycol oxidation reaction (EGOR) and HER activities, effectuating low potentials of merely 1.300 and -0.112 V versus RHE at 100 mA cm-2 for the EGOR and HER, respectively, also attaining an ultralow cell bias of 1.300 V at 10 mA cm-2 for EG oxidation assisted-water splitting. DFT and characterization results validate that the as-formed built-in electric fields in the Co2P-Ni2P heterointerface can accelerate electrons transfer and deepen structural self-reconstruction, thereby boosting effectively water dissociation and ethylene glycol (EG) dehydrogenation. Impressively, coupling HER with PET-derived EG-to-formate in a flow-cell electrolyzer assembled with Co2P-Ni2P/CC pair achieves an intriguing formate Faradaic efficiency of 90.6% and an extraordinary stable operation of over 70 h at 100 mA cm-2. The work exemplifies a facile and effective strategy for synthesizing metal phosphides electrocatalysts with extraordinary performance toward H2 generation of water splitting and recycling of PET.

RESUMEN

During fractionated radiotherapy, DNA damage repair intensifies in tumor cells, culminating in cancer radioresistance and subsequent radiotherapy failure. Despite the recent development of nanoradiosensitizers targeting specific DNA damage repair pathways, the persistence of repair mechanisms involving multiple pathways remains inevitable. To address this challenge, a nucleophilicity-engineered DNA ligation blockade nanoradiosensitizer (DLBN) comprising Au/CeO2 heteronanostructure modified with trans-acting activator of transcription peptides is reported, which targets and inhibits the DNA ligation inside cancer cell nuclei via heterointerface-mediated dephosphorylation of DNA, a crucial step in overcoming cancer radioresistance. First, the Schottky-type heteronanostructure of cancer cell nucleus-targeting DLBN effectively intensifies radiation-induced DNA damage via catalase-mimetic activity and radiation-triggered catalytic reactions. Notably, by leveraging Au/CeO2 heterointerface, DLBN spontaneously dissociates H2O to hydroxide, a nucleophile with higher nucleophilicity, thereby exhibiting remarkable dephosphorylation capability at DNA nicks through facilitated nucleophilic attack. This enables the blockade of DNA ligation, a pivotal step in all DNA damage repair pathways, effectively interrupting the repair process. Consequently, DLBN resensitizes radioresistant cells by overcoming therapy-induced radioresistance, leading to a substantial accumulation of unrepaired DNA damage. These findings offer insight into the dephosphorylation of DNA within nuclei, and underscore the potential of heteronanostructure-based nanoradiosensitizer to block DNA ligation against therapy-induced radioresistance.

RESUMEN

The rational construction of a hierarchical noble metal-metal-organic frameworks (MOFs) structure is anticipated to yield enduring and highly efficient performance in alkaline electrocatalytic water splitting. Herein, a sandwich construction strategy is employed to enhance the stability, wherein active RutheniRu (Ru) nanosheets are incorporated onto nickel foam (NF) and subsequently covered with porphyrinic MOFs (PMOFs). In addition, activated PMOF-NiOOH-Ru20/NF-C/A electrodes are obtained by electrochemical self-reconstruction as cathode and anode, respectively. Density functional theory (DFT) calculations demonstrated that the resulting PMOF-NiOOH-Ru heterointerface effectively facilitated electron transfer, enhanced H2O adsorption capacity, and optimized ΔG values for *H and *O to *OOH. Consequently, PMOF-NiOOH-Ru20/NF-C/A exhibited low overpotentials for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), accompanied by minimal Ru leakage. Furthermore, stable overall water splitting can be achieved with a low voltage of 1.456 V@10 mA cm-2 for over 120 h. Even when operated in simulated seawater, the prepared electrodes demonstrated similar activity and stability. This study contributes to a deeper understanding of the regulation mechanism for the performance and stability of active sites in the electrocatalytic self-reconstruction process.

RESUMEN

Nociceptors are key sensory receptors that transmit warning signals to the central nervous system in response to painful stimuli. This fundamental process is emulated in an electronic device by developing a novel artificial nociceptor with an ultrathin, nonstoichiometric gallium oxide (GaOx)-silicon oxide heterostructure. A large-area 2D-GaOx film is printed on a substrate through liquid metal printing to facilitate the production of conductive filaments. This nociceptive structure exhibits a unique short-term temporal response following stimulation, enabling a facile demonstration of threshold-switching physics. The developed heterointerface 2D-GaOx film enables the fabrication of fast-switching, low-energy, and compliance-free 2D-GaOx nociceptors, as confirmed through experiments. The accumulation and extrusion of Ag in the oxide matrix are significant for inducing plastic changes in artificial biological sensors. High-resolution transmission electron microscopy and electron energy loss spectroscopy demonstrate that Ag clusters in the material dispersed under electrical bias and regrouped spontaneously when the bias is removed owing to interfacial energy minimization. Moreover, 2D nociceptors are stable; thus, heterointerface engineering can enable effective control of charge transfer in 2D heterostructural devices. Furthermore, the diffusive 2D-GaOx device and its Ag dynamics enable the direct emulation of biological nociceptors, marking an advancement in the hardware implementation of artificial human sensory systems.

RESUMEN

Developing efficient electrocatalyst in sulfides for hydrogen evolution reaction (HER) still poses challenges due to the lack of understanding the role of sulfide heterointerface. Here, we report a sulfide heterostructure RuSx/NbS2, which is composed of 3R-type NbS2 loaded by amorphous RuSx nanoparticles with S-S bonds formed at the interface. As HER electrocatalyst, the RuSx/NbS2 shows remarkable low overpotential of 38 mV to drive a current density of 10 mA cm-2 in acid, and also low Tafel slope of 51.05 mV dec-1. The intrinsic activity of RuSx/NbS2 is much higher than that of Ru/NbS2 reference as well as the commercial Pt/C. Both experiments and theoretical calculations unveil a reversed charge transfer at the interface from NbS2 to RuSx that driven by the formation of S-S bonds, resulting in electron-rich Ru configuration for strong hydrogen adsorption. Meanwhile, electronic redistribution induced by the sulfide heterostructure facilitates hydrogen spillover (HSo) effect in this system, leading to accelerated hydrogen desorption at the basal plane of NbS2. This study provides an effective S-S bond strategy in sulfide heterostructure to synergistically modulate the charge transfer and adsorption thermodynamics, which is very valuable for the development of efficient electrocatalysts in practical applications.

RESUMEN

Contemporary global industrialization, coupled with the relentless growth of the population, has led to a persistent escalation in the emission and accumulation of various toxic and harmful chemicals in the environment, severely disrupting the ecological balance. The development of efficient environmental cleanup materials is a crucial scientific and technological concern. Since the groundbreaking work on Ti3C2Tx in 2011, there has been a huge growing interest in MXene-based composites developed through heterointerface engineering due to its high surface area, hydrophilicity, eco-friendliness, biocompatibility, easy functionalization, excellent thermal/mechanical properties, metal conductivity and rich electronic density. In the area of environmental remediation, MXene-based composites obtained through heterointerface engineering strategies have the ability to effectively remove and systematically monitor contaminants in comparison to virgin MXene, thanks to the synergistic effects and complementary benefits. Heterointerface engineering strategy increases specific surface area, introduces catalytic sites, constructs heterojunctions/Schottky junctions, and facilitates carrier migration and electron-hole separation. These novel MXene-based composites represent significant advances in MXene research and deserve a comprehensive review. Although several excellent reviews and perspectives on the application of MXene-based composites in environmental remediation have been published, there is still a scarcity of comprehensive and systematic assessments on the reliable data and mechanisms of various MXene-based composite materials for pollutant removal and monitoring. In this focused review, the first part briefly introduces the common preparation strategies and characterization methods of single MXene and MXene-based composites, and the second part details the innovative application of MXene-based composites (involving the amalgamation of MXene with metal oxides, metal sulfide, g-C3N4, layered double hydroxides, metal-organic frameworks, single atom/quantum dots, polymers, etc.) in the field of environmental remediation, including carbon dioxide reduction, nitrogen monoxide and volatile organic compounds removal, antibiotic and heavy metal ions degradation, summarizing the relevant performance and mechanisms. Furthermore, the recent advancements in the utilization of MXene-based composites for the sensing of emerging environmental contaminants (antibiotic and antibiotic resistance genes) are summarized. Finally, an outline of the existing challenges and future prospects on this exciting field was narrated for plausible real-world use. This review will help to inspire the diverse design of MXene-based composites and to advance research related to their application in the environmental sector.

RESUMEN

Lithium niobate (LiNbO3) is emerging as an appealing candidate for integrated optical applications with enhanced complexity, owing to its inherent abundant optoelectronic properties. To compensate for the inability of LiNbO3 to generate indistinguishable single photons, the evanescent coupling heterointerface constructed between III-V compound semiconductors (e.g., InP) and LiNbO3 through plasma activation provides a feasible solution for balancing the integration efficiency and interfacial stability while achieving sub-50 nm alignment accuracy between devices, thus offering ultracompact on-chip light sources for classical optoelectronics and quantum optics. However, a challenge remains in the formation of the InP/LiNbO3 platform due to the huge mismatch in the coefficient of thermal expansion. Here, we demonstrate the InP/LiNbO3 covalent heterointerface using an asymmetric plasma activation strategy. Different plasmas are used for the activation of InP and LiNbO3 specifically, balancing the enhancement of surface functional group density with the avoidance of defect generation effectively. More importantly, combined with surface comprehensive characterizations and interface performance, we determine that the introduction of ammonia solution enables the surface hydroxyl groups to be "effective" as LiNbO3 surface relaxation increases the chance of -OH groups' contact. Therefore, a robust covalent bond network is established across the InP/LiNbO3 interface at 80 °C with an enhanced bonding strength of 9.7 MPa. Moreover, a hybrid quantum photonic chip based on the InP/LiNbO3 platform is designed to compute the coupling efficiency and the impact of misalignment on it, demonstrating the potential of extending the platform to hybrid integrated quantum systems.

RESUMEN

Smart metal-metal oxide heterointerface construction holds promising potentials to endow an efficient electron redistribution for electrochemical CO2 reduction reaction (CO2RR). However, inhibited by the intrinsic linear-scaling relationship, the binding energies of competitive intermediates will simultaneously change due to the shifts of electronic energy level, making it difficult to exclusively tailor the binding energies to target intermediates and the final CO2RR performance. Nonetheless, creating specific adsorption sites selective for target intermediates probably breaks the linear-scaling relationship. To verify it, Ag nanoclusters were anchored onto oxygen vacancy-rich CeO2 nanorods (Ag/OV-CeO2) for CO2RR, and it was found that the oxygen vacancy-driven heterointerface could effectively promote CO2RR to CO across the entire potential window, where a maximum CO Faraday efficiency (FE) of 96.3% at -0.9 V and an impressively high CO FE of over 62.3% were achieved at a low overpotential of 390 mV within a flow cell. The experimental and computational results collectively suggested that the oxygen vacancy-driven heterointerfacial charge spillover conferred an optimal electronic structure of Ag and introduced additional adsorption sites exclusively recognizable for *COOH, which, beyond the linear-scaling relationship, enhanced the binding energy to *COOH without hindering *CO desorption, thus resulting in the efficient CO2RR to CO.

RESUMEN

The development of productive and durable non-precious metal catalysts for the sluggish oxygen evolution reaction (OER) is critical for water splitting. Herein, a novel NiSe-FeOx heterojunction encapsulated in lignin-derived carbon layer (NiSe-FeOx@LC) was synthesized via hydrothermal self-assembly and in-situ pyrolysis. NiSe-FeOx@LC exhibited excellent OER performance with an overpotential of 265 mV at 50 mA·cm-2, a Tafel slope of 83 mV·dec-1, as well as long-term stability. Both experimental and DFT calculation results indicated that the doping of FeOx into NiSe@LC successfully optimized the dual interface structure between NiSe and FeOx, thereby promoted the d-bands orbital hybridization, that facilitated electron transfer. Besides, the carbon coating effectively protected the NiSe-FeOx components from leaching and agglomerating during the reaction. This study provides insight into the significance of lignin-derived carbon-encapsulated metallic catalyst for electrocatalytic OER process.

Asunto(s)

RESUMEN

Electrochemical water splitting stands out as a promising avenue for green hydrogen production, yet its efficiency is fundamentally governed by the oxygen evolution reaction (OER). In this work, we investigated the growth mechanism of CoFe hydroxide formed by in situ self-corrosion of iron foam for the first time and the significant influence of dissolved oxygen in the immersion solution on this process. Based on this, the CoP2-FeP4/IF heterostructure catalytic electrode demonstrates exceptional OER activity in a 1 M KOH electrolyte, with an overpotential of only 253 ± 4 mV (@10 mA cm-2), along with durability exceeding 1000 h. Density functional theory calculations indicate that constructing heterojunction interfaces promotes the redistribution of interface electrons, optimizing the free energy of adsorbed intermediate during the water oxidation process. This research highlights the importance of integrating self-corroding in-situ growth with interface engineering techniques to develop efficient water splitting materials.

RESUMEN

The interaction between light and moiré superlattices presents a platform for exploring unique light-matter phenomena. Tailoring these optical properties holds immense potential for advancing the utilization of moiré superlattices in photonics, optoelectronics, and valleytronics. However, the control of the optical polarization state in moiré superlattices, particularly in the presence of moiré effects, remains elusive. Here, we unveil the emergence of optical anisotropy in moiré superlattices by constructing twisted WSe2/WSe2/SiP heterostructures. We report a linear polarization degree of ∼70% for moiré excitons, attributed to the spatially nonuniform charge distribution, corroborated by first-principles calculations. Furthermore, we demonstrate the modulation of this linear polarization state via the application of a magnetic field, resulting in polarization angle rotation and a magnetic-field-dependent linear polarization degree, influenced by valley coherence and moiré potential effects. Our findings demonstrate an efficient strategy for tuning the optical polarization state of moiré superlattices using heterointerface engineering.

RESUMEN

The design of cheap, noble-metal-free, and efficient electrocatalysts for an enhanced hydrogen evolution reaction (HER) to produce hydrogen gas as an energy source from water splitting is an ideal approach. Herein, we report the synthesis of Fe2O3 nanorods-NiFe2O4 nanoparticles on cotton fiber cloth (Fe2O3-NiFe2O4/CF) at a low temperature as an efficient electrocatalyst for HERs. Among the as-prepared samples, the optimal Fe2O3-NiFe2O4/CF-3 electrocatalyst exhibits good HER performance with an overpotential of 127 mV at a current density of 10 mA cm-2, small Tafel slope of 44.9 mV dec-1, and good stability in 1 M KOH alkaline solution. The synergistic effect between Fe2O3 nanorods and NiFe2O4 nanoparticles of the heterojunction composite at the heterointerface is mainly responsible for improved HER performance. The CF is an effective substrate for the growth of the Fe2O3-NiFe2O4 nanocomposite and provides conductive channels for the active materials' HER process.

RESUMEN

Rechargeable aqueous batteries adopting Fe-based materials are attracting widespread attention by virtue of high-safety and low-cost. However, the present Fe-based anodes suffer from low electronic/ionic conductivity and unsatisfactory comprehensive performance, which greatly restrict their practicability. Concerning the principle of physical chemistry, fabricating electrodes that could simultaneously achieve ideal thermodynamics and fast kinetics is a promising issue. Herein, hierarchical Fe3O4@Fe foam electrode with enhanced interface/grain boundary engineering is fabricated through an in situ self-regulated strategy. The electrode achieves ultrahigh areal capacity of 31.45 mA h cm-2 (50 mA cm-2), good scale application potential (742.54 mA h for 25 cm2 electrode), satisfied antifluctuation capability, and excellent cycling stability. In/ex situ characterizations further validate the desired thermodynamic and kinetic properties of the electrode endowed with accurate interface regulation, which accounts for salient electrochemical reversibility in a two-stage phase transition and slight energy loss. This work offers a suitable strategy in designing high-performance Fe-based electrodes with comprehensive inherent characteristics for high-safety large-scale energy storage.

RESUMEN

Developing non-platinum group metal catalysts for the sluggish hydrogen oxidation reaction (HOR) is critical for alkaline fuel cells. To date, Ni-based materials are the most promising candidates but still suffer from insufficient performance. Herein, we report an unconventional hcp/fcc Ni (u-hcp/fcc Ni) heteronanocrystal with multiple epitaxial hcp/fcc heterointerfaces and coherent twin boundaries, generating rugged surfaces with plenty of asymmetric convex sites. Systematic analyses discover that such convex sites enable the adsorption of *H in unusual bridge positions with weakened binding energy, circumventing the over-strong *H adsorption on traditional hollow positions, and simultaneously stabilizing interfacial *H2O. It thus synergistically optimizes the HOR thermodynamic process as well as reduces the kinetic barrier of the rate-determining Volmer step. Consequently, the developed u-hcp/fcc Ni exhibits the top-rank alkaline HOR activity with a mass activity of 40.6 mA mgNi -1 (6.3 times higher than fcc Ni control) together with superior stability and high CO-tolerance. These results provide a paradigm for designing high-performance catalysts by shifting the adsorption state of intermediates through configuring surface sites.

RESUMEN

Heterogeneous electrode materials possess abundant heterointerfaces with a localized "space charge effect", which enhances capacity output and accelerates mass/charge transfer dynamics in energy storage devices (ESDs). These promising features open new possibilities for demanding applications such as electric vehicles, grid energy storage, and portable electronics. However, the fundamental principles and working mechanisms that govern heterointerfaces are not yet fully understood, impeding the rational design of electrode materials. In this study, the heterointerface evolution during charging and discharging process as well as the intricate interaction between heterointerfaces and charge/mass transport phenomena, is systematically discussed. Guidelines along with feasible strategies for engineering structural heterointerfaces to address specific challenges encountered in various application scenarios, are also provided. This review offers innovative solutions for the development of heterogeneous electrode materials, enabling more efficient energy storage beyond conventional electrochemistry. Furthermore, it provides fresh insights into the advancement of clean energy conversion and storage technologies. This review contributes to the knowledge and understanding of heterointerfaces, paving the way for the design and optimization of next-generation energy storage materials for a sustainable future.

RESUMEN

The performance of zinc-air battery is constrained by the sluggish rate of oxygen electrode reaction, particularly under high current discharge conditions where the kinetic process of the oxygen reduction reaction (ORR) decelerates significantly. To address this challenge, we present a novel phase transition strategy that facilitates the creation of a heteroatom-doped heterointerface (CoN/CoS2). The meticulously engineered CoN/CoS2/NC electrocatalyst displays a superior ORR half-wave potential of 0.87 V and an OER overpotential of 320 mV at 10 mA cm-2. Experimental and computational analysis confirm that the CoN/CoS2 heterostructure optimizes local charge distribution, accelerates electron transfer, and tunes active sites for enhanced catalysis. Notably, this heterojunction improves stability by resisting corrosion and degradation under harsh alkaline conditions, thus demonstrating superior performance and longevity in a custom-made liquid zinc-air battery. This research provides valuable practical and theoretical foundations for designing efficient heterointerfaces in electrocatalysis applications.