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1.
Proc Natl Acad Sci U S A ; 120(3): e2207080119, 2023 Jan 17.
Article in English | MEDLINE | ID: mdl-36623198

ABSTRACT

The electrochemical conversion of waste nitrate (NO3-) to valuable ammonia (NH3) is an economical and environmentally friendly technology for sustainable NH3 production. It is beneficial for environmental nitrogen pollution management and is also an appealing alternative to the current Haber-Bosch process for NH3 production. However, owing to the competing hydrogen evolution reaction, it is necessary to design highly efficient and stable electrocatalysts with high selectivity. Herein, we report a rational design of Fe nanoparticles wrapped in N-doped carbon (Fe@N10-C) as a high NH3 selective and efficient electrocatalyst using a metal-organic framework precursor. We constructed a catalyst with new active sites by doping with nitrogen, which activated neighboring carbon atoms and enhanced metal-to-carbon electron transfer, resulting in high catalytic activity. These doped N sites play a key role in the NO3- electroreduction. As a result, the Fe@N10-C nanoparticles with optimal doping of N demonstrated remarkable performance, with a record-high NO3- removal capacity of 125.8 ± 0.5 mg N gcat-1 h-1 and nearly 100 % (99.7 ± 0.1%) selectivity. The catalyst also delivers an impressive NH3 production rate of 2647.7 µg h-1 cm-2 and high faradaic efficiency of 91.8 ± 0.1%. This work provides a new route for N-doped carbon-iron catalysis application and paves the way for addressing energy and environmental issues.

2.
Nano Lett ; 24(34): 10699-10709, 2024 Aug 28.
Article in English | MEDLINE | ID: mdl-39141437

ABSTRACT

The insufficient antioxidant reserves in tumor cells play a critical role in reactive oxygen species (ROS)-mediated therapeutics. Metallothionein-2 (MT-2), an intracellular cysteine-rich protein renowned for its potent antioxidant properties, is intricately involved in tumor development and correlates with a poor prognosis. Consequently, MT-2 emerges as a promising target for tumor therapy. Herein, we present the development of copper-doped carbon dots (Cu-CDs) to target MT-2 to compromise the delicate antioxidant reserves in tumor cells. These Cu-CDs with high tumor accumulation and prolonged body retention can effectively suppress tumor growth by inducing oxidative stress. Transcriptome sequencing unveils a significant decrease in MT-2 expression within the in vivo tumor samples. Further mechanical investigations demonstrate that the antitumor effect of Cu-CDs is intricately linked to apolipoprotein E (ApoE)-mediated downregulation of MT-2 expression and the collapse of the antioxidant system. The robust antitumor efficacy of Cu-CDs provides invaluable insights into developing MT-2-targeted nanomedicine for cancer therapies.


Subject(s)
Antioxidants , Carbon , Copper , Metallothionein , Quantum Dots , Metallothionein/genetics , Metallothionein/metabolism , Copper/chemistry , Copper/pharmacology , Carbon/chemistry , Carbon/pharmacology , Humans , Animals , Mice , Antioxidants/pharmacology , Antioxidants/chemistry , Quantum Dots/chemistry , Quantum Dots/therapeutic use , Cell Line, Tumor , Oxidative Stress/drug effects , Reactive Oxygen Species/metabolism , Antineoplastic Agents/pharmacology , Antineoplastic Agents/chemistry , Neoplasms/drug therapy , Neoplasms/metabolism
3.
Nano Lett ; 24(39): 12218-12225, 2024 Oct 02.
Article in English | MEDLINE | ID: mdl-39263891

ABSTRACT

Neutral electrochemical nitrate (NO3-) reduction to ammonia involves sluggish and complex kinetics, so developing efficient electrocatalysts at low potential remains challenging. Here, we report a domain-confined etching strategy to construct RuxMoy nanoalloys on porous nitrogen-doped carbon by optimizing the Ru-to-Mo ratio, achieving efficient neutral NH3 electrosynthesis. Combining in situ spectroscopy and theoretical simulations demonstrated a rational synergic effect between Ru and Mo in nanoalloys that reinforces *H adsorption and lowers the energy barrier of NO3- hydrodeoxygenation for NH3 production. The resultant Ru5Mo5-NC surpasses 92.8% for NH3 selectivity at the potential range from -0.25 to -0.45 V vs RHE under neutral electrolyte, particularly achieving a high NH3 selectivity of 98.3% and a corresponding yield rate of 1.3 mg h-1 mgcat-1 at -0.4 V vs RHE. This work provides a synergic strategy that sheds light on a new avenue for developing efficient multicomponent heterogeneous catalysts.

4.
Small ; 20(16): e2305513, 2024 Apr.
Article in English | MEDLINE | ID: mdl-38032150

ABSTRACT

Precious-metal single-atom catalysts (SACs), featured by high metal utilization and unique coordination structure for catalysis, demonstrate distinctive performances in the fields of heterogeneous and electrochemical catalysis. Herein, gold SACs are constructed on hierarchical nitrogen-doped carbon nanocages (hNCNC) via a simple impregnation-drying process and first exploited for electrocatalytic carbon dioxide reduction reaction (CO2RR) to produce syngas. The as-constructed Au SAC exhibits the high mass activity of 3319 A g-1 Au at -1.0 V (vs reversible hydrogen electrode, RHE), much superior to the Au nanoparticles supported on hNCNC. The ratio of H2/CO can be conveniently regulated in the range of 0.4-2.2 by changing the applied potential. Theoretical study indicates such a potential-dependent H2/CO ratio is attributed to the different responses of HER and CO2RR on Au single-atom sites coordinating with one N atom at the edges of micropores across the nanocage shells. The catalytic mechanism of the Au active sites is associated with the smooth switch between twofold and fourfold coordination during CO2RR, which much decreases the free energy changes of the rate-determining steps and promotes the reaction activity.

5.
Small ; 20(12): e2306928, 2024 Mar.
Article in English | MEDLINE | ID: mdl-37953415

ABSTRACT

The development of lithium-sulfur batteries is seriously hindered by the shuttle effect of lithium polysulfides (LiPSs) and the low electrical conductivity of sulfur. To solve these problems, efficient catalysts can be used to improve the conversion rate of LiPSs and the conductivity of sulfur cathode. Herein, annealed melamine foam supported MoSe2 (NCF@MoSe2) is used as interlayer and the MoSe2/MoP heterojunction obtained by phosphating MoSe2 is further used as the catalyst material for metal fusion with a sulfur element. The interlayer can not only improve the electrical conductivity and effectively adsorb and catalyze LiPSs, but more importantly, the MoSe2/MoP heterojunction can also effectively adsorb and catalyze LiPSs, so that the batteries have a dual inhibition shuttling effect strategy. Furthermore, the rapid anchor-diffusion transition of LiPSs, and the suppression of shuttling effects by catalyst materials are elucidated using theoretical calculations and in situ Raman spectroscopy. The two-step catalytic strategy exhibits a high reversibility of 983 mAh g-1 after 200 cycles at 0.5 C and a high-rate capacity of 889 mAh g-1 at 5 C. This work provides a feasible solution for the rational design of interlayer and heterojunction materials and is also conducive to the development of more advanced Li-S batteries.

6.
Small ; 20(1): e2303836, 2024 Jan.
Article in English | MEDLINE | ID: mdl-37670221

ABSTRACT

The battery performance declines significantly in severely cold areas, especially discharge capacity and cycle life, which is the most significant pain point for new energy consumers. To address this issue and improve the low-temperature characteristic of aluminum-ion batteries, in this work, polydopamine-derived N-doped carbon nanospheres are utilized to modify the most promising graphite material. More active sites are introduced into graphite, more ion transport channels are provided, and improved ionic conductivity is achieved in a low-temperature environment. Due to the synergistic effect of the three factors, the ion diffusion resistance is significantly reduced and the diffusion coefficient of aluminum complex ions in the active material become larger at low temperatures. Therefore, the battery delivers an improved capacity retention rate from 23% to 60% at -20 °C and excellent ultra-long cycling stability over 5500 cycles at -10 °C. This provides a novel strategy for constructing low-temperature aluminum-ion batteries with high energy density, which is conducive to promoting the practicality of aluminum-ion batteries.

7.
Small ; 20(7): e2304663, 2024 Feb.
Article in English | MEDLINE | ID: mdl-37821413

ABSTRACT

Carbon materials with unique sp2 -hybridization are extensively researched for catalytic applications due to their excellent conductivity and tunable physicochemical properties. However, the development of economic approaches to tailoring carbon materials into desired morphologies remains a challenge. Herein, a convenient "bottom-up" strategy by pyrolysis of graphitic carbon nitride (g-C3 N4 ) (or other carbon/nitrogen (C, N)-enriched compounds) together with selected metal salts and molecules is reported for the construction of different carbon-based catalysts with tunable morphologies, including carbon nano-balls, carbon nanotubes, nitrogen/sulfur (S, N) doped-carbon nanosheets, and single-atom catalysts, supported by carbon layers. The catalysts are systematically investigated through various microscopic, spectroscopic, and diffraction methods and they demonstrate promising and broad applications in electrocatalysis such as in the oxygen reduction reaction and water splitting. Mechanistic monitoring of the synthesis process through online thermogravimetric-gas chromatography-mass spectrometry measurements indicates that the release of C─N-related moieties, such as dicyan, plays a key role in the growth of carbon products. This enables to successfully predict other widely available precursor compounds beyond g-C3 N4 such as caffeine, melamine, and urea. This work develops a novel and economic strategy to generate morphologically diverse carbon-based catalysts and provides new, essential insights into the growth mechanism of carbon nanomaterials syntheses.

8.
Small ; 20(4): e2305965, 2024 Jan.
Article in English | MEDLINE | ID: mdl-37702142

ABSTRACT

Developing high-efficiency and stable oxygen evolution reaction (OER) electrocatalysts is an imperative requirement to produce green and clean hydrogen energy. In this work, the FeCoSy /NCDs composite with nitrogen-doped carbon dots (NCDs) modified Fe-Co sulfide (FeCoSy ) nanosheets is prepared by using a facile and mild one-pot solvothermal method. Benefiting from the low crystallinity and the synergistic effect between FeCoSy and NCDs, the optimal FeCoSy /NCDs-3 composite exhibits an overpotential of only 284 mV at 10 mA cm-2 , a small Tafel value of 52.1 mV dec-1 , and excellent electrochemical durability in alkaline solution. Remarkably, unlike ordinary metal sulfide electrocatalysts, the morphology, components, and structure of the FeCoSy /NCDs composite can be well retained after OER test. The NCDs modified FeCoSy composite with excellent electrocatalytic performance provides an effective approach to boost metal sulfide electrocatalysts for practical application.

9.
Small ; 20(40): e2403314, 2024 Oct.
Article in English | MEDLINE | ID: mdl-39152932

ABSTRACT

Efficient and durable electrocatalysts for the hydrogen evolution reaction (HER) in alkaline seawater environments are essential for sustainable hydrogen production. Zeolitic imidazolate framework-8 (ZIF-8) is synthesized through pulsed laser ablation in liquid, followed by pyrolysis, producing N-doped porous carbon (NC). NC matrix serves as a self-template, enabling Pt nanocluster decoration (NC-Pt) via pulsed laser irradiation in liquid. NC-Pt exhibits a large surface area, porous structure, high conductivity, N-rich carbon, abundant active sites, low Pt content, and a strong NC-Pt interaction. These properties enhance efficient mass transport during the HER. Remarkably, the optimized NC-Pt-4 catalyst achieves low HER overpotentials of 52, 57, and 53 mV to attain 10 mA cm-2 in alkaline, alkaline seawater, and simulated seawater, surpassing commercial Pt/C catalysts. In a two-electrode system with NC-Pt-4(-)ǀǀIrO2(+) as cathode and anode, it demonstrates excellent direct seawater electrolysis performance, with a low cell voltage of 1.63 mV to attain 10 mA cm-2 and remarkable stability. This study presents a rapid and efficient method for fabricating cost-effective and highly effective electrocatalysts for hydrogen production in alkaline and alkaline seawater environments.

10.
Small ; : e2404540, 2024 Sep 09.
Article in English | MEDLINE | ID: mdl-39246204

ABSTRACT

The ethylene glycol oxidation reaction (EGOR) has attracted attention because ethylene glycol (EG), which exhibits large-scale production and a low market price, can be reformed into valuable glycolic acid (GCA) with the cogeneration of high-purity hydrogen gas during the reaction. In this study, a noble catalyst material of Pt nanoparticles supported on Se-doped porous carbon (Pt/SePC) is prepared and investigated for the selective electrochemical oxidation of EG to GCA. Pt/SePC achieved a maximum EG conversion of 94.6% and GCA selectivity of 84.4% and maintained this high performance with negligible degradation during durability tests. Furthermore, the EGOR required lower overpotential rather than the oxygen evolution reaction, thus the EGOR coupled with the hydrogen evolution reaction can reduce the cell overpotential to 0.60 V, which is much lower than that of water electrolysis (1.58 V). The effect of Se doping is investigated through experimental analyses and density functional theory (DFT) calculations, and they shows that Se modified the binding energy of Pt nanoparticles and the adsorption energy of reactants by lattice deformation and charge density modification. This study provides scientific insights and strategies for electrocatalyst design for the selective oxidation of polyols to value-added chemicals via the cogeneration of hydrogen gas.

11.
Small ; 20(29): e2400158, 2024 Jul.
Article in English | MEDLINE | ID: mdl-38415969

ABSTRACT

Noble metallic aerogels with the self-supported hierarchical structure and remarkable activity are promising for methanol fuel cells, but are limited by the severe poisoning and degradation of active sites during electrocatalysis. Herein, the highly stable electrocatalyst of N-doped carbon dots-PtNi (NCDs-PtNi) aerogels is proposed by confining NCDs with alloyed PtNi for methanol oxidation and oxygen reduction reactions. Comprehensive electrocatalytic measurements and theoretical investigations suggest the improvement in structure stability and regulation in electronic structure for better electrocatalytic durability when confining NCDs with PtNi aerogels. Notably, the NCDs-PtNi aerogels perform 12-fold higher activity than that of Pt/C and maintain 52% of their initial activity after 5000 cycles toward acidic methanol oxidation. The enhanced stability and activity of NCDs-PtNi aerogels are also evident for oxygen reduction reactions in different electrolytes. These results highlight the effectiveness of stabilizing metallic aerogels with NCDs, offering a feasible pathway to develop robust electrocatalysts for fuel cells.

12.
Small ; 20(32): e2311667, 2024 Aug.
Article in English | MEDLINE | ID: mdl-38507721

ABSTRACT

The designing and fabricating highly active hydrogen evolution reaction (HER) electrocatalysts that can superior to Pt/C is extremely desirable but challenging. Herein, the fabrication of Ru/TiO2/N-doped carbon (Ru/TiO2/NC) nanofiber is reported as a novel and highly active HER electrocatalyst through electrospinning and subsequent pyrolysis treatment, in which Ru nanoclusters are dispersed into TiO2/NC hybrid nanofiber. As a novel support, experimental and theoretical calculation results reveal that TiO2/NC can more effectively accelerate water dissociation as well as optimize the adsorption strength of *H than TiO2 and NC, thus leading to a significantly enhanced HER activity, which merely requires an overpotential of 18 mV to reach 10 mA cm-2, outperforming Pt/C in an alkaline solution. The electrolytic cell composed of Ru/TiO2/NC nanofiber and NiFe LDH/NF can generate 500 and 1000 mA cm-2 at voltages of 1.631 and 1.753 V, respectively. Furthermore, the electrolytic cell also exhibits remarkable durability for at least 100 h at 200 mA cm-2 with negligible degradation in activity. The present work affords a deep insight into the influence of support on the activity of electrocatalyst and the strategy proposed in this research can also be extended to fabricate various other types of electrocatalysts for diverse electrocatalytic applications.

13.
Small ; : e2400641, 2024 Jul 11.
Article in English | MEDLINE | ID: mdl-38989690

ABSTRACT

Li-rich manganese-based cathode (LRMC) has attracted intense attention to developing advanced lithium-ion batteries with high energy density. However, LRMC is still plagued by poor cyclic stability, undesired rate capacity, and irreversible oxygen release. To address these issues, herein, a feasible polyvinylidene fluoride (PVDF)-assisted interface modification strategy is proposed for modulating the surface architecture and electronic conductivity of LRMC by intruding the F-doped carbon coating, spinel structure, and oxygen vacancy on the LRMC, which can greatly enhance the cyclic stability and rate capacity, and restrain the oxygen release for LRMC. As a result, the modified material delivers satisfactory cyclic performance with a capacity retention of 90.22% after 200 cycles at 1 C, an enhanced rate capacity of 153.58 mAh g-1 at 5 C and 126.32 mAh g-1 at 10 C, and an elevated initial Coulombic efficiency of 85.63%. Moreover, the thermal stability, electronic conductivity, and structure stability of LRMC are also significantly improved by the PVDF-assisted interface modification strategy. Therefore, the strategy of simultaneously modulating the surface architecture and the electronic conductivity of LRMC provides a valuable idea to improve the comprehensive electrochemical performance of LRMC, which offers a promising reference for designing LRMC with high electrochemical performance.

14.
Small ; 20(28): e2310523, 2024 Jul.
Article in English | MEDLINE | ID: mdl-38295042

ABSTRACT

Electrochemical capacitors (ECs) show great perspective in alternate current (AC) filtering once they simultaneously reach ultra-fast response and high capacitance density. Nevertheless, the structure-design criteria of the two key properties are often mutually incompatible in electrode construction. Herein, it is proposed that combining vertically oriented porous carbon with enhanced interfacial capacitance (Ci) can efficiently solve this issue. Theoretically, the density function theory calculation shows that the Ci of a carbon electrode can be enhanced by boron doping due to the corresponding compact induced charge layer. Experimentally, the vertical-oriented boron-doped graphene nanowalls (BGNWs) electrodes, whose Ci is enhanced from 4.20 to 10.16 µF cm-2 upon boron doping, are prepared on a large scale (480 cm2) using a hot-filament chemical vapor deposition technique (HFCVD). Owing to the high Ci and vertically oriented porous structure, BGNWs-based EC has a high capacitance density of 996 µF cm-2 with a phase angle of - 79.4° at 120 Hz in aqueous electrolyte and a high energy density of 1953 µFV2 cm-2 in organic electrolyte. As a result, the EC is capable of smoothing 120 Hz ripples for 60 Hz AC filtering. These results provide enlightening insights on designing high-performance ECs for high-frequency applications.

15.
Small ; 20(19): e2308453, 2024 May.
Article in English | MEDLINE | ID: mdl-38221691

ABSTRACT

Despite great efforts on economical and functionalized carbon materials, their scalable applications are still restricted by the unsatisfying energy storage capability under high-rate conditions. Herein, theoretical and methodological insights for surface-to-bulk engineering of multi-heteroatom-doped hollow porous carbon (HDPC), with subtly designed Zn(OH)F nanoarrays as the template are presented. This fine-tuned HDPC delivers an ultrahigh-rate energy storage capability even at a scan rate of 3000 mV s-1 (fully charged within 0.34 s). It preserves a superior capacitance of 234 F g-1 at a super-large current density of 100 A g-1 and showcases an ultralong cycling life without capacitance decay after 50 000 cycles. Through dynamic and theoretical analysis, the key role of in situ surface-modified heteroatoms and defects in decreasing the K+-adsorption/diffusion energy barrier is clarified, which cooperates with the porous conductive highways toward enhanced surface-to-bulk activity and kinetics. In situ Raman aids in visualizing the reversibly dynamic adsorption/releasing of the electrolyte ions on the tailored carbon structure during the charge/discharge process. The potential of the design concept is further evidenced by the enhanced performances in water-in-salt electrolytes. This surface-to-bulk nanotechnology opens the path for developing high-performance energy materials to better meet the practical requirements in the future.

16.
Small ; 20(22): e2309176, 2024 May.
Article in English | MEDLINE | ID: mdl-38150625

ABSTRACT

Metal nanoclusters providing maximized atomic surface exposure offer outstanding hydrogen evolution activities but their stability is compromised as they are prone to grow and agglomerate. Herein, a possibility of blocking metal ion diffusion at the core of cluster growth and aggregation to produce highly active Ru nanoclusters supported on an N, S co-doped carbon matrix (Ru/NSC) is demonstrated. To stabilize the nanocluster dispersion, Ru species are initially coordinated through multiple Ru─N bonds with N-rich 4'-(4-aminophenyl)-2,2:6',2''-terpyridine (TPY-NH2) ligands that are subsequently polymerized using a Schiff base. After the pyrolysis of the hybrid composite, highly dispersed ultrafine Ru nanoclusters with an average size of 1.55 nm are obtained. The optimized Ru/NSC displays minimal overpotentials and high turnover frequencies, as well as robust durability both in alkaline and acidic electrolytes. Besides, outstanding mass activities of 3.85 A mg-1 Ru at 50 mV, i.e., 16 fold higher than 20 wt.% Pt/C are reached. Density functional theory calculations rationalize the outstanding performance by revealing that the low d-band center of Ru/NSC allows the desorption of *H intermediates, thereby enhancing the alkaline HER activity. Overall, this work provides a feasible approach to engineering cost-effective and robust electrocatalysts based on carbon-supported transition metal nanoclusters for future energy technologies.

17.
Small ; : e2406630, 2024 Oct 07.
Article in English | MEDLINE | ID: mdl-39375991

ABSTRACT

Owing to the low potential (vs K/K+), good cycling stability, and sustainability, carbon-based materials stand out as one of the optimal anode materials for potassium-ion batteries (PIBs). However, achieving high-rate performance and excellent capacity with the current carbon-based materials is challenging because of the sluggish reaction kinetics and the low capacity of carbon-based anodes. The doping of nitrogen proves to be an effective way to improve the rate performance and capacity of carbon-based materials as PIB anode. However, a review article is lacking in systematically summarizing the features and functions of nitrogen doping types. In this sense, it is necessary to provide a fundamental understanding of doped nitrogen types in nitrogen-doped(N-doped) carbon materials. The types, functions, and applications of nitrogen-doped carbon-based materials are overviewed in this review. Then, the recent advances in the synthesis, properties, and applications of N-doped carbon as both active and modification materials for PIBs anode are summarized. Finally, doped nitrogen's main features and functions are concluded, and critical perspectives for future research in this field are outlined.

18.
Small ; : e2405261, 2024 Sep 12.
Article in English | MEDLINE | ID: mdl-39263773

ABSTRACT

Lithium (Li) metal is considered a hopeful anode for next-generation Li-ion batteries thanks to its ultra-high theoretical specific capacity, extra-low theoretical density, and low negative potential. However, the uncontrolled growth of Li dendrites and volume fluctuation during plating/stripping processes severely hamper its commercial application. Herein, ZnS seeds sealed in N, P, S co-doped carbon hollow rhombic dodecahedra (ZnS@NPS-C HRD) is fabricated as a superlithiophilic host for Li metal anodes (LMAs) to solve the above problems. In addition, the Li nucleation and deposition mechanism on ZnS@NPS-C HRD is investigated by in situ optical microscopy, ex-situ X-ray diffraction, scanning electron microscopy, and theoretical calculations. Owing to the synergistic strategy of ZnS seeds-inducing nucleation and Li-limited growth, the as-prepared composite exhibits stability for 300 cycles in asymmetric cells and a long lifespan over 1100 h in symmetric cells. Moreover, the ZnS@NPS-C HRD@Li|LiFePO4 full cell demonstrates a reversible capacity of 100.91 mAh g-1 after 400 cycles at 1 C.

19.
Small ; 20(33): e2400374, 2024 Aug.
Article in English | MEDLINE | ID: mdl-38566523

ABSTRACT

Highly efficient water splitting electrocatalyst for producing hydrogen as a renewable energy source offers potential to achieve net-zero. However, it has significant challenges in using transition metal electrocatalysts as alternatives to noble metals due to their low efficiency and durability, furthermore, the reliance on electricity generation for electrocatalysts from fossil fuels leads to unavoidable carbon emissions. Here, a highly efficient self-powered water splitting system integrated is designed with triboelectric nanogenerator (TENG) and Ni3FeN@Fe24N10 catalyst with improved catalytic activity and durability. First, the durability of the Ni3FeN catalyst is improved by forming N, P carbon shell using melamine, polyetherimide, and phytic acid. The catalyst activity is improved by generating Fe24N10 in the carbon shell through the Kirkendall effect. The synthesized Ni3FeN@Fe24N10 catalyst exhibited excellent bifunctional catalytic activity (ηOER = 261.8 mV and ηHER = 151.8 mV) and remarkable stability (91.7% in OER and 90.5% in HER) in 1 m KOH. Furthermore, to achieve ecofriendly electricity generation, a rotation-mode TENG that sustainably generate high-performance is realized using butylated melamine formaldehyde. As a result, H2 is successfully generated using the integrated system composed of the designed TENG and catalyst. The finding provides a promising approach for energy generation to achieve net-zero.

20.
Small ; 20(31): e2311151, 2024 Aug.
Article in English | MEDLINE | ID: mdl-38456785

ABSTRACT

As vitally prospective candidates for next-generation energy storage systems, room-temperature sodium-sulfur (RT-Na/S) batteries continue to face obstacles in practical implementation due to the severe shuttle effect of sodium polysulfides and sluggish S conversion kinetics. Herein, the study proposes a novel approach involving the design of a B, N co-doped carbon nanotube loaded with highly dispersed and electron-deficient cobalt (Co@BNC) as a highly conductive host for S, aiming to enhance adsorption and catalyze redox reactions. Crucially, the pivotal roles of the carbon substrate in prompting the electrocatalytic activity of Co are elucidated. The experiments and density functional theory (DFT) calculations both demonstrate that after B doping, stronger chemical adsorption toward polysulfides (NaPSs), lower polarization, faster S conversion kinetics, and more complete S transformation are achieved. Therefore, the as-assembled RT-Na/S batteries with S/Co@BNC deliver a high reversible capacity of 626 mAh g-1 over 100 cycles at 0.1 C and excellent durability (416 mAh g-1 over 600 cycles at 0.5 C). Even at 2 C, the capacity retention remains at 61.8%, exhibiting an outstanding rate performance. This work offers a systematic way to develop a novel Co electrocatalyst for RT-Na/S batteries, which can also be effectively applied to other transition metallic electrocatalysts.

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