Lithium-sulfur (Li-S) batteries are considered a leading candidate for advanced energy storage applications, primarily because of their exceptional energy density. However, their commercialization remains challenged by persistent obstacles, including slow reaction kinetics, volumetric electrode changes, and shuttle effects. Herein, a novel configuration of Li-S batteries is proposed. It is constructed by a S-free cathode, a polypropylene (PP) separator modified by CMK-3, and an electrolyte containing Li2S6. This simplifies the fabrication process of Li-S batteries, greatly improving active material utilization and mitigating the shuttle effect. The porous cathode effectively absorbs long-chain polysulfides and facilitates their redox. Similarly, the CMK-3 modified separator can also serve as a second reaction field, which suppresses polysulfide shuttle and enhances the utilization efficiency of active materials. The results indicate that under the synergistic effects of the S-free cathode and modified separator, the batteries exhibit excellent performance at low temperature or high rate. The fabricated batteries exhibit an initial capacity of 1082 mAhu2219gu22121 at 2 C, and retain 906 mAhu2219gu22121 after 200 cycles. Furthermore, these batteries demonstrate a discharge capacity reaching 1189 mAhu2219gu22121 at u221215 u00B0C and 0.1 C. This method introduces an innovative approach to simplify the preparation process of Li-S cathodes.

Metal-organic framework (MOF) membranes have emerged as promising candidates for hydrogen separation, but the fabrication of defect-free and flexible MOF membranes is still challenging. Here, we propose a thermally induced in-situ growth strategy to develop flexible membranes consisting of amorphous Zn-2-methylimidazole complex (a-Zn-MeIM) and crystalline zeolitic imidazolate framework-8 (c-ZIF-8) on polysulfone substrate, denoted as amorphous Zn-MeIM/crystalline ZIF-8 (a-Zn-MeIM/c-ZIF-8) membranes. During the thermal treatment of pre-sprayed mixture containing a-Zn-MeIM on the top surface of polysulfone substrate, a-Zn-MeIM is converted to c-ZIF-8. Similar coordination environments featured with Zn2+-2-methylimidazolate coordination configurations between flexible a-Zn-MeIM and rigid c-ZIF-8 provides enhanced interfacial compatibility, effectively eliminating cracks and grain boundary defects. Benefitting from both the flexibility of amorphous phase and well-defined pore structure of crystalline phase, the resulting a-Zn-MeIM/c-ZIF-8 membranes show flexibility and preferential diffusion of H2 molecules. The membrane structure can be modulated by adjusting cZIF-8 concentration of sprayed colloid and thermal treatment temperature. The optimized a-Zn-MeIM/c-ZIF-83.75 membrane with flexibility exhibits a H2/CH4 mixed separation selectivity up to 96.9 at 90 degrees C. Additionally, a-ZnMeIM/c-ZIF-83.75 membrane with an area of 644 cm2 has been prepared, promoting the practical applications of MOF membranes with good processability.

Solid-state lithium batteries (SSLBs) have attracted much attention due to their good thermal stability and high energy density. However, solid-state electrolytes with low conductivity and prominent interfacial issues have hindered the further development of SSLBs. In this research, inspired from a selective confinement structure of anions, a novel HMOF-DNSE composite solid electrolyte with a dual selective confinement interface structure is proposed based on the semi-interpenetrating structure generated by poly(vinylidene fluoride)-hexafluoropropylene (PVDF-HFP), poly(di-n-butylmethylammonium) bis(trifluoromethanesulfonyl)imide (PDADMATFSI), and a metal-organic frameworks MOF derivative (HMOF) as a filler. The dual-network structure of PVDF-HFP/PDADMATFSI combined with HMOF formed a dual selective confinement interface structure to confine out the movement of large anions TFSI-, thereby enhancing the transfer ability of Li+. Subsequently, the addition of HMOF further improves the transfer of Li+ by binding up TFSI- through its crystal structure. The results show that HMOF-DNSE possesses a high room-temperature ionic conductivity (0.7 mS cm-1), a wide electrochemical window (up to 4.5 V), and a high Li+ transfer number (tLi+) (0.56). LiFePO4/HMOF-DNSE/Li cell shows an excellent capacity of 141.5 mAh g-1 at 1C rate under room temperature, with a high retention of 80.1% after 500 cycles. The material design strategy, which is based on selective confinement interface structures of anions, offers valuable insights into enhancing the electrochemical performance of solid-state lithium batteries.

In order to pursue optimize antifouling performance and protect the metal substrate from direct contact with external environment, the sodium chloride (NaCl) modified cuprous oxide (Cu2O)/Biochar (BC)/styrene-acrylic (SA)-SA double-layer coatings with the effective and controllable release rate of Cu2+ were prepared. The NaCl particles were dispersed and dissolved in the Cu2O/BC/SA layer (the functional layer) as the pore-forming agent, which can increase the contact between Cu2O/BC and external environment in order to control the release rate of Cu2+ of coatings. A large capacity photobioreactor was designed to conduct adhesion tests of marine microalgae Nannochloropsis oceanica (N. oceanica) and fresh Chlorella vulgaris (C. vulgaris) on the coatings, aiming to evaluate the antifouling performance. Results show that the Cu2O/BC/SA-SA coating modified with 3 wt% NaCl possesses the best antifouling property, which is 63.7 % higher than that of unmodified coating and 92.8 % higher than that of pure SA membrane.

Amorphous metal‐organic frameworks (MOFs) with aperiodic atomic arrangements, featuring high intrinsic activity and rich active sites, have emerged as promising oxygen evolution reaction (OER) catalysts. However, the quantitative structure‐activity relationships (SARs) that determine the OER activity, the key to a rational catalyst design, remain unresolved. Inspired by controllable amorphization engineering, the amorphous MOF structures are rationally constructed as an ideal platform to explore the SAR in catalyzing OER. The mechanistic studies show that the OER activity could be volcano‐shape correlated with either constant adsorption energy difference between OOH* and O* (Δ G OOH* − Δ G O* ) or the position of the d band center. The amorphous MOF (Ni 8 Co 2 ‐BDC), situated close to the volcano summit, possesses an appropriate E d energy level, which exhibits the balanced intermediates adsorption/desorption ability and consequently results in the boosted catalytic activity and long‐term stability. This work supplies new perspectives to investigate the SAR in amorphous MOF structures, thereby guiding the rational design of advanced OER catalysts.

In lithium-sulfur batteries, the shuttling effect and sluggish redox conversion of soluble polysulfides lead to unsatisfactory sulfur utilization and capacity retention. In this research, we used a one-pot hydrothermal method to prepare graphene with single-atom Co and B, N codoped as a sulfur host in Li-S batteries, thereby suppressing the shuttling effect and facilitating the redox conversion of lithium polysulfides (LiPSs). A series of characterizations demonstrated that dual doping of B and N introduces more lattice defects and structural deformations in graphene oxide, thus enhancing its adsorption of polysulfides. Simultaneously, single-atom cobalt can also polarize adsorption and accelerate the conversion reaction of LiPSs. The Li-S cell with the as-prepared Co-BN-G sulfur host materials exhibited an excellent capacity of 1034 mAh g(-1) at 0.5 C and satisfactory cycle performance (retention of 69% over 500 cycles). Even at a rate of 2 C, a discharge capacity of 851 mAh g(-1) is achieved. The results show that the Co-BN-G configuration efficiently captures LiPSs and enhances their rate conversion kinetics in redox reactions, demonstrating significant practical potential.

Integrating dual sites of hydrazine oxidation reaction (HzOR) and hydrogen evolution reaction (HER) into a catalyst is highly desirable for energy-saving hydrogen production but remains challenges. Herein, we fabricate a heterogeneous nanowire array consisting of CoP and N-doped Ni5P4 on carbon fiber paper (N-Ni5P4@CoP/CFP), in which the N atoms can be selectively incorporated into Ni5P4 to change the Ni coordination that can regulate interfacial electronic field and thus improve the charge transfer from CoP to N-Ni5P4. Such an interfacial charge redistribution can induce the formation of well-defined electrophilic and nucleophilic sites, which could optimize hydrazine dehydrogenation kinetics and hydrogen adsorption free energy (ΔGH*), thus achieving splendid HzOR and HER activities. The commercial solar cells and homemade lemon batteries driven overall hydrazine splitting (OHzS) electrolyzer inspires its practical applications. Integrating the electrophilic and nucleophilic dual sites via interfacial electronic field regulation provides a new inspiration for efficiently catalyzing HzOR and HER.

Large-scale industrial application of urea electrolysis has prompted one to explore inexpensive and efficient urea oxidation reaction (UOR) catalysts that can achieve large current densities (>= 500 mA cm-2) at relatively low potentials. In response, for the first time the robust UOR catalysts are developed via in-situ construction of the Fe -doped Ni12P5/Ni3P heterojunction nanosheets on the macroporous 3D NiFe foam skeleton (denoted as Fe-(Ni12P5/Ni3P)). The introduction of Fe element can not only strengthen the interfacial electric field and induce the spontaneous charge redistribution for heterogeneous Ni12P5/Ni3P, but also effectively lower the reaction energy barrier during stepwise UOR process. Benefiting from the unique ultra-thin nanosheets and the optimized electronic structure, the well-designed Fe-(Ni12P5/Ni3P) possesses more exposed active sites and faster electron and mass transfer, thus exhibiting superior catalytic UOR activity. Encouragingly, the Fe-(Ni12P5/Ni3P) can deliver the industrial-level current density of 800 mA cm-2 just at 1.4 V as well as a splendid Tafel slope of 28.2 mV dec- 1. This catalyst also manifests remarkable durability under high current densities. As a consequence, our work opens up a brand-new-path in rational design of excellent UOR catalysts with high activity and stability to enable energy-saving electrolytic hydrogen production on industrial scale.

Deliberate modulation of the electronic structure via interface engineering is one of promising perspectives to build advanced catalysts for urea oxidation reaction (UOR) at high current densities. However, it still remains some challenges originating from the intrinsically sluggish UOR dynamics and the high energy barrier for urea adsorption. In response, we report the coupled NiSe 2 nanowrinkles with Ni 5 P 4 nanorods heterogeneous structure onto Ni foam (denoted as NiSe 2 @Ni 5 P 4 /NF) through successive phosphorization and selenization strategy, in which the produced closely contacted interface could provide high-flux electron transfer pathways. Theoretical findings decipher that the fast charge transfer takes place at the interfacial region from Ni 5 P 4 to NiSe 2 , which is conducive to optimizing adsorption energy of urea molecules. As expected, the well-designed NiSe 2 @Ni 5 P 4 /NF only requires the low potential of 1.402 V at the current density of 500 mA·cm −2 . More importantly, a small Tafel slope of 27.6 mV·dec −1 , a high turnover frequency (TOF) value of 1.037 s −1 as well as the prolonged stability of 950 h at the current density of 100 mA·cm −2 are also achieved. This study enriches the understanding on the electronic structure modulation via interface engineering and offers bright prospect to design advanced UOR catalysts.

Single-atom catalysts (SACs) have received considerable attention in hydrogenation of nitroaromatic compounds to aromatic amines. In order to enhance the exposure of single atoms and overcome the mass transfer limitation, construction of hierarchical porous supports for single atoms is highly desirable. Herein, we report a straightforward method to synthesize Co single-atoms supported on a hollow-on-hollow structured carbon monolith (Co 1 /HOHC-M) by pyrolysis of α-cellulose monolith loaded with PS-core@ZnCo-zeolite imidazolate frameworks-shell nanospheres (PS@Zn-ZIFs/α-cellulose). The hollow-on-hollow structure consists of a large hollow void with a diameter of ~ 290 nm (derived from the decomposition of polystyrene (PS) nanospheres) and a thin shell with hollow spherical pores with a diameter of ~ 10 nm (derived from the evaporation of ZnO nanoparticles that are in-situ formed during pyrolysis in the presence of CO 2 from α-cellulose decomposition). Benefitting from the hierarchically porous architecture, the Co 1 /HOHC-M exhibits excellent catalytic performance (reaction rate of 421.6 mmol·g Co −1 ·h −1 ) in the transfer hydrogenation of nitrobenzene to aniline, outperforming the powdered sample of Co 1 /HCS without the hollow spherical mesopores (reaction rate of 353.8 mmol·g Co −1 ·h −1 ). It is expected that this strategy could be well extended in heterogeneous catalysis, given the wide applications of porous carbon-supported single-atom catalysts.

Substrata selection is a key problem for engineering application of microalgae biofilm attached cultivation technology. In this work, 40 kinds of mortar plates with different surface patterns were fabricated and evaluated using Spirulina platensis biofilm cultivation. Results show surface patterns have great influences on S. platensis cultivation behaviors. Surface pitted patterns have the highest algal holding capacities, furrowed patterns are the second and bossed patterns are the lowest. After three days of cultivation, furrow patterned mortar plates have the fastest growth rate ranging at 13- 15 g m(-2) d(-1), the highest surface coverage ratio over 99 % and the strongest water erosion resistibility. Pit patterned mortar plates are the second, while surface bossed patterns are the worst, having the slowest grow rate, only 85-93 % surface coverage and more than 40- 50 % water erosion ratio. The surface furrow patterned mortar plates are the best engineerable supporting materials for S. platensis biofilm attached cultivation. A mathematical model has been constructed and successfully simulated the complex processes of S. platensis biofilm cultivation from inoculation adhesion, growth to biofilm development and water erosion.

In order to alleviate some disadvantages such as slow switch speed, small light modulation, and poor cycle stability, which hinder the large-scale application of electrochromic (EC) materials, element doping has become one of important routes to improve their microstructure and performance. In this work, tin-doped nickel oxide (Sn-doped NiO) porous EC films were prepared, and the influence of Sn-doping amount on the microstructure and EC performance of NiO films was investigated by comparing with undoped NiO film. Based on the electrochemical tests and energy-band structure analyses, the influence mechanism of Sn doping was discussed. The results show that the Sn doping changed the surface energy of NiO nanoparticles, and then changed the microstructure, increased the diffusion rate of ions, and improved the light modulation of NiO films obviously. And the Sn doping reduced the interface barrier of FTO/NiO heterojunction, resulting into the rapid EC response. The Sn-doped NiO film with doping amount of 10.0 mol.% showed the best EC properties, including large light modulation (64.1% at 550 nm), short response time (0.4 s for bleaching time and 3.0 s for coloring time), high coloration efficiency (48.9 cm2 C-1), and long cycle life (30000 cycles), and its semiconductor type changed into n-type from the p-type of undoped NiO film.

The fundamental understanding of the transition from a homogeneous nanostructure to a heterogeneous one is essential for controllably exploiting the heterostructure catalysts, however, it still remains a challenge. Herein, through simply tailoring the selenization temperature, for the first time we achieve the controllable transition engineering from the homogeneous NiSe2 nanowrinkles (NiSe2 NWs) to heterogeneous Ni3Se4/NiSe2 nanorods (Ni3Se4/NiSe2 NRs) on Ni foam substrate. The unique rod-like nanoarray architecture with high surface roughness can greatly improve the mass transport efficiency. More importantly, the density function theory calculations decipher that the electron redistribution spontaneously takes place at the interfacial region between Ni3Se4 and NiSe2, which could optimize the adsorption/desorption of reaction intermediates and decrease the Gibbs free energy of rate determining step for urea oxidation reaction (UOR). As a consequence, the heteroge-neous Ni3Se4/NiSe2 NRs manifests superior UOR performance than its counterpart of homogeneous NiSe2 NWs, especially at large current densities.

A robust NiS2/polyvinylpyrrolidone/(CuIn)(0.2)Zn1.6S2 (NiS2/PVP/CIZS) photocatalyst was successfully synthesized through a sequential hydrothermal treatment. Firstly, the addition of PVP reduces the size of CIZS nanoparticles, resulting in appearing surface effect, and hence an improvement of chemical activity. Moreover, the small size of PVP/CIZS possesses a shorten transfer distance of photo-induced carriers. The photocatalytic H-2 evolution rate of 0.8 g PVP/CIZS elevates to 3112.7 mmol/g/h under visible light. After coupling with NiS2, the light absorption range and separation efficiency of photo-induced carriers for NiS2/PVP/CIZS composites have been elevated and the optimal photocatalytic hydrogen evolution rate of 15% NiS2/PVP/CIZS reaches up to 5369.4 mmol/g/h. There forms a type II heterostructure on NiS2/PVP/CIZS, and the heterostructure facilitates to suppress the recombination and elevate the separation of photo generated electrons and holes. Therefore, the synergistic effect of size control and constructing a type II heterostructure with NiS2 on PVP/CIZS floriform photocatalyst helps to enhance photocatalytic performance of the composites. This work opens up a new way to prepare highly efficient photocatalysts under visible light. (C) 2022 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Biofouling by microalgae and other organism is a harmful phenomenon shared among all floating and subwater facilities. Using the antifouling coatings is the major measure to reduce the adhesion. This paper reports a kind of composite coating made of cuprous oxide (Cu2O), biochar and styrene-acrylic (SA) resin. Microalgae Spirulina platensis was used to prepare the biochar by pyrolysis, and then different amount of Cu2O particles were loaded on the biochar by chemical liquid deposition. Greater specific surface area to 181.3 m2 center dot g(-1)of the Spirulina platensis biochar was obtained after pyrolysis at 600 degrees C. Cubic Cu2O particles with the size of about 100-200 nm were uniformly deposited in the folds and pores of the biochar. The SA composite coating has a faster release of Cu2+ to maintain about 60 mu g center dot L-1 with a longer term compared those SA coatings without biochar. Adhesion experiments with microalgae Chlorella vulgaris and Nannochloropsis oceanica showed that the antifouling efficiencies increased 49.1%, 30.3% for the Cu2O loaded SA coatings (0.05 wt%), and 93.0%, 92.8% for the Cu2Obiochar-SA composite coatings respectively. The synergistic effect of the biocide of copper ions and the photocatalysis of Cu2O improved by compositing with biochar contribute to the promotion of the antifouling performance.

In this paper, the non-contact ZnO@NiO core-shell rod array films with black-white electrochromic performance were designed and constructed by electrochemical deposition method. The blank porous NiO films were also prepared for comparison. The morphology, component and microstructure of the films were characterized using X-ray diffractometer (XRD), scanning electron microscope (SEM) and high resolution transmission electron microscope (HRTEM). And their electrochromic (EC) performance was examined. The results show that the ZnO transition layer presents a hexagonal rod array nature, which is approximately perpendicular to the surface of substrate, thus, offered a three-dimensional frame for the growth of porous NiO. The ZnO@NiO film is composed of a large number of non-contact core-shell rods. The introduction of ZnO rod array transition layer not only led to the improvement of film/substrate connection but also resulted into the high EC performance including sharp black-white contrast, rapid switch speed and good stability. The heterojunction and P-N junction formed at the SnO2/ZnO/NiO interfaces might also play a role in the EC performance.

An enhanced OER catalyst based on Fe doped CePO4 exhibits higher turnover frequency, more active sites and more oxygen vacancies than CePO4.

To simultaneously achieve high power density and robust stability under high current density for neutral Zn-air batteries (ZABs), it is significant yet still remains challenging for the rational design of advanced air-cathode electrocatalyst with fast electron transfer, rapid oxygen/electrolyte transport and timely water removal. Herein, we synthesized the single Co atoms embedded in sandwich-like multimodally porous N-doped dual-carbon architecture (denoted as the NMCS-rGO-Co) via a facile self-assembly method and subsequent pyrolysis strategy. By taking advantage of abundant Co-N4 active sites and the optimized multimodally porous structure, the obtained NMCS-rGO-Co catalyst possesses stable three-phase reaction interfaces (catalysts, electrolyte and oxygen), which could be beneficial to simultaneously achieving fast electron transfer, accelerated oxygen/electrolyte diffusion and timely water removal. In response, the NMCS-rGO-Co catalyst displays excellent ORR performance in neutral electrolyte. More importantly, the NMCS-rGO-Co-based neutral ZABs exhibit the robust stability accompanied with continuously discharging for 36 h under high current density of 50 mA cm-2. This is the first time to rationally design efficient catalysts for achieving the long-term stability of neutral ZABs at high current density from the perspective of constructing stable three-phase interfaces. This work also sheds new lights on the development of neutral ORR catalysts for the application of sustainable energy conversion technologies. Superscript/Subscript Available

Two kinds of core–shell composite particles, i.e., mesoporous-SiO2@Cu (m-SiO2@Cu) and mesoporous-SiO2@TiO2@Cu (m-SiO2@TiO2@Cu) microspheres, were synthesized by coating Cu nanoparticles on the surfaces of m-SiO2 and m-SiO2@TiO2 microspheres. Results show that the m-SiO2 spheres have rougher surfaces and larger specific surface areas than the SiO2 microspheres. Compared with the m-SiO2@Cu microsphere, the m-SiO2@TiO2@Cu microsphere has a hollow structure. Both catalysts showed high catalytic activity to degrade methyl violet and methylene blue dyes. The degradations of two dyes using the m-SiO2@Cu approached 100% after 30 min, while it is slightly less, around 90% for the m-SiO2@TiO2@Cu. The catalytic activity of m-SiO2@Cu lies in Cu nanoparticles, which have large specific surface areas and are insensitive to light. The catalytic activity of m-SiO2@TiO2@Cu not only lies in Cu nanoparticles, but also in TiO2, which is sensitive to light. What’s more, Cu and TiO2 work as metal/semiconductor heterojunction, which enhances the electron–hole separation in m-SiO2@TiO2@Cu.