Cu-based catalysts attract considerable attention because of their exceptional CO2 photo-/electro-/thermo-reduction capacities, where Cu(I) is generally treated as the active species. However, a significant problem hindering the large-scale applications of Cu-based catalysts is the inactivation of Cu(I) via irreversible redox to Cu(II)/Cu(0). This study proposes a Cu(I) valence pinning method based on hydroxyapatite (HAP). Experimental and theoretical studies demonstrate that the phonon resonance among the Cu(I) ions, their adjacent heteroatoms, and the intermediates adsorbed at the Cu(I) sites yields Cu(I) valence electrons in their lowest energy states. Thus, Cu(I) is stabilized, stable, and efficient photothermal CO2 hydrogenation is promoted. However, because of the change of Cu(I) coordination environment during the CO2 hydrogenation reaction, Cu(I) ions migrate into the bulk phase, leading to activity attenuation. Nevertheless, Cu(I) ions can be pulled out to the surface of HAP under the oxidative humid air condition, and the catalytic activity can be easily recovered. Thus, we propose a simple cyclic reaction/regeneration process. This enables the Ca-5(FeCuCe)(5)-HAP catalyst to achieve the CO yield of 402.8 mmol g(-1) h(-1) and a CO2 conversion rate of 27.7%, which is close to the thermodynamic equilibrium. This catalyst also displays a selectivity of approximately 100% and cycle stability of 156 h at 500 degrees C under a pressure of 1 atmospheric. Our study provides a viable method for the scale applications of Cu(I) based catalysts in the negative carbon industries. (c) 2025 Science China Press. Published by Elsevier B.V. and Science China Press. All rights are reserved, including those for text and data mining, AI training, and similar technologies.

Engineering triple-phase boundaries in low Pt-loaded catalyst layers is highly desired yet challenging due to the poor Pt utilization caused by inhomogeneous Nafion ionomer coverage over catalyst nanoparticles and high mass transport resistance near catalyst surface. Herein, an effective Pt catalyst/support design strategy by using urea to modify the carbon supports is reported, in which the balance between nitrogen doping and Pt nanoparticle deposition can be well achieved without sacrificing catalyst performance. The nitrogen-modified carbon with the positively charged surface can electrostatically attract with ionomer with negative charges in a catalyst ink. Meanwhile, ionomer can be preserved into a solid catalyst layer, forming a desirable ionomer/catalyst interface with improved dry proton accessibility and lowered oxygen transport resistance. Consequently, this interface leads to striking performance improvement in the kinetic and mass transport regions in the membrane electrode assembly level, with the current density of 1.11 A cm-2 at 0.65 V under 50% RH and 85 degrees C operating conditions, reaching 2.8 times this value compared with the one without modification. The nitrogen-doped carbon with a positively charged surface can attract negatively charged Nafion ionomer via Coulombic interaction, allowing the realization of building an active triple-phase boundary at the Pt catalyst layer. With this ideal catalyst layer, better management of oxygen, electrons, and protons occurring on the triple-phase boundary gives rise to enhanced catalytic performance for proton exchange membrane fuel cells.image

High entropy alloys and metallic glasses, as two typical metastable nanomaterials, have attracted tremendous interest in energy conversion catalysis due to their high reactivity in nonequilibrium states. Herein, a novel nanomaterial, layered high entropy metallic glass (HEMG), in a higher energy state than low-entropy alloys and its crystalline counterpart due to both the disordered elemental and structural arrangements, is synthesized. Specifically, the MnNiZrRuCe HEMG exhibits highly enhanced photothermal catalytic activity and long-term stability. An unprecedented CO2 methanation rate of 489 mmol g-1 h-1 at 330 °C is achieved, which is, to the authors' knowledge, the highest photothermal CO2 methanation rate in flow reactors. The remarkable activity originates from the abundant free volume and high internal energy state of HEMG, which lead to the extraordinary heterolytic H2 dissociation capacity. The high-entropy effect also ensures the excellent stability of HEMG for up to 450 h. This work not only provides a new perspective on the catalytic mechanism of HEMG, but also sheds light on the great catalytic potential in future carbon-negative industry.

Despite stunning progress in single-atom catalysis (SAC), it remains a grand challenge to yield a high loading of single atoms (SAs) anchored on substrates. Herein, we report a one-step laser-planting strategy to craft SAs of interest under an atmospheric temperature and pressure on various substrates including carbon, metals, and oxides. Laser pulses render concurrent creation of defects on the substrate and decomposition of precursors into monolithic metal SAs, which are immobilized on the as-produced defects via electronic interactions. Laser planting enables a high defect density, leading to a record-high loading of SAs of 41.8 wt %. Our strategy can also synthesize high-entropy SAs (HESAs) with the coexistence of multiple metal SAs, regardless of their distinct characteristics. An integrated experimental and theoretical study reveals that superior catalytic activity can be achieved when the distribution of metal atom content in HESAs resembles the distribution of their catalytic performance in a volcano plot of electrocatalysis. The noble-metal mass activity for a hydrogen evolution reaction within HESAs is 11-fold over that of commercial Pt/C. The laser-planting strategy is robust, opening up a simple and general route to attaining an array of low-cost, high-density SAs on diverse substrates under ambient conditions for electrochemical energy conversion.

Developing active and cost-effective bifunctional electrocatalysts for overall water splitting is challenging but mandatory for renewable energy technologies. We report a high-entropy alloy (HEA) of PtIrCuNiCr as a bifunctional electrocatalyst for overall water splitting, which shows a low overpotential of ca. 190 mV at the current density of 10 mA cm-2. Compared with pure metals, HEAs exhibit remarkable surface strain due to severe lattice distortion in their crystal structures. Theoretical calculations reveal that the strain can regulate the binding energy of intermediates on catalysts by adjusting the metal-metal bonding energy. It pushes the HEA toward the top of volcano plots to achieve superior electrocatalytic activity for both hydrogen and oxygen evolution reactions. The strain effect of HEAs on electrocatalysis can be well engineered by tuning the catalyst radius or configurational entropy. This work renders a systematic strain regulation strategy for designing a high-performance HEA catalyst for overall water splitting.

There is an urgent demand for antibacterial bone grafts in clinics. Worryingly, the misuse and overuse of antibiotics accelerate the emergence of drug-resistant bacteria. Therefore, this study prepared a novel injectable bioceramic cement without antibiotics (FS-BCS), which showed good antibacterial properties by loading iron and strontium onto a matrix composed of brushite and calcium sulfate. The setting time, injectability, microstructure, antibacterial properties, anti-biofilm properties, and cytocompatibility of the novel bioceramic cement were evaluated thoroughly. The results showed that the material was highly injectable and antiwashout. The antibacterial tests revealed that FS-BCS inhibited the growth of 99.9% E. coli and S. aureus separately in the broth due to the synergistic effect of strontium and iron. Simultaneously, crystal violet and fluorescent staining tests revealed that the material could significantly inhibit the formation of E. coli and S. aureus biofilms. In addition, the co-incorporation of iron and strontium promoted the proliferation and migration of osteoblasts. Therefore, FS-BCS has good application potential in antibiotic-free anti-infection bone grafting using minimally invasive surgery.

An intrinsic Faradaic layer on the surface of a metal electrocatalyst is usually considered an active site for CO2 reduction. Different strategies have been used to improve the performance of CO2 reduction by adjusting the intrinsic Faradaic layer. However, it is still challenging to achieve CO2 reduction with high activity, selectivity, and stability. In this study, for the first time, we improve the three parameters simultaneously by introducing a Zn(OH)(x) over layer onto a CuSn electrocatalyst. We find that the intrinsic Faradaic layer of Sn(OH)(x) on the surface of CuSn provides active sites for CO2 reduction, while Zn(OH)(x) plays multiple roles as an adsorption/activation layer, a cover layer, and a protective layer. Further studies suggest that the enhanced activity comes from a Faradaic reaction of Zn(OH)(x) during CO2 reduction, which can be considered as an extrinsic Faradaic layer. This new strategy of introducing an extrinsic Faradaic layer can deepen understanding of electrocatalytic process and offers guidance to design other high-performance electrocatalysts. [GRAPHICS] .

Since the beginning of the 21st century, energy shortage and environmental pollution have been the major challenges faced by human beings.Photocatalytic carbon dioxide (CO 2 ) reduction is one of the promising strategies to solve the energy crisis and promote the carbon cycle, in which semiconductor captures solar energy to obtain hydrocarbon fuel.However, the low activity and poor selectivity of the products greatly limit the practical application of this technology.Thus, it is of great significance to regulate product selectivity, improve photocatalytic efficiency, and deeply understand the mechanism of CO 2 reduction reaction.In recent years, ultrathin materials have attracted extensive attention from researchers due to their high specific surface area, abundant unsaturated coordination surfaceatoms, shortened charge migration path from inside to surface, and tailorable energy band structure, and have achieved promising results in the field of photocatalytic CO 2 reduction.In this paper, the reaction mechanism of photocatalytic CO 2 reduction is firstly summarized.Next, the research results of promoting electron hole separation and regulating charge transport path of ultrathin nanostructures by constructing heterostructures, designing Z-scheme systems, introducing cocatalysts, and defect engineering are introduced.Finally, the prospect and challenge of improving the efficiency of photocatalytic CO 2 reduction and optimizing the product selectivity are pointed out.

The photothermal effect has recently been applied to oxygen evolution reaction (OER) electrodes, which can effectively convert solar energy into heat to promote the reaction kinetics. However, optimized materials that can more efficiently collect and utilize solar energy are demanded. Here, inspired by the thermal insulation ability of polar bear hairs, we fabricated a villous carbon frameworks (VCF) embedded with FeNi3 alloys. Under illumination, the achieved local temperature surpassed the bare carbon frameworks (CF). This highly promoted the OER performance of the inner electrocatalysts. With light illumination intensity of 0.25 W cm(-2), the VCF demonstrated an overpotential of 194 mV to deliver 100 mA cm(-2) current density. The current density at 1.45 V could reach over 300 mA cm(-2), about 8.5-fold of that without illumination, outperforming traditional photothermal electrocatalysts. Meanwhile, quasi-operando soft X-ray absorption spectroscopy (SXAS) manifested that the photothermal effect of the VCF would boost the electron rearrangement of iron-nickel species during OER and optimize the adsorption of oxygen intermediates. Our design principle was transferable to other catalysts whose performance could be accelerated by the photothermal effect.

Photocatalytic materials absorb photons ranging from the ultraviolet to near-infrared region to initiate photocatalytic reactions and have broad application prospects in various fields. However, high-energy ionizing radiations are rarely involved in photocatalytic research. In this study, we proposed a high-energy radiation-based photocatalysis method, namely "radiocatalysis", and prepared a TiO2-coated lanthanide pyrosilicate scintillator (LnPS@TiO2) as the radiocatalytic material. The lanthanide pyrosilicate post-radiation scintillators can efficiently convert radiation energy into ultraviolet energy, which can be resonantly transferred to TiO2 to selectively generate high-yield superoxide radicals (). Compared with traditional radiotherapy, this radiocatalytic process can significantly kill cancer cells while achieving long-term DNA damage by inhibiting the DNA self-repair process. Our research expands the energy response range of photocatalysis and is expected to extend radiocatalysis to the tumor treatment field.

High-entropy materials, which include high-entropy alloys and high-entropy ceramics, show promise for their use in many fields, yet a robust synthesis strategy is lacking. Here we present a simple and general approach, laser scanning ablation, to synthesize a library of high-entropy alloy and ceramic nanoparticles. The laser scanning ablation method takes only five nanoseconds per pulse to ablate the corresponding nanoparticle precursors at atmospheric temperature and pressure. The ultrarapid process ensures that dissimilar metallic elements combine regardless of their thermodynamic solubility. As a laser pulse confines energy to the desired microregions, the laser scanning ablation method renders a high-entropy material nanoparticle loading on various substrates, which include thermally sensitive substrates. Applied as electrocatalysts for overall water splitting, the as-prepared high-entropy material nanoparticles can achieve an overpotential of 185 mV @ 10 mA cm–2. This versatile strategy enables the preparation of materials useful for a range of fields, such as biomedicine, catalysis, energy storage and sensors. High-entropy materials are used in a range of applications but their synthesis at the nanoscale remains challenging. Now, a robust and general strategy to prepare high-entropy alloy and ceramic nanoparticles has been developed using laser scanning ablation. This approach takes only five nanoseconds per pulse to ablate precursors at atmospheric temperature and pressure.

Energy band alignment theory has been widely used to understand interface charge transfer in semiconductor/semiconductor heterojunctions for solar conversion or storage, such as quantum-dot sensitized solar cells, perovskite solar cells and photo(electro)catalysis. However, abnormally high open-circuit voltage and charge separation efficiency in these applications cannot be explained by the classic theory. Here, we demonstrate a Faradaic junction theory with isoenergetic charge transfer at semiconductor/semiconductor interface. Such Faradaic junction involves coupled electron and ion transfer, which is substantively different from the classic band alignment theory only involving electron transfer. The Faradaic junction theory can be used to explain these abnormal results in previous studies. Moreover, the characteristic of zero energy loss of charge transfer in a Faradaic junction also can provide a possibility to design a solar conversion device with a large open-circuit voltage beyond the Shockley-Queisser limit by the band alignment theory.

Bi based electrocatalysts for CO2 reduction have recently attracted much research attention. Although Cu substrates were mainly used in these material investigations, whether the Cu substrates act as the CO2 reduction electrocatalysts is questionable, and yet disregarded. Herein to comprehensively investigate the influence of Cu substrate on the electrochemical performance, we electro-deposited Bi catalysts on Cu foams. It was found that during the whole process, the morphology and composition of Bi/Cu electrocatalysts varied, indicating that Cu acted as not only the electrode substrates but also the active materials for CO2 reduction. After optimization, Bi/Cu materials achieved high activity of 59.7 mA cm(-2) and selectivity of 95% for CO2 converted formate. Our work provides experimental evidence for the material design and optimization of Bi-based materials for CO2 reduction.

Aerospace milestones in human history, including returning to the moon and manned Martian missions, have been implemented in recent years. Space exploration has become one of the global common goals, and to ensure the survival and development of human beings in the extraterrestrial extreme environment has been becoming the basic ability and technology of manned space exploration. For the purpose of fulfilling the goal of extraterrestrial survival, researchers in Nanjing University and the China Academy of Space Technology proposed extraterrestrial artificial photosynthesis (EAP) technology. By simulating the natural photosynthesis of green plants on the Earth, EAP converts CO2/H2O into fuel and O2 in an in-situ, accelerated and controllable manner by using waste CO2 in the confined space of spacecraft, or abundant CO2 resources in extraterrestrial celestial environments, e.g. Mars. Thus, the material loading of manned spacecraft can be greatly reduced to support affordable and sustainable deep space exploration. In this paper, EAP technology is compared with existing methods of converting CO2/H2O into fuel and O2 in the aerospace field, especially the Sabatier method and Bosch reduction method. The research progress of possible EAP materials for in-situ utilization of extraterrestrial resources are also discussed in depth. Finally, this review lists the challenges that the EAP process may encounter, which need to be focused on for future implementation and application. We expect to deepen the understanding of artificial photosynthetic materials and technologies, and aim to strongly support the development of manned spaceflight.

High-entropy materials (HEMs) with unique configuration and physicochemical properties have attracted intensive research interest. However, 2D HEMs have not been reported yet. To find out unique properties of combining 2D materials and HEMs, a series of 2D high-entropy hydrotalcites (HEHs) is created by coprecipitation method, including quinary, septenary, and even novenary metallic elements. It is found that the fast synthetic kinetics of coprecipitation process conquers the thermodynamically solubility limitation of different elements, which is the prerequisite condition to form HEHs. As the oxygen evolution reaction (OER) electrocatalysts, HEHs show significantly decreased apparent activation energy compared with low-entropy hydrotalcites (LEHs) due to the lattice distortion induced by the multimetallic character of HEHs. This work opens up a new avenue for the development of 2D HEMs, which broadens the family of HEMs and presents a most promising platform for exploring the unknown properties of HEMs.

Developing highly active,cost-effective,and environmental friendly oxygen evolution reaction(OER)electrocatalysts facilitates various(photo)electrochemical processes.In this work,Fe 3 N nanoparticles encapsulated into N-doped graphene nanoshells(Fe 3 N@NG) as OER electrocatalysts in alkaline media were reported.Both the experimental and theoretical comparison between Fe 3 N@NG and Fe 3 N/NG,specifically including in situ Mossbauer analyses,demonstrated that the NG nanoshells improved interfacial electron transfer process from Fe 3 N to NG to form high-valence Fe 4+ ions(Fe 4+ @NG), thus modifying electronic properties of the outer NG shells and subsequently electron transfer from oxygen intermediate to NG nanoshells for OER catalytic process.Meanwhile,the NG nanoshells also protected Fe-based cores from forming OER inactive and insulated Fe 2 O 3 ,leading to high OER stability.As a result,the as-formed Fe 4+ @NG shows one of the highest electrocatalytic efficiency among reported Fe-based OER electrocatalysts,which can as well highly improve the photoelectrochemical water oxidation when used as the cocatalysts for the Fe 2 O 3 nanoarray photoanode.

Thin-film graphene/polymer nanocomposite sensors have been shown to be exceptionally sensitive to ultrasonic waves, making them promising next-generation candidates for structural integrity monitoring. However, the ultrasonic sensing mechanism of these sensors has never been scrutinized, restricting the deployment of these sensors to real-life applications. Herein, we carry out the first-ever study on the ultrasonic sensing mechanism of thin-film graphene/polymer nanocomposite sensors, through complementary physical experiments and analytical modelling. At first, sensors were precisely fabricated from nanofillers of different sizes and different matrix materials, and their electrical conductivities and ultrasonic sensitivities were measured. Analytical models that are based on the effective medium theory and the various contact modes between graphene nanofillers, entailing interphase regions and the quantum tunneling effect, were then established and fitted to the experimental results to reveal a series of microscopic characteristics of the sensors fabricated. Through a systematic analysis, it was found that the sizes of nanofillers and the properties of matrices significantly influence the microscopic morphologies and strain-induced dynamics of the sensors, in turn dictating their electrical conductivities and ultrasonic sensitivities. This insightful study will serve as the foundation for realizing applications of high-sensitivity thin-film graphene/polymer nanocomposite sensors in real-life ultrasound-based structural integrity monitoring scenarios.

Green production of NH 3 , especially the Li-mediated electrochemical N 2 reduction reaction (NRR) in non-aqueous solutions, is attracting research interest. Controversies regarding the NRR mechanism greatly impede its optimization and wide applications. To understand the electrocatalytic process, we treated Au coated carbon fibrous paper (Au/CP) as the model catalyst. In situ XRD confirmed the transformation of lithium intermediates during NRR. Au greatly improved electron transfer kinetics to catalyze metallic Li formation, and accordingly highly accelerated spontaneous NRR. The Faradaic efficiency of NRR on Au/CP reached 34.0 %, and NH 3 yield was as high as 50 μg h −1  cm −2 . Our research shows that the key step of Li-mediated non-aqueous NRR is electrocatalytic Li reduction and offers a novel electrocatalyst design method for Li reduction.

21世纪以来,随着CO2为主的温室气体排放量不断增加,寻求新型能源来构建低碳型社会的诉求越来越迫切.其中以太阳能驱动转化CO2为碳氢燃料的技术,可将CO2转化成甲烷、甲醇、甲酸或C2+等高附加值的碳氢燃料,是实现全球碳平衡的有效途径之一,具有巨大潜力.半导体材料是决定光催化还原CO2过程进行的重要因素之一,因此探索和开发高效光催化功能材料是当今研究的主要方向.本文综述了近几年来作者课题组在光催化还原CO2为碳氢燃料方面的重要研究进展,主要涉及TiO2基系列光催化材料,V、W、Ge、Ga、C3N4基等系列光催化材料的结构组分调控.

This review highlights the impacts of four core effects (i.e. high entropy, cocktail effect, lattice distortion and sluggish diffusion) and the microstructures of HEAs on their catalytic properties.