Bioorthogonal Cu Single-Atom Nanozyme for Synergistic Nanocatalytic Therapy, Photothermal Therapy, Cuproptosis and Immunotherapy.

Single-atom nanozymes (SAzymes) with atomically dispersed active sites are potential substitutes for natural enzymes. A systematic study of its multiple functions can in-depth understand SAzymes's nature, which remains elusive. Here, we develop a novel ultrafast synthesis of sputtered SAzymes by in situ bombarding-embedding technique. Using this method, sputtered copper (Cu) SAzymes (CuSA) is developed with unreported unique planar Cu-C3 coordinated configuration. To enhance the tumor-specific targeting, we employ a bioorthogonal approach to engineer CuSA, denoted as CuSACO. CuSACO not only exhibits minimal off-target toxicity but also possesses exceptional ultrahigh catalase-, oxidase-, peroxidase-like multienzyme activities, resulting in reactive oxygen species (ROS) storm generation for effective tumor destruction. Surprisingly, CuSACO can release Cu ions in the presence of glutathione (GSH) to induce cuproptosis, enhancing the tumor treatment efficacy. Notably, CuSACO's remarkable photothermal properties enables precise photothermal therapy (PTT) on tumors. This, combined with nanozyme catalytic activities, cuproptosis and immunotherapy, efficiently inhibiting the growth of orthotopic breast tumors and gliomas, and lung metastasis. Our research highlights the potential of CuSACO as an innovative strategy to utilize multiple mechanism to enhance tumor therapeutic efficacy, broadening the exploration and development of enzyme-like behavior and physiological mechanism of action of SAzymes.

Direct Observation of Hollow Bimetallic Nanoparticle Formation through Galvanic Replacement and Etching Reactions.

Hollow bimetallic nanoparticles (NPs) formed from metal oxide NP templates are widely used catalysts for hydrogen evolution and CO2 reduction reactions. Despite their importance in catalysis, the details of how these NPs form on the NP templates remain unclear. Here, using in situ liquid-phase transmission electron microscopy (TEM) imaging, we describe the conversion of Cu2O template NPs to hollow PdCu NPs. Our observations show that a polycrystalline PdCu shell forms on the surface of the template via a galvanic replacement reaction while the template undergoes anisotropic etching. This study provides important insights into the synthesis of hollow metallic nanostructures from metal oxide templates.

Oxide-Derived Bismuth as an Efficient Catalyst for Electrochemical Reduction of Flue Gas.

Post-combustion flue gas (mainly containing 5-40% CO2 balanced by N2 ) accounts for about 60% global CO2 emission. Rational conversion of flue gas into value-added chemicals is still a formidable challenge. Herein, this work reports a ß-Bi2 O3 -derived bismuth (OD-Bi) catalyst with surface coordinated oxygen for efficient electroreduction of pure CO2 , N2, and flue gas. During pure CO2 electroreduction, the maximum Faradaic efficiency (FE) of formate reaches 98.0% and stays above 90% in a broad potential of 600 mV with a long-term stability of 50 h. Additionally, OD-Bi achieves an ammonia (NH3 ) FE of 18.53% and yield rate of 11.5 µg h-1 mgcat -1 in pure N2 atmosphere. Noticeably, in simulated flue gas (15% CO2 balanced by N2 with trace impurities), a maximum formate FE of 97.3% is delivered within a flow cell, meanwhile above 90% formate FEs are obtained in a wide potential range of 700 mV. In-situ Raman combined with theory calculations reveals that the surface coordinated oxygen species in OD-Bi can drastically activate CO2 and N2 molecules by selectively favors the adsorption of *OCHO and *NNH intermediates, respectively. This work provides a surface oxygen modulation strategy to develop efficient bismuth-based electrocatalysts for directly reducing commercially relevant flue gas into valuable chemicals.

Tunability of the Superconductivity of NbSe2 Films Grown by Two-Step Vapor Deposition.

Layered metallic transition-metal dichalcogenides (TMDCs) are ideal platforms for exploring their fascinating electronic properties at two-dimensional limits, such as their charge density wave (CDW) and superconductivity. Therefore, developing ways to improve the crystallization quality of TMDCs is urgently needed. Here we report superconductively tunable NbSe2 grown by a two-step vapor deposition method. By optimizing the sputtering conditions, superconducting NbSe2 films were prepared from highly crystalline Nb films. The bilayer NbSe2 films showed a superconducting transition temperature that was up to 3.1 K. Similar to the salt-assisted chemical vapor deposition (CVD) method, superconducting monolayer NbSe2 crystals were also grown from a selenide precursor, and the growth strategy is suitable for many other TMDCs. Our growth method not only provides a way to improve the crystalline quality of TMDC films, but also gives new insight into the growth of monolayer TMDCs. It holds promise for exploring two-dimensional TMDCs in fundamental research and device applications.

Metallic bismuth nanoclusters confined in micropores for efficient electrocatalytic reduction of carbon dioxide with long-term stability.

Electrochemical reduction of CO2 to formate via renewable electricity is a cost-effective route. However, the existing bismuth-based electrocatalysts are in oxide form and involve in-situ reduction to metallic bismuth during CO2 reduction. In this work, we demonstrate a nanocomposite electrocatalyst by confining Bi nanoclusters into porous carbons (Bi NCs@PC). In particular, the Bi NCs show excellent stability that can maintain zero valences during long-term electrocatalysis or after months of storage in the air. The as-synthesized Bi NCs@PC catalyst achieves up to 96 % formate Faradaic efficiency (FE) at -1.15 V versus reversible hydrogen electrode. Notably, the FE only attenuates by 7.3 % after 30 days of storage under ambient conditions. In-situ Raman spectrum identify the key intermediates during formate formation. Moreover, Bi NCs encapsulated in carbon micropores could significantly reduce the formation energy of the intermediate *OCHO by density functional theory.

Phosphorus-Doped Graphene Aerogel as Self-Supported Electrocatalyst for CO2 -to-Ethanol Conversion.

Electrochemical reduction of carbon dioxide (CO2 ) to ethanol is a promising strategy for global warming mitigation and resource utilization. However, due to the intricacy of C─C coupling and multiple proton-electron transfers, CO2 -to-ethanol conversion remains a great challenge with low activity and selectivity. Herein, it is reported a P-doped graphene aerogel as a self-supporting electrocatalyst for CO2 reduction to ethanol. High ethanol Faradaic efficiency (FE) of 48.7% and long stability of 70 h are achieved at -0.8 VRHE . Meanwhile, an outstanding ethanol yield of 14.62 µmol h-1 cm-2 can be obtained, outperforming most reported electrocatalysts. In situ Raman spectra indicate the important role of adsorbed *CO intermediates in CO2 -to-ethanol conversion. Furthermore, the possible active sites and optimal pathway for ethanol formation are revealed by density functional theory calculations. The graphene zigzag edges with P doping enhance the adsorption of *CO intermediate and increase the coverage of *CO on the catalyst surface, which facilitates the *CO dimerization and boosts the EtOH formation. In addition, the hierarchical pore structure of P-doped graphene aerogels exposes abundant active sites and facilitates mass/charge transfer. This work provides inventive insight into designing metal-free catalysts for liquid products from CO2 electroreduction.

Delicate Tuning of the Ni/Co Ratio in Bimetal Layered Double Hydroxides for Efficient N2 Electroreduction.

Electroreduction of N2 to NH3 at ambient conditions using renewable electricity is promising, but developing efficient electrocatalysts is still challenging due to the inertness of N≡N bonds. Layer double hydroxides (LDHs) composed of first-row transition metals with empty d-orbitals are theoretically promising for N2 electroreduction (NRR) but rarely reported. Herein, hollow NiCo-LDH nanocages with different Ni/Co ratios were prepared, and their electronic structures and atomic arrangements were critical. The synergetic mechanisms of Ni and Co ions were revealed, and the optimized catalytic sites were proposed. Besides, in-situ Raman spectroscopy and 15 N2 isotopic labeling studies were applied to detect reaction intermediates and confirm the origin of NH3 . As a result, high NH3 yield of 52.8 µg h-1 mgcat -1 and faradaic efficiency of 11.5 % were obtained at -0.7 V, which are top-ranking among Co/Ni-based NRR electrocatalysts. This work elucidates the structure-activity relationship between LDHs and NRR and is instructive for rational design of LDH-based electrocatalysts.

Strategies in catalysts and electrolyzer design for electrochemical CO2 reduction toward C2+ products.

In light of environmental concerns and energy transition, electrochemical CO2 reduction (ECR) to value-added multicarbon (C2 +) fuels and chemicals, using renewable electricity, presents an elegant long-term solution to close the carbon cycle with added economic benefits as well. However, electrocatalytic C─C coupling in aqueous electrolytes is still an open challenge due to low selectivity, activity, and stability. Design of catalysts and reactors holds the key to addressing those challenges. We summarize recent progress in how to achieve efficient C─C coupling via ECR, with emphasis on strategies in electrocatalysts and electrocatalytic electrode/reactor design, and their corresponding mechanisms. In addition, current bottlenecks and future opportunities for C2 + product generation is discussed. We aim to provide a detailed review of the state-of-the-art C─C coupling strategies to the community for further development and inspiration in both fundamental understanding and technological applications.

Fabrication of dual-hollow heterostructure of Ni2CoS4 sphere and nanotubes as advanced electrode for high-performance flexible all-solid-state supercapacitors.

High-energy-density and flexible supercapacitors have shown numerous application potential in modern portable electronics. However, the relatively low specific capacity, poor rate retentions, and limited durability have hindered their implement. Herein, a novel hierarchical dual-hollow electrode, composed of a hollow Ni2CoS4 sphere and outer hollow Ni2CoS4 nanotubes (Ni2CoS4HS-HTs), is elaborately constructed. The Ni2CoS4HS-HT-5 exhibits a high specific capacity of 817.5 C g-1 at a current density of 1 A g-1 with remarkable rate retention of 75.3% at 50 A g-1. In an all-solid-state asymmetric supercapacitor of Ni2CoS4HS-HT-5//CAC, a high capacitance of 1511.5 mF cm-2 at 5 mA cm-2 is obtained with an exceptional energy density of 13.6 mWh cm-3 at a power density of 92.6 mW cm-3. In addition, the capacity retention reaches 96% over 2000 cycles at 20 mA cm-3, implying the outstanding durability. The flexibility and mechanical stability are demonstrated by the intact electrochemical performances under different bending angles. As a proof-of-concept, two Ni2CoS4HS-HT-5//CACs in series could successfully illuminate 31 LED indicators for more than 8 mins. These fascinating electrochemical performances benefit from the novel electrode structure and depict great potential for modern energy storage applications.