Highly selective electrocatalytic reduction of CO2 to HCOOH over an in situ derived Ag-loaded Bi2O2CO3 electrocatalyst.

The electrochemical reduction of CO2 to HCOOH is considered one of the most appealing routes to alleviate the energy crisis and close the anthropogenic CO2 cycle. However, it remains challenging to develop electrocatalysts with high activity and selectivity towards HCOOH in a wide potential window. In this regard, Ag/Bi2O2CO3 was prepared by an in situ electrochemical transformation from Ag/Bi2O3. The Ag/Bi2O2CO3 catalyst achieves a faradaic efficiency (FE) of over 90% for HCOOH in a wide potential window between -0.8 V and -1.3 V versus the reversible hydrogen electrode (RHE). Moreover, a maximum FE of 95.8% and a current density of 15.3 mA cm-2 were achieved at a low applied potential of -1.1 V. Density functional theory (DFT) calculations prove that the high catalytic activity of Ag/Bi2O2CO3 is ascribed to the fact that Ag can regulate the electronic structure of Bi, thus facilitating the adsorption of *OCHO and hindering the adsorption of *COOH. This work expands the in situ electrochemical derivatization strategy for the preparation of electrocatalysts.

V-O Species-Doped Carbon Frameworks Loaded with Ru Nanoparticles as Highly Efficient and CO-Tolerant Catalysts for Alkaline Hydrogen Oxidation.

Efficient and CO-tolerant catalysts for alkaline hydrogen oxidation (HOR) are vital to the commercial application of anion exchange membrane fuel cells (AEMFCs). Herein, a robust Ru-based catalyst (Ru/VOC) with ultrasmall Ru nanoparticles supported on carbon frameworks with atomically dispersed V-O species is prepared elaborately. The catalyst exhibits a remarkable mass activity of 3.44 mA µgPGM, which is 31.3 times that of Ru/C and even 4.7 times higher than that of Pt/C. Moreover, the Ru/VOC anode can achieve a peak power density (PPD) of 1.194 W cm-2, much superior to that of Ru/C anode and even better than that of Pt/C anode. In addition, the catalyst also exhibits superior stability and exceptional CO tolerance. Experimental results and density functional theory (DFT) calculations demonstrate that V-O species are ideal OH- adsorption sites, which allow Ru to release more sites for hydrogen adsorption. Furthermore, the electron transfer from Ru nanoparticles to the carbon substrate regulates the electronic structure of Ru, reducing the hydrogen binding energy (HBE) and the CO adsorption energy on Ru, thus boosting the alkaline HOR performance and CO tolerance of the catalyst. This is the first report that oxophilic single atoms distributed on carbon frameworks serve as OH- adsorption sites for efficient hydrogen oxidation, opening up new guidance for the elaborate design of high-activity catalysts for the alkaline HOR.

Microbial synthesis of Prussian blue for potentiating checkpoint blockade immunotherapy.

Cancer immunotherapy is revolutionizing oncology. The marriage of nanotechnology and immunotherapy offers a great opportunity to amplify antitumor immune response in a safe and effective manner. Here, electrochemically active Shewanella oneidensis MR-1 can be applied to produce FDA-approved Prussian blue nanoparticles on a large-scale. We present a mitochondria-targeting nanoplatform, MiBaMc, which consists of Prussian blue decorated bacteria membrane fragments having further modifications with chlorin e6 and triphenylphosphine. We find that MiBaMc specifically targets mitochondria and induces amplified photo-damages and immunogenic cell death of tumor cells under light irradiation. The released tumor antigens subsequently promote the maturation of dendritic cells in tumor-draining lymph nodes, eliciting T cell-mediated immune response. In two tumor-bearing mouse models using female mice, MiBaMc triggered phototherapy synergizes with anti-PDL1 blocking antibody for enhanced tumor inhibition. Collectively, the present study demonstrates biological precipitation synthetic strategy of targeted nanoparticles holds great potential for the preparation of microbial membrane-based nanoplatforms to boost antitumor immunity.

Missing-Linker-Confined Single-Atomic Pt Nanozymes for Enzymatic Theranostics of Tumor.

Conventional nanozymes often possess low active site density. Pursuing effective strategies for constructing highly active single-atomic nanosystems with maximum atom utilization efficiency is exceptionally attractive. Herein, we develop a facile "missing-linker-confined coordination" strategy to fabricate two self-assembled nanozymes, i.e., conventional nanozyme (NE) and single-atomic nanozyme (SAE), which respectively consist of Pt nanoparticles and single Pt atoms as active catalytic sites anchored in metal-organic frameworks (MOFs) with encapsulated photosensitizers for catalase-mimicking enhanced photodynamic therapy. Compared to a Pt nanoparticle-based conventional nanozyme, a Pt single-atomic nanozyme shows enhanced catalase-mimicking activity in generating oxygen for overcoming tumor hypoxia, thus exhibiting a more efficient reactive oxygen species generation and high tumor inhibition rate.

Room-Temperature Sodium-Sulfur Batteries: Rules for Catalyst Selection and Electrode Design.

Seeking an optimal catalyst to accelerate conversion reaction kinetics of room-temperature sodium-sulfur (RT Na-S) batteries is crucial for improving their electrochemical performance and promoting the practical applications. Herein, theoretical calculations of interfacial interactions of catalysts and polysulfides in terms of the surface adsorption state, interfacial ions migration, and electronic concentration around the Fermi level are systematically proposed as guiding principles of catalyst selection for RT Na-S batteries. As a case, MoN catalyst is accurately selected from transition metal nitrides with different d orbital electrons, and for experiment, it is introduced into the carbon nanofibers as a dual-functioning host (MoN@CNFs). The MoN@CNFs can effectively anchor polysulfides and accelerate their conversion reaction. In addition, for the sodium anode, the MoN@CNFs can also induce uniform deposition of Na and inhibit dendrite growth, which are supported by in situ characterizations and finite element simulation technique. As a result, the as-prepared RT Na-S battery displays high reversible capacity of 990 mAh g-1 at 0.2 A g-1 after 100 cycles and long lifespan over 1500 cycles at 2 A g-1 . Even with high S loading of 5 mg cm-2 , the RT Na-S battery still exhibits a high areal capacity of 2.5 mAh cm-2 .

Ultrasmall Cu Nanocrystals Dispersed in Nitrogen-Doped Carbon as Highly Efficient Catalysts for CO2 Electroreduction.

The electroreduction of carbon dioxide (CO2) to a liquid product is a viable method for establishing an artificial carbon cycle. Unfortunately, most electrocatalysts' low efficiency and instability prevent them from being used in practical applications. In the current study, we developed ultrasmall Cu nanocrystals embedded in nitrogen-doped carbon nanosheets (Cu/NC-NSs) for selective CO2 electroreduction by adjusting the potential. Cu/NC-NSs had 43.7 and 63.5% Faradaic efficiencies for the synthesis of ethanol and formate with applied potentials of -0.37 and -0.77 V vs reversible hydrogen electrode (RHE) using a flow cell architecture, respectively. Moreover, these Cu/NC-NSs show a steady catalytic performance up to 16 h. Density functional theory (DFT) calculations were performed to investigate the reaction mechanism. Furthermore, the synergistic effect formed by nitrogen-doped carbon and highly dispersed copper atoms led to their excellent performance in CO2 electroreduction.

One-Step Construction of V5S8 Nanoparticles Embedded in Amorphous Carbon Nanorods for High-Capacity and Long-Life Potassium Ion Half/Full Batteries.

Potassium ion batteries (KIBs) have attracted great attention recently as a promising large-scale energy storage system by virtue of the bountiful K resource and low standard hydrogen potential of K+/K. However, their development is hindered by the limited capacity and inferior cycling stability resulting from the large size of K+. Here, a unique vanadium sulfide@carbon nanorod is designed and synthesized for high-performance KIBs. Thanks to the hybrid structure, abundant active sites, fast ion diffusion, and capacitive-like electrochemical behavior of the electrode, the anode exhibits a large specific capacity (468 mA h g-1 after 100 cycles at 0.1 A g-1), predominant rate performance (205 mA h g-1 at 5 A g-1), and impressive cycling stability (171 mA h g-1 for 4000 cycles at 3 A g-1). Furthermore, the constructed KIB full cell demonstrates 229 mA h g-1 at 0.5 A g-1 and 86% capacity retention over 300 cycles.

Tuning the p-Orbital Electron Structure of s-Block Metal Ca Enables a High-Performance Electrocatalyst for Oxygen Reduction.

Most previous efforts are devoted to developing transition metals as electrocatalysts guided by the d-band center model. The metals of the s-block of the periodic table have so far received little attention in the application of oxygen reduction reactions (ORR). Herein, a carbon catalyst with calcium (Ca) single atom coordinated with N and O is reported, which displays exceptional ORR activities in both acidic condition (E1/2  = 0.77 V, 0.1 m HClO4 ) and alkaline condition (E1/2  = 0.90 V, 0.1 m KOH). The CaN, O/C exhibits remarkable performance in zinc-air battery with a maximum power density of 218 mW cm-2 , superior to a series of catalysts reported so far. X-ray absorption near-edge structure (XANES) characterization confirms the formation of N- and O-atom-coordinated Ca in the carbon matrix. Density functional theory (DFT) calculations reveal that the high catalytic activity of main-group Ca is ascribed to the fact that its p-orbital electron structure is regulated by N and O coordination so that the highest peak (EP ) of the projected density of states (PDOS) for the Ca atom is moved close to the Fermi level, thereby facilitating the adsorption of ORR intermediates and electron transfer.

Cage-Confinement Pyrolysis Strategy to Synthesize Hollow Carbon Nanocage-Coated Copper Phosphide for Stable and High-Capacity Potassium-Ion Storage.

Metal phosphides with a high theoretical capacity and low redox potential have been proposed as promising anodes for potassium-ion batteries (PIBs). A reasonable configuration design and introduction of a hollow structure with adequate internal void spaces are effective strategies to overcome the volume expansion of metal phosphides in potassium-ion batteries. Herein, we report a cage-confinement pyrolysis strategy to obtain hollow nanocage-structured nitrogen/phosphorus dual-doped carbon-coated copper phosphide (Cu3P/CuP2@NPC), which exhibits a high initial charge capacity (409 mA h g-1 at 100 mA g-1) and an outstanding cycle performance (100 mA h g-1 after 5000 cycles at 1000 mA g-1) as an anode material for PIBs. The novel hollow nanocage structure could prevent volume expansion during cycling and reduce the electron/ion diffusion distance. Besides, the nitrogen/phosphorus dual-doped carbon-coated layer could promote electronic conductivity. In situ X-ray diffraction (XRD) measurements are conducted to study the potassiation/depotassiation mechanism of Cu3P/CuP2@NPC and reveal the structure stability during the cycle process, which further proves that the design ideas of the conductive carbon layer and the hollow structure with adequate internal void spaces are successful.

Lewis-Basic EDTA as a Highly Active Molecular Electrocatalyst for CO2 Reduction to CH4.

The most active catalysts so far successful in hydrogenation reduction of CO2 are mainly heterogeneous Cu-based catalysts. The complex coordination environments and multiple active sites in heterogeneous catalysts result in low selectivity of target product, while molecular catalysts with well-defined active sites and tailorable structures allow mechanism-based performance optimization. Herein, we firstly report a single ethylenediaminetetraacetic acid (EDTA) molecular-level immobilized on the surface of carbon nanotube as a catalyst for transferring CO2 to CH4 with an excellent performance. This catalyst exhibits a high Faradaic efficiency of 61.6 % toward CH4 , a partial current density of -16.5 mA cm-2 at a potential of -1.3 V versus reversible hydrogen electrode. Density functional theory calculations reveal that the Lewis basic COO- groups in EDTA molecule are the active sites for CO2 reduction reaction (CO2 RR). The energy barrier for the generation of CO from *CO intermediate is as high as 0.52 eV, while the further protonation of *CO to *CHO follows an energetic downhill path (-1.57 eV), resulting in the high selectivity of CH4 . This work makes it possible to control the product selectivity for CO2 RR according to the relationship between the energy barrier of *CO intermediate and molecular structures in the future.

High Catalytic Performance of Au/Bi2O3 for Preferential Oxidation of CO in H2.

Preferential oxidation (PROX) of CO in hydrogen is of great significance for proton exchange membrane fuel cells (PEMFCs) that need a CO-free hydrogen stream as fuel. The key technical problem is developing catalysts that can efficiently remove CO from the H2-rich stream within the working temperature range of PEMFCs. Herein, we design a Au/Bi2O3 interfacial catalyst for PROX with excellent catalytic performance, which can achieve 100% CO conversion in the PROX reaction over a wide temperature window (70-200 °C) and is perfectly compatible with the operating temperature window (80-180 °C) of PEMFCs. Moreover, the catalyst also demonstrates excellent high flow performance and long-term stability. Density functional theory (DFT) calculations reveal that the electrons transferring from Bi2O3 to Au and then to adsorbed perimeter CO and O2 molecules promote the activation of CO and O2, thus enhancing the catalytic performance of PROX.

Boosting Hydrazine Oxidation Reaction on CoP/Co Mott-Schottky Electrocatalyst through Engineering Active Sites.

The hydrazine oxidation reaction (HzOR), as a substitute for the sluggish oxygen evolution reaction (OER), is identified as a promising powerfrugal strategy for hydrogen production through water splitting. However, the HzOR activity of the present electrocatalysts is unsatisfying because the work potential is much higher than the theoretical value. Herein, we design a typical Mott-Schottky electrocatalyst consisting of CoP/Co nanoparticles for the HzOR, which exhibits remarkable HzOR activity with ultralow potentials of -69 and 177 mV at 10 and 100 mA cm-2, respectively. It stands out in a range of cobalt-based materials and is even comparable to some precious-metal-based materials composed of Pt or Ru. A shown by with structural characterization and density functional theory (DFT) calculations, the interfaces between CoP/Co nanoparticles not only provide the active sites of HzOR but also promote the multistep dehydrogenation reaction of N2H4, thus enhancing the HzOR activity.

N and O multi-coordinated vanadium single atom with enhanced oxygen reduction activity.

Recently, atomically dispersed transition-metal single atom in nitrogen-doped carbon matrix as electrocatalysts has aroused general interest. However, there is no report about vanadium single atom for ORR in the literature. According to d-band center theory for transition-metals, the performance of catalysts is regulated by the electronic structure of the catalytic center which determines the intermediate adsorption kinetics. Indeed, the valence of vanadium is variable, its electron structure could be modulated by an appropriate coordination structure. Here, a novel method is developed to prepare the N and O co-coordinated vanadium single atom (V-N1O4) embedded in the carbon matrix. The catalyst displays a half-wave potential of 865 mV in base solution which surpasses 20% Pt/C, and also shows a high power density of 180 mW/cm2 in Zn-air batteries. DFT calculations reveal that the N and O coordination configuration could regulate the electron structure and geometry of vanadium to boost the electrocatalytic activity.

Self-Assembled Single-Site Nanozyme for Tumor-Specific Amplified Cascade Enzymatic Therapy.

Nanomaterials with enzyme-mimicking activity (nanozymes) show potential for therapeutic interventions. However, it remains a formidable challenge to selectively kill tumor cells through enzymatic reactions, while leaving normal cells unharmed. Herein, we present a new strategy based on a single-site cascade enzymatic reaction for tumor-specific therapy that avoids off-target toxicity to normal tissues. A copper hexacyanoferrate (Cu-HCF) nanozyme with active single-site copper exhibited cascade enzymatic activity within the tumor microenvironment: Tumor-specific glutathione oxidase activity by the Cu-HCF single-site nanozymes (SSNEs) led to the depletion of intracellular glutathione and the conversion of single-site CuII species into CuI for subsequent amplified peroxidase activity through a Fenton-type Harber-Weiss reaction. In this way, abundant highly toxic hydroxyl radicals were generated for tumor cell apoptosis. The results show that SSNEs could amplify the tumor-killing efficacy of reactive oxygen species and suppress tumor growth in vivo.

Energetic Metal-Organic Frameworks Derived Highly Nitrogen-Doped Porous Carbon for Superior Potassium Storage.

The carbonaceous materials with low cost and high safety have been considered as promising anodes for potassium-ion batteries (PIBs). However, it is still a challenge to design a carbonaceous material with long cycle life and high rate performance due to the poor K+ reaction kinetics. Herein, this article reports a N-doped porous carbon framework (NPCF) with a high nitrogen content of 13.57 at% within high doping level of the pyrrolic N and pyridinic N, which exhibits a high reversible capacity of 327 mA h g-1 over 100 cycles at a current density of 100 mA g-1 , excellent rate capability (144 and 105 mA h g-1 at 10 and 20 A g-1 , respectively) and great cyclability of 258.9 mA h g-1 after 2000 cycles at 1 A g-1 . Such a high rate performance and excellent cycling stability anode material is seldom reported in PIBs. Density functional theory (DFT) calculations reveal that the pyrrolic and pyridinic N-doping are helpful to enhance the K adsorption ability, thereby increasing the specific capacity.

Turning main-group element magnesium into a highly active electrocatalyst for oxygen reduction reaction.

It is known that the main-group metals and their related materials show poor catalytic activity due to a broadened single resonance derived from the interaction of valence orbitals of adsorbates with the broad sp-band of main-group metals. However, Mg cofactors existing in enzymes are extremely active in biochemical reactions. Our density function theory calculations reveal that the catalytic activity of the main-group metals (Mg, Al and Ca) in oxygen reduction reaction is severely hampered by the tight-bonding of active centers with hydroxyl group intermediate, while the Mg atom coordinated to two nitrogen atoms has the near-optimal adsorption strength with intermediate oxygen species by the rise of p-band center position compared to other coordination environments. We experimentally demonstrate that the atomically dispersed Mg cofactors incorporated within graphene framework exhibits a strikingly high half-wave potential of 910 mV in alkaline media, turning a s/p-band metal into a highly active electrocatalyst.

The Enhancement of the Catalytic Oxidation of CO on Ir/CeO2 Nanojunctions.

Heterogeneous catalysts facilitate various chemical reactions through the changing of their surface charge density. Herein, we demonstrate an interface engineering strategy to enhance the Ir catalytic performance for oxidation of CO by constructing Ir/CeO2 nanojunctions using a wet chemical reduction process. The as-prepared Ir/CeO2 nanojunctions show a complete CO conversion temperature (T100) of 110 °C under 1 vol % CO and retains long-term durability even after 24 h. The Ir atoms and CeO2 supports were connected by O atoms, which changes the surface electronic structure of Ir atoms. DFT calculations demonstrate that the significant increase in electron density at the interface between Ir and CeO2 plays a pivotal role in the enhancement of CO oxidation.

Dual Graphitic-N Doping in a Six-Membered C-Ring of Graphene-Analogous Particles Enables an Efficient Electrocatalyst for the Hydrogen Evolution Reaction.

Graphene-based materials still exhibit poor electrocatalytic activities for the hydrogen evolution reaction (HER) although they are considered to be the most promising electrocatalysts. We fabricated a graphene-analogous material displaying exceptional activity towards the HER under acidic conditions with an overpotential (57 mV at 10 mA cm-2 ) and Tafel slope (44.6 mV dec-1 ) superior to previously reported graphene-based materials, and even comparable to the state-of-the art Pt/C catalyst. X-ray absorption near-edge structure (XANES) and solid-state NMR studies reveal that the distinct feature of its structure is dual graphitic-N doping in a six-membered carbon ring. Density functional theory (DFT) calculations show that the unique doped structure is beneficial for the activation of C-H bonds and to make the carbon atom bonded to two graphitic N atoms an active site for the HER.

Enhancing the Capacitance of Battery-Type Hybrid Capacitors by Encapsulating MgO Nanoparticles in Porous Carbon as Reservoirs for OH- Ions from Electrolytes.

A novel design of no-loading and bifunctional positive electrode, serving as an active material and current collector simultaneously, has been constructed by grass-like nickel foam which shows a battery-type performance and excellent areal specific capacity at 0.540 mA h·cm-2 (over 4500 mF·cm-2). To obtain a high-performance hybrid capacitor, layered porous carbonaceous composites C/MgO negative electrodes were fabricated, in which MgO nanoparticles serve as "reservoirs" for OH- ions from the electrolyte. Compared with other carbon materials, such as carbon fibers, hollow nanospheres, and nanotubes, the three-dimensional (3D) hierarchical heterostructures of the C/MgO electrode exhibit a higher storage performance of 424.1 mF·cm-2. Assembled by these two working electrodes, a hybrid capacitor with uncommon galvanostatic charge/discharge cycling curve has been well-investigated in an alkaline aqueous electrolyte system. This as-coupled hybrid capacitor exhibits an engaging activation process during multiple cycling tests and leads to a drastically improved energy density of 60% (from 80.4 to 128.8 µW h·cm-2), which can be attributed to a "match behavior" between its positive and negative electrodes.

Incorporation of Cu-Nx cofactors into graphene encapsulated Co as biomimetic electrocatalysts for efficient oxygen reduction.

Unlike metals with incomplete d-shells such as Pt and Fe, copper (Cu) with a filled d-electron shell is generally regarded as a sluggish oxygen reduction reaction (ORR) electrocatalyst. However, laccase and other copper enzymes could catalyze the ORR efficiently in nature. Inspired by this, we incorporated Cu-Nx cofactors (Cu-N2 and Cu-N4) into graphene encapsulated Co frameworks by direct annealing of MOFs with a post etching process. The bioinspired electrocatalyst exhibits excellent performance and stability for ORR which is comparable to or even better than Pt/C. Meanwhile, it also illustrates a fantabulous performance in a zinc-air battery device. The excellent performance can be ascribed to the abundant atomically dispersed Cu-Nx cofactors in the graphene frameworks confirmed by aberration corrected HAADF-STEM and XAFS analyses. Density functional theory calculations suggest that when Cu atoms are coordinated with the surrounding N atoms, the valence electrons of Cu atoms will transfer to nitrogen atoms, simultaneously tuning the d electronic states near the Fermi level to realize fast ORR kinetics.