Enhancing activity and stability of FeNC catalysts through co incorporation for oxygen reduction reaction.

FeNC single atom catalysts (SACs) have attracted great interest due to their highly active FeN4 sites. However, the pyrolysis treatment often leads to inevitable metal migration and aggregation, which reduces the catalytic activity. Moreover, due to the Fenton reaction caused by FeNC in alkaline and acidic solutions, the presence of Fe and peroxide in electrodes may generate free radicals, resulting in serious degradation of the organic ionomer and the membrane. Herein, we report an original strategy of introducing Co single atoms into FeNC catalysts, forming atomically dispersed bimetallic active sites (FeCoNC) and improving the activity and stability of the catalyst. Benefiting from this strategy, FeCoNC catalyst exhibits excellent oxygen reduction reaction (ORR) activity in alkaline media (E1/2 = 0.88 V) and in acidic media (E1/2 = 0.77 V). As the cathode of Zn-air battery (ZAB), FeCoNC shows an excellent peak power density of 142.8 mW cm-2 and a specific capacity of 806.6 mAh/gZn. This work provides a novel avenue to optimize and enhance the ORR performance of atomic dispersed FeNC catalysts.

Engineering Atomic Ag1-N6 Sites with Enhanced Performance of Eradication Drug-Resistant Bacteria over Visible-Light-Driven Antibacterial Membrane.

Utilizing visible light for water disinfection is a more convenient, safe, and practical alternative to ultraviolet-light sterilization. Herein, we developed silver (Ag) single-atom anchored g-C3N4 (P-CN) nanosheets (Ag1/CN) and then utilized a spin-coating method to fabricate the Ag1/CN-based-membrane for effective antibacterial performance in natural water and domestic wastewater. The incorporated Ag single atom formed a Ag1-N6 motif, which increased the charge density around the N atoms, resulting in a built-in electric field ∼17.2 times stronger than that of pure P-CN and optimizing the dynamics of reactive oxygen species (ROS) production. Additionally, the Ag1-N6 motif inhibited the release of Ag ions, ensuring good biocompatibility. Based on the first-principles calculation, the adsorption energy of O2 on the Ag1/CN (-0.32 eV) was lower than that of P-CN (-0.07 eV), indicating that loaded Ag single atom can lower the energy barrier for O2 activation, generating extra *OH radicals that cooperated with *O2- to effectively neutralize bacteria. As a result, the Ag1/CN powder-catalyst with the concentration of 30 ppm demonstrated a 99.9% antibacterial efficiency against drug-resistant bacteria (Escherichia coli, Staphylococcus aureus, kanamycin-resistant Escherichia coli, and methicillin-resistant Staphylococcus aureus) under visible-light irradiation for 4 h. This efficacy was 24.8 times higher than that of the P-CN powder catalyst. Moreover, the Ag1/CN-based-membrane can maintain a 99.9% bactericidal efficiency for natural water and domestic wastewater treatment using a homemade flow device, demonstrating its potential for water disinfection. Notably, the visible-light-driven antibacterial efficiency of the Ag1/CN catalyst outperformed the majority of the reported g-C3N4-based catalysts/membranes.

In situ synthesis of graphitic carbon nitride nanosheet/Ti3C2Tx MXene/TiO2 Z-scheme heterojunctions boosting charge transfer for full-spectrum driven photocatalytic sterilization.

The development of a full-spectrum responsive photocatalytic germicide with excellent charge separation efficiency to harvest high antimicrobial efficacy is a key goal yet a challenging conundrum. Herein, graphitic carbon nitride nanosheet (PCNS)/Ti3C2Tx MXene/TiO2 (PMT) Z-scheme heterojunctions with robust interface contact were crafted by in situ interfacial engineering. The strong internal electrical field (IEF) from PCNS to TiO2, evinced by the Kelvin Probe Force Microscopy (KPFM) characterization, can obtain high charge separation efficiency with 73.99%, compared to Schottky junction PCNS/Ti3C2Tx (PM, 32.88%) and PCNS (17.70%). The Ti3C2Tx component can not only serve as a transfer pathway to accelerate the recombination of photoexcited electrons of TiO2 and holes of PCNS under the Ultraviolet-visible (UV-vis) light irradiation, but also replenish the photogenic electron concentrations to semiconductors in the near-infrared (NIR) light illumination. Meanwhile, the increased temperature due to the localized surface plasmon resonance (LSPR) can further boost the electronic activity to the generation of reactive oxygen species (ROS). Taken together, the PMT performs a high disinfection efficiency up to 99.40% under full solar spectrum illumination, 3.88 and 9.75 times higher than PCNS and TiO2, respectively, surpassing many reported Z-scheme heterojunctions. This work offers guidance for the design of Z-scheme heterojunction with the implanting of plasmons to secure excellent full-spectrum responsive photocatalytic sterilization performance.

In Situ Fabrication of a 2D/2D MXene/CN Heterojunction for Photothermally Assisted Photocatalytic Sterilization under Visible Light Irradiation.

Constructing an efficient visible light-responsive antibacterial material for water treatment remains a principal goal yet is a huge challenge. Herein, a 2D/2D heterojunction composite with robust interfacial contact, named MXene/CN (MCN), was controllably fabricated by using a urea molecule intercalated into MXene following an in situ calcination method, which can realize the rapid separation and migration of photogenerated carriers under visible light irradiation and significantly improve the carrier concentration of the MXene surface, thus generating more reactive oxygen species. The generation of heat induced by MXene could also increase photogenic electron activity to facilitate the photocatalytic reaction using in situ time-resolved photoluminescence characterization. The visible light-activated germicide exhibits a sterilization efficacy against Escherichia coli of 99.70%, higher than those of pure CN (60.21%) and MXene (31.75%), due to the effect of photothermally assisted photocatalytic treatment. This work is an attempt to construct a visible light-driven antimicrobial material using Schottky junctions achieving photothermally assisted photocatalytic disinfection.

Dimensional-matched two dimensional/two dimensional TiO2/Bi2O3 step-scheme heterojunction for boosted photocatalytic performance of sterilization and water splitting.

A Step-scheme (S-scheme) heterojunction can regulate the directional migration of powerful photogenerated carriers and realize high photocatalytic activity. Herein, we propose a novel dimensional matched S-scheme photocatalyst comprising of two-dimensional (2D) TiO2 nanosheets and 2D Bi2O3 nanosheets for environmental and energy applications, such as water sterilization and water splitting. X-ray photoelectron spectroscopy (XPS), electron paramagnetic resonance, in-situ irradiated XPS and theoretical calculations provided strong evidence that the photocarrier migration in the TiO2/Bi2O3 composite followed the S-scheme mode, which efficiently prevented the recombination of powerful photocarriers, thereby enabling the heterojunction with a strong redox ability for producing abundant reactive oxygen species. The tight and large 2D/2D interface minimized the distance of photocarrier migration to further extend the lifetime of useful photocarriers (active radicals for sterilization and photoelectrons for H2 generation). The 2D/2D TiO2/Bi2O3 heterojunction demonstrated an improved photocatalytic antibacterial performance with complete inactivation of 4.63 × 107 CFU mL-1Escherichia coli cells within 6 h in water. In addition, the heterojunction displayed a H2 generation rate of 12.08 mmol h-1g-1 through water splitting process. This study provides a potential bifunctional photocatalyst for minimizing the adverse impact of pollution on the environment.

Surface Structure Engineering of PtPd Nanoparticles for Boosting Ammonia Oxidation Electrocatalysis.

Achieving high catalytic ammonia oxidation reaction (AOR) performance of Pt-based catalysts is of paramount significance for the development of direct ammonia fuel cells (DAFCs). However, the high energy barrier of dehydrogenation of *NH2 to *NH and easy deactivation by *N on the Pt surface make the AOR show sluggish kinetics. Here, we have put forward an alloying and surface modulation tactic to optimize Pt catalysts. Several spherical PtM (M = Co, Ni, Cu, and Pd) binary nanoparticles were controllably loaded on reduced graphene oxide (rGO). Among others, spherical PtPd nanoparticles displayed the most efficient catalytic activity. Further surface engineering of PtPd nanoparticles with a cubic-dominant structure has resulted in dramatic AOR activity improvements. The optimized (100)Pt85Pd15/rGO exhibited a low onset potential (0.467 V vs reversible hydrogen electrode (RHE)) and high peak mass activity (164.9 A g-1), much better than commercial Pt/C. Nevertheless, a short-term stability test along with morphology, structure, and composition characterizations indicate that the leaching of Pd atoms from PtPd alloy nanoparticles, their structure transformations, and the possible poisoning effects by the N-containing intermediates could result in the catalyst's activity loss during the AOR electrocatalysis. A temperature-dependent electrochemical test confirmed a reduced activation energy (∼12 kJ mol-1 decrease) of cubic-dominant PtPd compared to Pt/C. Density functional theory calculations further demonstrated that Pd atoms in Pt decrease the reaction energy barrier of electrochemical dehydrogenation of *NH2 to *NH, resulting in an excellent catalytic activity for the AOR.