Single-Atom Iron Catalyst as an Advanced Redox Mediator for Anodic Oxidation of Organic Electrosynthesis.

Homogeneous electrocatalysts can indirect oxidate the high overpotential substrates through single-electron transfer on the electrode surface, enabling efficient operation of organic electrosynthesis catalytic cycles. However, the problems of this chemistry still exist such as high dosage, difficult recovery, and low catalytic efficiency. Single-atom catalysts (SACs) exhibit high atom utilization and excellent catalytic activity, hold great promise in addressing the limitations of homogeneous catalysts. In view of this, we have employed Fe-SA@NC as an advanced redox mediator to try to change this situation. Fe-SA@NC was synthesized using an encapsulation-pyrolysis method, and it demonstrated remarkable performance as a redox mediator in a range of reported organic electrosynthesis reactions, and enabling the construction of various C-C/C-X bonds. Moreover, Fe-SA@NC demonstrated a great potential in exploring new synthetic method for organic electrosynthesis. We employed it to develop a new electro-oxidative ring-opening transformation of cyclopropyl amides. In this new reaction system, Fe-SA@NC showed good tolerance to drug molecules with complex structures, as well as enabling flow electrochemical syntheses and gram-scale transformations. This work highlights the great potential of SACs in organic electrosynthesis, thereby opening a new avenue in synthetic chemistry.

Rational Design of Non-Noble Metal Single-Atom Catalysts in Lithium-Sulfur Batteries through First Principles Calculations.

Lithium-sulfur (Li-S) batteries with a high theoretical energy density of 2600 Wh·kg-1 are hindered by challenges such as low S conductivity, the polysulfide shuttle effect, low S reduction conversion rate, and sluggish Li2S oxidation kinetics. Herein, single-atom non-noble metal catalysts (SACs) loaded on two-dimensional (2D) vanadium disulfide (VS2) as the potential host materials for the cathode in Li-S batteries were investigated systematically by using first-principles calculations. Based on the comparisons of structural stability, the ability to immobilize sulfur, electrochemical reactivity, and the kinetics of Li2S oxidation decomposition between these non-noble metal catalysts and noble metal candidates, Nb@VS2 and Ta@VS2 were identified as the potential candidates of SACs with the decomposition energy barriers for Li2S of 0.395 eV (Nb@VS2) and of 0.162 eV (Ta@VS2), respectively. This study also identified an exothermic reaction for Nb@VS2 and the Gibbs free energy of 0.218 eV for Ta@VS2. Furthermore, the adsorption and catalytic mechanisms of the VS2-based SACs in the reactions were elucidated, presenting a universal case demonstrating the use of unconventional graphene-based SACs in Li-S batteries. This study presents a universal surface regulation strategy for transition metal dichalcogenides to enhance their performance as host materials in Li-S batteries.

Single-Atom Nanoenzyme-Based Autoluminescence System for Cancer Cell Imaging and Mitochondrial-Targeted Therapy.

The autoluminescence nanoplatform based on a single-atom catalyst has the potential to achieve accurate tumor diagnosis and treatment. Taking advantage of this, glycyrrhetinic acid (GA) and chitosan-modified single Fe-N-C atom catalysts (SAF NPs) loaded with luminol-curcumin (Cur) were fabricated (SAF-LCCG). Once delivered to the tumor, this autoluminescence SAF-LCCG could target the mitochondria to restrain tumor metastasis and promote the production of hydrogen peroxide (H2O2). Then, SAF NPs with Fenton-like properties could actively utilize intracellular H2O2 to produce ·OH for chemodynamic therapy. After that, excess ·OH and H2O2 were transmitted to luminol to emit blue-violet chemiluminescence (CL) for cancer cell imaging. Synchronously, light was transferred to Cur to produce reactive oxygen species (ROS) which realized photodynamic therapy. Besides, Cur could be served as a chemotherapeutic drug to enhance intracellular ROS for penetrating therapy. More importantly, the massive accumulation of ROS in cancer cells can promote the CL intensity of luminol, which realized the cyclic ROS amplification. This autoluminescence nanoplatform was developed for accurate cancer cell imaging, effective inhibition of tumor metastasis, and synergistic and penetrated treatment of tumors.

Water dispersible cobalt single-atom catalysts with efficient Chemiluminescence enhancement for sensitive bioassay.

Single-atom catalysts (SACs) have been applied in various fields as they display extremely high utilization efficiency of catalytic sites. A majority of SACs prepared by high-temperature calcination suffer from poor water dispersion and lose of labelling groups. Herein cobalt SACs (CSACs) were synthesized with a solvothermal method by adopting hybridized MOFs Fe2O3/MIL-100(Fe) as the carriers to load cobalt atoms. Compared with original MOFs MIL-100(Fe), the carriers possess superior loading capacity, and the loading amount of cobalt element is up to 4.69 wt%. The implantation of cobalt atoms in hybridized MOFs Fe2O3/MIL-100(Fe) vastly improved the specific surface of the carriers for 68 times. CSACs at 1.0 µg mL-1 can catalyze H2O2 to generate numerous reactive oxygen species and enormously boost the chemiluminescent emission of luminol-H2O2 system up to 2297 times. The CSACs also exhibit satisfactory dispersion in aqueous medium. Benefiting from these attracting features, the CSACs were applied as sensitive signal probes for detecting carbendazim in Chinese medicinal herbs with a chemiluminescent immunoassay method. The dynamic range is 10 pg mL-1 - 50 ng mL-1 and the limit of detection is 1.8 pg mL-1. The proof-of-principle work paves a pathway to the exploitation of SACs as sensitive probes for tracing biological recognition events.

MOF-Templated Sulfurization of Atomically Dispersed Manganese Catalysts Facilitating Electroreduction of CO2 to CO.

To reach a carbon-neutral future, electrochemical CO2 reduction reaction (eCO2RR) has proven to be a strong candidate for the next-generation energy system. Among potential materials, single-atom catalysts (SACs) serve as a model to study the mechanism behind the reduction of CO2 to CO, given their well-defined active metal centers and structural simplicity. Moreover, using metal-organic frameworks (MOFs) as supports to anchor and stabilize central metal atoms, the common concern, metal aggregation, for SACs can be addressed well. Furthermore, with their turnability and designability, MOF-derived SACs can also extend the scope of research on SACs for the eCO2RR. Herein, we synthesize sulfurized MOF-derived Mn SACs to study effects of the S dopant on the eCO2RR. Using complementary characterization techniques, the metal moiety of the sulfurized MOF-derived Mn SACs (MnSA/SNC) is identified as MnN3S1. Compared with its non-sulfur-modified counterpart (MnSA/NC), the MnSA/SNC provides uniformly superior activity to produce CO. Specifically, a nearly 30% enhancement of Faradaic efficiency (F.E.) in CO production is observed, and the highest F.E. of approximately 70% is identified at -0.45 V. Through operando spectroscopic characterization, the probing results reveal that the overall enhancement of CO production on the MnSA/SNC is possibly caused by the S atom in the local MnN3S1 moiety, as the sulfur atom may induce the formation of S-O bonding to stabilize the critical intermediate, *COOH, for CO2-to-CO. Our results provide novel design insights into the field of SACs for the eCO2RR.

Exploiting Single Atom Iron Centers in a Porphyrin-like MOF for Efficient Cancer Phototherapy.

In recent years, single-atom catalysts (SACs) have attracted enormous attention due their effectiveness in promoting a variety of catalytic reactions. However, the ability of SACs to enhance cancer phototherapies has received little attention to date. Herein, we synthesized a metal organic framework (MOF) rich in porphyrin-like single atom Fe(III) centers (denoted herein as porphyrin-MOF or P-MOF) and then evaluated the performance of the P-MOF for cancer treatment by photodynamic therapy (PDT) and photothermal therapy (PTT) under NIR (808 nm) irradiation, as well as photoacoustic imaging (PAI) of tumors. On acccount of the abundance of single atom Fe(III) centers, the P-MOF material demonstrated excellent performance for modulation of the hypoxic tumor microenvironment of Hela cell tumors in mice, while also demonstrating good properties as a photoacoustic imaging (PAI) agent. Density functional theory (DFT) calculations were used to elucidate the superior performance of P-MOF in these applications relative to Fe2O3 (a Fe(III) reference compound). The calculations revealed that the narrow band gap energy of P-MOF (1.31 eV) enabled strong absorption of NIR photons, thereby inducing nonradiative transitions that converted incident light into heat to promote PTT. Further, a facile change of the spin state of the single atom Fe(III) centers in P-MOF under NIR irradiation transformed coordinated triplet oxygen (3O2) to singlet oxygen (1O2), benefiting PDT. This work demonstrates the great future potential of both SACs and MOFs as multifunctional agents for cancer treatment and tumor imaging.