Two-Dimensional Metal–Organic Framework Nanosheets with Cobalt-Porphyrins for High-Performance CO2 Electroreduction

The electrochemical reduction of CO₂ presents a promising strategy to mitigate the greenhouse effect and reduce excess carbon dioxide emission to realize a carbon-neutral energy cycle, but it suffers from the lack of high-performance electrocatalysts. In this work, catalytic active cobalt porphyrin [TCPP(Co)=(5,10,15,20)-tetrakis(4-carboxyphenyl)porphyrin-Co^II] was precisely anchored onto water-stable 2D metal–organic framework (MOF) nanosheets (Zr-BTB) to obtain ultrathin 2D MOF nanosheets [TCPP(Co)/Zr-BTB] with accessible catalytic sites for the CO₂ reduction reaction. Compared with molecular cobalt porphyrin, the TCPP(Co)/Zr-BTB exhibits an ultrahigh turnover frequency (TOF=4768 h⁻¹ at −0.919 V vs. reversible hydrogen electrode, RHE) owing to high active-site utilization. In addition, three post-modified 2D MOF nanosheets [TCPP(Co)/Zr-BTB-PABA, TCPP(Co)/Zr-BTB-PSBA, TCPP(Co)/Zr-BTB-PSABA] were obtained, with the modifiers of p-(aminomethyl)benzoic acid (PABA), p-sulfobenzoic acid potassium (PSBA), and p-sulfamidobenzoic acid (PSABA), to change the micro-environments around TCPP(Co) through the tuning of steric effects. Among them, the TCPP(Co)/Zr-BTB-PSABA exhibited the best performance with a faradaic efficiency (FE_CO) of 85.1 %, TOF of 5315 h⁻¹, and j_total of 6 mA cm⁻² at −0.769 V (vs. RHE). In addition, the long-term durability of the electrocatalysts is evaluated and the role of pH buffer is revealed.     

Fighting Deactivation: Classical and Emerging Strategies for Efficient Stabilization of Molecular Electrocatalysts

Development of highly active molecular electrocatalysts for fuel-forming reactions has relied heavily on understanding mechanistic aspects of the electrochemical transformations. Careful fine-tuning of the ligand environment oriented mechanistic pathways towards higher activity and optimal product distribution for several catalysts. Unfortunately, many catalysts deactivate in bulk electrolysis conditions, diminishing the impact of the plethora of highly tuned molecular electrocatalytic systems. This Minireview covers classical and emerging methods developed to circumvent catalyst deactivation and degradation, with an emphasis on successes with molecular electrocatalysts.     

Synthesis of 3D IrRuMn Sphere as a Superior Oxygen Evolution Electrocatalyst in Acidic Environment

The design of a three-dimensional structure for an Ir-based catalyst offers a great opportunity to improve the electrocatalytic performance and maximize the use of the precious metal. Herein, a novel wet chemical strategy is reported for the synthesis of an IrRuMn catalyst with a sphere structure and porous features. In the synthetic process, the combined use of citric acid and formamide is requisite for the formation of the sphere structure. This method leads to a favorable 3D IrRuMn sphere structure with many fully exposed active sites. Furthermore, an alloying noble metal, such as Ir or Ru, with the transition metal leads to enhanced oxygen evolution reaction (OER) activity. The doping of a transition metal, such as Mn, is an interesting example, because it exhibits stability and activity in both acidic and alkaline media. For the OER, the IrRuMn sphere catalyst exhibits an overpotential of 260 mV at a current density of 10 mA cm⁻² in strongly acidic 0.1 m HClO₄, which is superior to that of a commercial IrO₂/C catalyst. This approach provides a novel way to synthesize an Ir-based multimetallic spherical electrocatalyst, which exhibits exceptional efficiency for the acidic OER. It will pave the way for new approaches to the practical utilization of PEM electrolyzers.     

Phosphorene-Based Electrocatalysts

Phosphorene, generally defined as two-dimensional (2D) black phosphorus (BP) with monolayered or few-layered structure, has emerged as a promising member of the family of 2D materials. Since its discovery in 2014, extensive research has been focused on broadening its applications, covering the biological, photoelectric, and electrochemical fields, owing to the unique physicochemical and structural properties. As a single-elemental material, phosphorene has demonstrated its applicability for the preparation of efficient electrocatalysts for hydrogen evolution reaction (HER), oxygen evolution reaction (OER), nitrogen reduction reaction (NRR), and other electrocatalytic applications. In this Minireview, a summary of the very recent research progresses of phosphorene in electrocatalysis is offered, with a special focus on the effective synthetic strategies towards performance improvement. In the concluding section, challenges and perspectives are also discussed.     

ZrN6-Doped Graphene for Ammonia Synthesis: A Density Functional Theory Study

Considering the pivotal role of ammonia in the modern chemical industry, designing effective catalysts for the N₂-to-NH₃ conversion stimulates great research enthusiasms. In this work, by means of density functional theory calculations, we systematically investigated the electrocatalysis of six-coordinated transition metal atom anchored graphene for nitrogen fixation. The free energy analysis shows that the ZrN₆ configuration has a good activity toward ammonia synthesis under overpotential of 0.51 V. According to the electron transfer analysis, ZrN₆ site plays a bridging role in charge transfer between the functional graphene and the reactant. Furthermore, the presence of N₆ coordination increases the electron accumulation on the NNH_x intermediates, which weakens the intermolecular N−N bond, reducing the thermodynamic barrier of protonation process. This work provides a basic understanding of the interaction between transition metal and the adjacent coordination in tuning the reactivity.     

Flower-like Fe-Co-M (M=S,O, P and Se) Nanosheet Arrays Grown on Nickel Foam as High-efficiency Bifunctional Electrocatalysts

The development of highly efficient, inexpensive, abundant and non-precious metal electrocatalysts is the lifeblood of the hydrogen production industry, especially the hydrogen production industry by electrolysis of water. A Fe-Co-S/NF bifunctional electrocatalyst with nanoflower-like structure was synthesized on three-dimensional porous nickel foam through one-step hydrothermal and one-step high-temperature sulfuration operations, and the material displays high-efficiency electrocatalytic performance. As a catalyst for the hydrogen evolution reaction, Fe-Co-S/NF can drive a current density of 10 mA/cm² at an overpotential of 143 mV with a Tafel slope of 80.2 mV/dec. When it was used as an oxygen evolution reaction catalyst, it exhibits good OER reactivity with a low Tafel slope (82.6 mV/dec) and with requiring only 117 mV overpotential to drive current densities up to 50 mA/cm². In addition, the Fe-Co-S/NF//Fe-Co-S/NF electrolytic cell was assembled, an electrolysis voltage of 1.64 V is required to drive a current density of 50 mA/cm², which is one of the most active catalysts reported so far. This work indicates that the introduction of S, P and Se treating processes could effectively improve electrical conductivity of the material and enhance the catalytic activity of the material. This work offers an effective and convenient method for improving the morphology of the catalyst, increasing the surface area of the catalyst and developing high-efficiency and low-cost catalysts.     

N,S-Co-Doped Porous Carbon Nanofiber Films Derived from Fullerenes (C60) as Efficient Electrocatalysts for Oxygen Reduction and a Zn–Air Battery

The development of highly efficient metal-free electrocatalysts for the oxygen reduction reaction (ORR) has attracted great attention for the creation of electrochemical energy devices. In this study, one-dimensional (1 D) fullerene nanofibers prepared from liquid–liquid interfacial precipitation are first fabricated into fullerene-derived carbon nanofiber films (FCNFs) through a simple filtration procedure. Then, pyrolysis of the FCNFs in the presence of ammonia and sulfur produces N- and S-co-doped porous carbon nanofiber films (N,S-PCNFs). As excellent metal-free electrocatalysts for the ORR, N,S-PCNFs exhibit remarkable catalytic activity, superior stability, and excellent methanol tolerance in both alkaline and acidic solution. Such a high ORR performance benefits from the robust porous nanofiber network structure with high concentrations of active N- and S- groups and abundant defects. Notably, upon practical use of N,S-PCNFs as catalysts in Zn-air batteries, a high power density and a large operating voltage are achieved, with a performance comparable to that of the commercial Pt/C catalyst. This work presents a facile strategy for the creation of a new class of energy nanomaterials based on fullerenes, demonstrating their practical uses in electrocatalytic ORR processes and Zn-air batteries.     

Designing AI-Aided Analysis and Prediction Models for Nonprecious Metal Electrocatalyst-Based Proton-Exchange Membrane Fuel Cells

Traditionally, a larger number of experiments are needed to optimize the performance of the membrane electrode assembly (MEA) in proton-exchange membrane fuel cells (PEMFCs) since it involves complex electrochemical, thermodynamic, and hydrodynamic processes. Herein, we introduce artificial intelligence (AI)-aided models for the first time to determine key parameters for nonprecious metal electrocatalyst-based PEMFCs, thus avoiding unnecessary experiments during MEA development. Among 16 competing algorithms widely applied in the AI field, decision tree and XGBoost showed good accuracy (86.7 % and 91.4 %) in determining key factors for high-performance MEA. Artificial neural network (ANN) shows the best accuracy (R2=0.9621) in terms of predictions of the maximum power density and a decent reproducibility (R2>0.99) on uncharted I–V polarization curves with 26 input features. Hence, machine learning is shown to be an excellent method for improving the efficiency of MEA design and experiments.     

The Use of the Electron-Reservoir Complexes [Fe(I)Cp(arene)] for the Electrocatalytic Synthesis of Redox-Reversible Metal-Carbonyl Clusters Containing Ferrocenyldiphenylphosphine

Starting from [M₃(CO)₁₂] (M = Fe or Ru) and [CH₃CCo₃(CO)₉], the electron-tranfer-chain catalyzed synthesis of new Fe, Ru, and Co carbonyl clusters in which one or several carbonyl ligands have been selectively substituted by one or several ferrocenyldiphenylphosphine (FDPP) ligands has been achieved using the electron-reservoir complexes [Fe(I)Cp(arene)] as electrocatalysts. The number of FDPP ligands selectively introduced can be chosen from one per cluster for the three clusters up to one per metal for the Ru and Co clusters. The advantage of this family of electrocatalysts is that the driving force for the initiation step can be varied by changing the number of methyl groups on the rings. The FDPP substituted clusters show one reversible wave by cyclic voltammetry.