Ethylene is an ideal CO2 product in an electrocatalytic CO2 reduction reaction (CO2RR), which has high economic value. In this paper, Al–doped octahedral Cu2O (Al–Cu2O) catalyst was synthesized by a simple wet chemical method. The selectivity of CO2RR products was improved by doping Al onto the surface of octahedral Cu2O by regulating the Al content. The Al–Cu2O was used as an efficient electrocatalyst for CO2RR with selective ethylene production. The Al–Cu2O exhibited a high Faradic efficiency (FEC2H4) of 44.9% at -1.23 V (vs. RHE) in CO2 saturated 0.1 M KHCO3 electrolyte. Charge transferring from Al atom to Cu atom take place after Al doping in Cu2O, thereby optimizing the electronic structure, which facilitates CO2RR to ethylene production. The DFT calculation showed that the Al–Cu2O catalyst can effectively reduce the adsorption energy of the *CHCOH intermediate and promote the mass transfer of charges, thus improving the FEC2H4. After Al doping into Cu2O, the center of d orbitals shift positively, which makes the d–band closer to the Fermi level. Furthermore, the density of electronic states increases, which was conducted to the interaction between Cu atoms and intermediates, thus accelerating the electrochemical CO2 reduction process. This work proved that the metal doping strategy can effectively improve the catalytic properties of Cu2O, thus providing a useful way for CO2 cycling and green production of C2H4.

Electrocatalytic reduction of CO2 to valuable chemicals can alleviate the energy crisis, and solve the greenhouse effect. The key is to develop non-noble metal electrocatalysts with high activity, selectivity and stability. Herein, bimetallic MOF materials (BiZn-MOF, BiSn-MOF and BiIn-MOF) were constructed by coordinating the P-zone transition metals Zn, In, Sn and Bi with the organic ligand 3-amino-1H-1,2,4-triazole-5-carboxylic acid (H2atzc) through a rapid microwave synthesis approach. The coordination centers in bimetallic MOF Catalyst were regulated to optimize the catalytic performance to CO2RR. The optimized catalyst BiZn-MOF exhibited high catalytic activity than those of Bi-MOF, BiSn-MOF and BiIn-MOF. The BiZn-MOF exhibited a higher selectivity for formate production with a Faradic efficiency (FE=92%) at a potential of -0.9 V (vs. RHE) with a current density of 13 mA/cm2. The current density maintained for 13 h continuous electrolysis. The electrochemical conversion of CO2 to formic acid mainly follows the *OCHO pathway. The good catalytic performance of BiZn-MOF may be attributed to the Bi-Zn bimetallic coordination centers in the MOF, which can reduce the binding energies of the reaction intermediates by tuning the electronic structure and atomic arrangement. This study provides a feasible strategy for performance optimization of bismuth-based catalysts.

Increasing the loading density of nanoparticles on carbon support is essential for making Pt-alloy/C catalysts practical in H2-air fuel cells. The challenge lies in increasing the load-ing while suppressing the sintering of Pt-alloy nanoparticles. This work presents a 40% Pt-weighted sub-3 nm PtCo/C alloy catalysts via a simple incipient wetness impregnation method. By carefully optimizing the synthetic conditions such as Pt/Co ratios, calcination temperature and time, the size of supported PtCo alloy nanoparticles is successfully con-trolled below 3 nm, and a high electrochemical surface area achieves of 94 m2/g is achieved, which is 2.8 times of commercial PtCo/C-TKK catalysts. Demonstrated by elec-trochemical oxygen reduction reaction, PtCo/C alloy catalysts present an enhanced mass activity of 0.45 A/mg at 0.9 V vs. RHE, which is 1.7 times that of PtCo/C-TKK catalyst. Therefore, the developed PtCo/C alloy catalyst can potentially be a highly practical cata-lyst for H2-air fuel cells.

Current hydrogen production is based on the reforming process leading to the emission of pollutants; therefore, a substitute production method is imminently required. Water electrolysis is an ideal alternative for large-scale hydrogen production, as it does not produce any carbon-based pollutant byproducts. Production of green hydrogen from water electrolysis using intermittent sources (e.g., solar, eolic) would facilitate clean energy storage. However, the electrocatalysts currently required for water electrolysis are noble metals, making this potential option expensive and inaccessible for industrial applications. Therefore, there is a need to develop electrocatalysts based on earth-abundant and low-cost metals. Nickel-based electrocatalysts are a fitting alternative because they are economically accessible. Extensive research has focused on developing nickel-based electrocatalysts for hydrogen and oxygen evolution. Theoretical and experimental work have addressed the elucidation of these electrochemical processes and the role of heteroatoms, structure, and morphology. Even though some works tend to be contradictory, they have lit up the path for efficient nickel-based electrocatalysts. For these reasons, herein, a review of recent progress is presented.

Electronic waste (e-waste), characterized by the widespread disposal of electronic devices, shows a growing environmental challenge. In this study, we explore the electrocatalytic potential of gold nanoparticles supported on Vulcan obtained from e-waste for their application as electrocatalysts for the methanol oxidation reaction in alkaline media. Gold nanoparticles are synthesized from gold coatings recovered from Intel Pentium 4 processor pins, highlighting their sustainability as electrocatalyst precursors. Comprehensive characterization, including UV-Vis spectroscopy, transmission electron microscopy (TEM), scanning electron microscopy (SEM) and X-ray dif-fraction, is performed to assess the electrocatalyst's structural properties. Electrochemical evalu-ation is carried out in 0.5 M KOH electrolyte employing the rotating disk electrode technique, us-ing cyclic voltammetry for the study of methanol oxidation. Remarkably, the gold nanoparticles show electrocatalytic activity on par with commercially synthesized counterparts, demonstrating the feasibility of this approach for sustainable electrocatalyst production. Thus, this research opens new routes for utilizing e-waste as a source of valuable catalyst materials, addressing en-vironmental and technological challenges in the field of alkaline fuel cells.

This manuscript presents the result of utilizing cellulose as a template to prepare na-nosized WO3-NiWO4 and its application as co-catalysts in Pt/WO3-C and Pt/WO3-NiWO4-C for ethanol and glycerol electro-oxidation. Microcrystalline cellulose was hydrolyzed with phosphotungstic acid (H3PW12O40) to prepare the nanosized template of crystalline cellulose. Next, the template was impregnated with Ni(NO3)2, rendering a precursor mate-rial that is subsequently air-calcinated, removing the carbon-template material to obtain the nanometric WO3 and NiWO4. Elemental analysis confirmed the coexistence of nickel and tungsten, whereas the thermal analysis evidenced the high thermal stability of these materials. The X-ray diffractograms displayed crystal facets of WO3 and, when added Ni, of NiWO4. The transmission electron micrographs corroborated the formation of na-nosized particles with average particle sizes close to 50 nm. Finally, to apply this material, Pt/WO3-C and Pt/WO3-NiWO4-C were prepared and used in ethanol and glycerol electro-oxidation in alkaline medium, observing a promotional effect of the oxide and tungstate by reducing the onset potential and increasing the current density. These materials show great potential to produce clean electricity or green hydrogen contributing to energetic transition.

Metal organic frameworks (MOFs) are used in catalysis due to their high specific surface area and porous structure. The dispersed active sites and limited reaction space render MOFs have the potential for highly selective electrocatalytic CO2 reduction reaction (ECO2RR). Meanwhile, formic acid (HCOOH) is attracting attention as a liquid product with high economic benefits. This review summarizes the MOFs and their derivatives applied for ECO2RR into HCOOH products. The preparation methods of MOFs as electrocatalysts and their unique advantages are discussed. A series of MOFs, and MOFs derivatives obtained by electrochemical reduction or carbonization processes are highlighted, including metal nanomaterials, carbon-based nanocomposites, single-atom catalysts, and bimetallic nanocomposites. Depending on the MOFs building units (metal ions and organic linkers) and the reaction conditions of derivatization, MOFs-based catalysts exhibit rich diversity and controllable modulation of catalytic performance. Finally, the challenges encountered at this stage and the future research directions of MOFs-based catalysts are proposed.

Low-dimensional carbon-based (LDC) materials have attracted extensive research attentions in electrocatalysis because of their unique advantages such as structural diversity, low cost, and chemical tolerance. They have been widely used in a broad range of electrochemical reactions to relief environmental pollution and energy crisis. Typical examples include hydrogen evolution reaction (HER), oxygen evolution reaction (OER), oxygen reduction reaction (ORR), carbon dioxide reduction reaction (CO₂RR), and nitrogen reduction reaction (NRR). Traditional “trial and error” strategies seriously slowed down the rational design of electrocatalysts for these important applications. Recent studies show that the combination of density functional theory (DFT) calculations and experimental research is capable of accurately predicting the structures of electrocatalysts, thus could reveal the catalytic mechanisms. Herein, current well-recognized collaboration methods of theory and practice are reviewed. The history of modern DFT, commonly used calculation methods, and basic functionals are briefly summarized. Special attention is paid to descriptors that are widely accepted as a bridge links the structure and activity, and the breakthroughs for high-volume accurate prediction of electrocatalysts. Importantly, correlating multiple descriptors are used to systematically describe the complicated interfacial electrocatalytic processes of LDC catalysts. In addition, machine learning and high-throughput simulations are crucial in assisting the discovery of new multiple descriptors and reaction mechanisms. This review will guide the further development of LDC electrocatalysts for extended applications from the aspect of DFT computations.

This review describes major advances in the use of functionalized molecular metal oxides (polyoxometalates, POMs) as water oxidation catalysts under electrochemical conditions. The fundamentals of POM-based water oxidation are described together with a brief overview of general approaches to designing POM water oxidation catalysts. Next, the use of POMs for homogeneous, solution-phase water oxidation is described together with a summary of theoretical studies shedding light on the POM-WOC mechanism. This is followed by a discussion of heterogenization of POMs on electrically conductive substrates for technologically more relevant application studies. Stability of POM water oxidation catalysts are discussed on selected examples where detailed data is already available. The review finishes with an outlook on future perspective and emerging themes in electrocatalytic polyoxometalate-based water oxidation research.

Molecular mechanisms for N2 fixation (solar NH3) and CO2 conversion to C2+ products in enzymatic conversion (Nitrogenase), electrocatalysis, metal-complexes and plasma-catalysis are analysed and compared. It is evidenced that differently from what present in thermal and plasma-catalysis, the electrocatalysis path requires not only the direct coordination and hydrogenation of undissociated N2 molecule, but to realize a series of features present in the Nitrogenase mechanism. There is the need of i) a multi-electron and -proton simultaneous transfer, not as sequential steps, ii) forming bridging metal hydride species, iii) generate intermediates stabilized by bridging multiple metal atoms, iv) have the capability of the same sites to be effective both in N2 fixation and in COx reduction to C2+ products. Only iron oxide/hydroxide stabilized at defective sites of nanocarbons was found to have these features. This comparison of the molecular mechanisms in solar NH3 production and relations with CO2 reduction is proposed to be a source of inspiration to develop the next generation electrocatalysts to address the challenging transition to a future sustainable energy and chemistry beyond fossil fuels.

Metal-organic frameworks (MOFs) are investigated for the oxygen evolution reaction (OER) due to their structure diversity, high specific surface area, adjustable pore size and abundant active sites. However, the poor conductivity of most MOFs restricts this application. Herein, through a facile one-step solvothermal method, the Ni-based pillared metal-organic framework [Ni2(BDC)2DABCO] (BDC = 1,4-benzenedicarboxylate, DABCO = 1,4-diazabicyclo[2.2.2]octane), its bimetallic nickel-iron form [Ni(Fe)(BDC)2DABCO] and their modified Ketjenblack (mKB) composites were synthesized and tested towards OER in an alkaline medium (KOH 1 mol L–1). A synergistic effect of the bimetallic nickel-iron MOF and the conductive mKB additive enhance the catalytic activity of the MOF/mKB composites. All MOF/mKB composite samples (7, 14, 22, 34 wt.% mKB) indicated much higher OER performances than the MOFs and mKB alone. The Ni-MOF/mKB14 composite (14 wt. % of mKB) demonstrated an overpotential of 294 mV at a current density of 10 mA cm–2 and Tafel slope of 32 mV dec–1, which is comparable with commercial RuO2 commonly used as a benchmark material for OER. The catalytic performance of Ni(Fe)MOF/mKB14 (0.57 wt% Fe) was improved further to an overpotential of 279 mV at a current density of 10 mA cm–2. The low Tafel slope of 25 mV dec–1 as well as a low reaction resistance due to electrochemical impedance spectroscopy (EIS) measurement confirm the excellent OER performance of the Ni(Fe)MOF/mKB14 composite. For practical applications, the Ni(Fe)MOF/mKB14 electrocatalyst was impregnated into commercial nickel foam (NF), where overpotentials of 247 and 291 mV at current densities of 10 and 50 mA cm–2, respectively, were realized. The activity was maintained for 30 h at the applied current density of 50 mA cm–2. The electrocatalytic system consisting of earth-abundant Ni and Fe metals only would be attractive for the development of efficient, practical and economical energy conversion materials for efficient OER activity.

Prebiotic organic synthesis reactions catalyzed by Earth-abundant metal sulfides are key processes for understanding the evolution of biochemistry from inorganic molecules, yet the catalytic functions of sulfides have remained poorly explored in the context of the origins of life. Past studies on prebiotic chemistry have mostly focused on a few types of metal sulfide catalysts, such as FeS or NiS, which form limited types of products with inferior activity and selectivity. To explore the potential of metal sulfides on catalyzing prebiotic chemical reactions, here, the chemical diversity (variations in chemical composition and phase structure) of 304 natural metal sulfide minerals in a mineralogy database was surveyed and approaches to rationally predict the catalytic functions of metal sulfides are discussed based on advanced theories and analytical tools of electrocatalysis such as proton-coupled electron transfer, structural comparisons between enzymes and minerals, and in-situ spectroscopy. To this end, we introduce a model of geo-electrochemistry driven prebiotic synthesis for chemical evolution, as it helps us to predict kinetics and selectivity of targeted prebiotic chemistry under “chemically messy conditions”. We expect that combining the data-mining of mineral databases with experimental methods and theories developed in the field of electrocatalysis will facilitate the prediction and verification of catalytic performance under a wide range of pH and Eh conditions, and aid in the rational screening of mineral catalysts involved in the origins of life.

In this review, we focus on a small section of the extensive literature that deals with the materials containing pristine defective CNs and those incorporated in the hybrid materials. We will discuss only those topics that focus on structural defects related to the introduction of perturbation into the surface topology of a nanostructure. We focus mainly on the method using microwave (MW) irradiation, which is a powerful tool for synthesizing and modifying carbon-based solid materials. In addition, the simplicity of the technique, economy, and the possibility of conducting the reaction in solvents and solid phase, in the presence of components of different chemical nature, allows use in various combinations. In this review, we will emphasize the advantages of synthesis using MW-assisted heating and indicate the influence of the structure of the obtained materials on their physical and chemical properties. We will also highlight the role of the occurrence of defects in the carbon material and the implication in designing their properties and applications.

The screen-printed carbon nanofibers electrodes (SPCNFE) represent an alternative with great acceptance due to their results, as well as their low impact for the environment. In order to improve their performance, in the present work they were modified with silver nanoparticles (Ag-NPs) and electrochemically characterized by using anodic stripping voltammetry. From the Ag-NPs synthesis, silver seeds (Ag-NS) and silver nanoprisms (Ag-NPr) were obtained. The Ag-NPs formation was confirmed by micrographs where Ag-NPs with diameters of 12.20±0.04 nm for Ag-NS, and 20.40±0.09 nm for Ag-NPr were observed. The electrodes were modified by using three different deposition methods: drop-casting, spin-coating and in-situ approaches. It was observed that the last methodology showed a low amount of Ag-NS deposited on the electrode surface and a deep alteration of this surface. Those facts suggested that the in situ synthesis methodology were not appropriate for the determination of heavy metals and it was discarded. The incorporation of the nanoparticles by spin-coating and drop-casting strategies showed different spatial distribution on the electrode surface as proved by scanning electron microscopy. The electrodes modified by these strategies, were evaluated for the cadmium(II) and lead(II) detection using differential pulse anodic stripping voltammetry, obtaining detection limit values of 2.1 and 2.8 µg L^-1, respectively. The overall results showed that the incorporation route does not change directly the electrocatalytic effect of the nanoparticles, but the shape of these nanoparticles (spherical for seeds and triangular for prisms) has a preferential electrocatalytical enhancement over Cd(II) or Pb(II).