Photoactive Earth‐Abundant Iron Pyrite Catalysts for Electrocatalytic Nitrogen Reduction Reaction

The generation of ammonia, hydrogen production, and nitrogen purification are considered as energy intensive processes accompanied with large amounts of CO₂ emission. An electrochemical method assisted by photoenergy is widely utilized for the chemical energy conversion. In this work, earth‐abundant iron pyrite (FeS₂) nanocrystals grown on carbon fiber paper (FeS₂/CFP) are found to be an electrochemical and photoactive catalyst for nitrogen reduction reaction under ambient temperature and pressure. The electrochemical results reveal that FeS₂/CFP achieves a high Faradaic efficiency (FE) of ≈14.14% and NH₃ yield rate of ≈0.096 µg min^?1 at ?0.6 V versus RHE electrode in 0.25 m LiClO₄. During the electrochemical catalytic reaction, the crystal structure of FeS₂/CFP remains in the cubic pyrite phase, as analyzed by in situ X‐ray diffraction measurements. With near‐infrared laser irradiation (808 nm), the NH₃ yield rate of the FeS₂/CFP catalyst can be slightly improved to 0.1 µg min^?1 with high FE of 14.57%. Furthermore, density functional theory calculations demonstrate that the N₂ molecule has strong chemical adsorption energy on the iron atom of FeS₂. Overall, iron pyrite‐based materials have proven to be a potential electrocatalyst with photoactive behavior for ammonia production in practical applications.     

Nanoporous Surface High-Entropy Alloys as Highly Efficient Multisite Electrocatalysts for Nonacidic Hydrogen Evolution Reaction

Electrocatalytic hydrogen evolution in alkaline and neutral media offers the possibility of adopting platinum-free electrocatalysts for large-scale electrochemical production of pure hydrogen fuel, but most state-of-the-art electrocatalytic materials based on nonprecious transition metals operate at high overpotentials. Here, a monolithic nanoporous multielemental CuAlNiMoFe electrode with electroactive high-entropy CuNiMoFe surface is reported to hold great promise as cost-effective electrocatalyst for hydrogen evolution reaction (HER) in alkaline and neutral media. By virtue of a surface high-entropy alloy composed of dissimilar Cu, Ni, Mo, and Fe metals offering bifunctional electrocatalytic sites with enhanced kinetics for water dissociation and adsorption/desorption of reactive hydrogen intermediates, and hierarchical nanoporous Cu scaffold facilitating electron transfer/mass transport, the nanoporous CuAlNiMoFe electrode exhibits superior nonacidic HER electrocatalysis. It only takes overpotentials as low as ≈240 and ≈183 mV to reach current densities of ≈1840 and ≈100 mA cm⁻² in 1 m  KOH and pH 7 buffer electrolytes, respectively; ≈46- and ≈14-fold higher than those of ternary CuAlNi electrode with bimetallic Cu–Ni surface alloy. The outstanding electrocatalytic properties make nonprecious multielemental alloys attractive candidates as high-performance nonacidic HER electrocatalytic electrodes in water electrolysis.     

Regulating the Interfacial Electronic Coupling of Fe2N via Orbital Steering for Hydrogen Evolution Catalysis

The capability of manipulating the interfacial electronic coupling is the key to achieving on-demand functionalities of catalysts. Herein, it is demonstrated that the electronic coupling of Fe₂N can be effectively regulated for hydrogen evolution reaction (HER) catalysis by vacancy-mediated orbital steering. Ex situ refined structural analysis reveals that the electronic and coordination states of Fe₂N can be well manipulated by nitrogen vacancies, which impressively exhibit strong correlation with the catalytic activities. Theoretical studies further indicate that the nitrogen vacancy can uniquely steer the orbital orientation of the active sites to tailor the electronic coupling and thus benefit the surface adsorption capability. This work sheds light on the understanding of the catalytic mechanism in real systems and could contribute to revolutionizing the current catalyst design for HER and beyond.     

Efficient Electron Transfer Processes and Enhanced Electrocatalytic Activity of Cobalt(II) Porphyrin Anchored on Graphene Oxide

We investigated the electronic perturbation between graphene oxide and cobalt porphyrin to reveal the origin of the enhanced electrocatalytic activity of a hybrid complex using time-resolved spectroscopic measurements and theoretical calculations. The impulsively generated charge-separated state, GO⁻-(Co^IIAPFP)⁺, undergoes fast charge recombination (<10 ps) between GO⁻ and (Co^IIAPFP)⁺ moieties. This fast charge recombination is directly related to the quick neutralization of (Co^IIAPFP)⁺, which shortens the dead time of inactive Co^IIIAPFP after the electrocatalytic reduction reaction. The fast transformation of inactive Co^IIIAPFP to active Co^IIAPFP is an important factor in the enhanced electrocatalytic activity of the hybrid complex.     

Comparison of different methods for determination of Pt surface site concentrations for supported Pt electrocatalysts

Platinum surface atom (or site) concentrations for a series of commercially available 10, 20, and 40 wt% Pt/C electrocatalysts have been determined using X-ray diffraction (XRD), high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), selective chemisorption, and cyclic voltammetry (CV) methods. Each method of analysis was repeated for a sufficient number of times to determine reproducibility and standard deviation limits. Comparison of the results shows that XRD and STEM methods give Pt surface site concentrations much higher than for chemisorption analysis due to assumptions regarding Pt particle shapes and particle size distributions. The results from CV analysis agree reasonably well with those from chemisorption if the sample amounts and methods of sample deposition preceding CV analysis can be well-controlled and there is no loss of surface exposure by the Nafion over-layer. Because both chemisorption and CV analyses more directly measure actual site concentrations with fewer assumptions, these methods should be considered superior to XRD and STEM analyses. Further, since chemisorption uses substantially larger sample sizes (up to 0.25 g) compared to CV (<0.01 g), reliability of chemisorption data is much more reliable and should be considered as the metric for surface Pt site determination.     

Additional doping of phosphorus into polypyrrole functionalized nitrogenous carbon nanotubes as novel metal-free oxygen reduction electrocatalyst in alkaline solution

Novel phosphorus-doped polypyrrole functionalized nitrogenous carbon nanotubes (P/NCNTs) was developed for the first time as metal-free electrocatalyst for enhancing the oxygen reduction reaction (ORR) activity in alkaline medium. The P/NCNTs was successfully synthesized by pyrolyzing PPy and triphenylphosphane (TPP) under N₂, using pyrrole as carbon and nitrogen precursors, TPP as phosphorus precursor. Various characterizations such as transmission electron microscopy (TEM), X-ray diffraction (XRD), Raman spectra, Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) reveal that the P/NCNTs material has covalently bound P atoms with carbon framework, which can introduce defect sites and can induce uneven charge distribution. Moreover, the content of pyridine N increased after P-doping, which is of great significance in improving the ORR activity. The electrochemical behavior of the resultant material shows that the P/NCNTs has much enhanced electroactivity and better stability for ORR. Additionally, a direct four-electron pathway occurred efficiently on P/NCNTs modified electrode. These enhanced performances indicate that P/NCNTs catalyst may be an excellent cathode catalyst for ORR.     

石墨烯载体上直接合成具有Pt(100)择优取向的催化剂及其电催化性能研究

以石墨烯为载体,乙二醇为还原剂,采用油浴法,通过加入不同添加剂作为形状导向剂合成了Pt(100)晶面择优取向的催化剂,并探讨了催化剂的性能。利用X射线衍射仪(XRD)、透射电镜(TEM)、感应耦合等离子原子发射光谱 (ICP-AES)及扫描电镜(SEM)对所合成的催化剂进行微观表征,利用电化学工作站对所合成的催化剂进行电化学性能测试。结果表明,添加KBr参与合成的Pt(100)晶面取向的催化剂,其微观粒子的立方体形貌最为规整,且形成最彻底。同时,其电催化性能最优,电化学活性表面积为42.43m2/g,对乙醇氧化的峰值电流密度为417.67A/g,1100s的稳态电流密度值为149.50A/g,对乙醇催化氧化反应的活化能最低,对乙醇氧化峰电流密度保持率为82.26%。     

Superior electrocatalytic activity of mesoporous Au film templated from diblock copolymer micelles

Mesoporous Au films consisting of a network of interconnected Au ligaments around ultra-large pores were found to exhibit a promising electrocatalytic activity towards sluggish reactions. Mesoporous Au films with pore sizes up to 25 nm were successfully fabricated using a polymeric micelle approach. A superior catalytic activity of the mesoporous Au films towards methanol oxidation was confirmed, which was thoroughly analyzed and compared with that of other Au materials. An intrinsic investigation on the high catalytic activity revealed that the superior performance of the as-prepared mesoporous Au film was related to its unique atomic structures around the mesopores with well-crystallized facets and several step/kink sites on the Au surfaces. These findings showcase a strategic and feasible design for preparing highly active Au-based catalysts that could be used as promising candidates in electrocatalytic applications.

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A simple synthesis method for nanostructured Co-WC/carbon composites with enhanced oxygen reduction reaction activity

Co nanoparticles (Co NPs) and nanoscale tungsten carbide (WC) are successfully synthesized simultaneously with mesoporous structured carbon black (C) using an innovative simple method, which is known as solution plasma processing (SPP), and NPs are also loaded onto carbon black at the same time by SPP. The introduction of Co NPs led to not only superior oxygen reduction reaction (ORR) activity in terms of onset potential and peak potential, but also to a more efficient electron transfer process compared to that of pure WC. Co-WC/C also showed durability for long-term operation better than that of commercial Pt/C. These results clearly demonstrate that the presence of Co NPs significantly enhanced the ORR and charge transfer number of neighboring WC NPs in ORR activities. In addition, it was proved that SPP is a simple method (from synthesis of NPs and carbon black to loading on carbon black) for the large-scale synthesis of NP-carbon composite. Therefore, SPP holds great potential as a candidate for next-generation synthetic methods for the production of NP-carbon composites.