Re-Looking into the Active Moieties of Metal X-ides (X- = Phosph-, Sulf-, Nitr-, and Carb-) Toward Oxygen Evolution Reaction

Non-precious metal-based catalysts for oxygen evolution reaction (OER) have been extensively studied, among which the transition metal X-ides (including phosph-ides, sulf-ides, nitr-ides, and carb-ides) materials are emerging as promising candidates to replace the benchmark Ir/Ru-based materials in alkaline media. However, it is controversial whether the metal Xides host the real active sites since these metal Xides are thermodynamically unstable under a harsh OER environment—it has been reported that the initial metal Xides can be electrochemically oxidized and transformed into corresponding oxides and (oxy)hydroxides. Therefore, the metal Xides are argued as “pre-catalysts”; the electrochemically formed oxides and (oxy)hydroxides are believed as the real active moieties for OER. Herein, the recent advances in understanding the transformation behavior of metal Xides during OER are re-looked; importantly, hypotheses are provided to understand why the electrochemically formed oxides and (oxy)hydroxides catalysts derived from metal Xides are superior for OER to the as-prepared metal oxides and (oxy)hydroxides catalysts.     

Heterogeneously Catalyzed Methanolysis of Gmelina Seed Oil to Biodiesel

The heterogeneous catalysis of transesterification of gmelina seed oil to biodiesel is evaluated. The oil was extracted from the seeds with n‐hexane by solvent extraction and characterized to determine its physiochemical properties. Response surface methodology was applied to optimize the effect of process variables on the biodiesel yield. The base‐activated clay catalyst performed as montmorillonite clay with the characteristic property of a Brønsted acid. It has an improved surface area after activation that enhanced its catalytic activity on transesterification reaction. Under optimal conditions, the biodiesel yield was 70.1 %, thus demonstrating that the model predicted well the biodiesel production.     

聚乙烯催化剂用烷氧基镁载体的研究进展

基于烷氧基镁载体的Ziegler-Natta聚乙烯催化剂具有活性高、氢调性能好等优点,是目前聚烯烃工业中的研究热点。介绍了烷氧基镁载体的发展进程,综述了烷氧基镁载体的制备及改进方法,分析了烷氧基镁载体在催化剂制备过程中的作用,并对开发适用于乙烯聚合的烷氧基镁载体提出了展望。     

On the Catalytic Activity of Sn Monomers and Dimers at Graphene Edges and the Synchronized Edge Dependence of Diffusing Atoms in Sn Dimers

In this study, in situ transmission electron microscopy is performed to study the interaction between single (monomer) and paired (dimer) Sn atoms at graphene edges. The results reveal that a single Sn atom can catalyze both the growth and etching of graphene by the addition and removal of C atoms respectively. Additionally, the frequencies of the energetically favorable configurations of an Sn atom at a graphene edge, calculated using density functional theory calculations, are compared with experimental observations and are found to be in good agreement. The remarkable dynamic processes of binary atoms (dimers) are also investigated and is the first such study to the best of the knowledge. Dimer diffusion along the graphene edges depends on the graphene edge termination. Atom pairs (dimers) involving an armchair configuration tend to diffuse with a synchronized shuffling (step-wise shift) action, while dimer diffusion at zigzag edge terminations show a strong propensity to collapse the dimer with each atom diffusing in opposite directions (monomer formation). Moreover, the data reveals the role of C feedstock availability on the choice a single Sn atom makes in terms of graphene growth or etching. This study advances the understanding single atom catalytic activity at graphene edges.     

Protection and confinement effect of carbon on Co/CoxOy nano-catalyst for efficient NaBH4 hydrolysis

The hydrolysis of sodium borohydride (NaBH₄) over catalysts is a promising method to produce hydrogen. Although Co-based catalysts exhibit high activity for NaBH₄ hydrolysis, they are still far from satisfying practical applications, especially their poor durability in alkaline media. Herein, a carbon shell structure was designed and synthesized to improve the stability of the mixture of Co⁰ and Co_xO_y nanofilms (Co/Co_xO_y@C) during NaBH₄ hydrolysis via a facile polymerization-pyrolysis strategy with Co/Co_xO_y nanofilms as the precursor. As a result, the Co/Co_xO_y@C catalyst can achieve a remarkable H₂ generation rate of 4348.6 mL min^?1 g_Co^?1 with a low activation energy of 43.6 kJ mol^?1, which is superior to most previously reported catalysts. Moreover, the catalyst shows high stability with an H₂ generation-specific rate of 79% after five cycles. The excellent performance of carbon substrate can well prevent the agglomeration of Co-based nanoparticle and improve the corrosion resistance of the active Co to BO₂^? and OH^?. This work would widen the road for the preparation of nanoconfined catalysts, which has prospective application potentials for H₂ production from NaBH₄ hydrolysis.     

Hydrogen production via ammonia decomposition catalyzed by Ni/M–Mo–N (M = Ni,Co) bimetallic nitrides

This study demonstrates the significant improvement in NH₃ decomposition using Ni-decorated M–Mo–N-based catalysts (M = Co and Ni) compared with conventional catalysts. Catalysts are prepared using a mixture of the corresponding metal salts and hexamethylenetetramine, and the impregnation method is used to decorate the Ni-particles on the catalysts. Among all the samples, 10 wt% Ni-decorated Co₃Mo₃N exhibits the highest NH₃ conversion rate (71%) at 500 °C, and the performance remains stable for 30 h of long-term testing. According to the gas chromatography measurements, the H₂/N₂ ratio is approximately 3 in all cases, which is consistent with the theoretical value. X-ray photoelectron spectroscopy results show that Co₃Mo₃N possesses the highest NH₃ conversion efficiency because of the weaker binding energy of Mo–N. Furthermore, Co₃Mo₃N exhibits a stronger Lewis acidity and higher NH₃ decomposition, which is attributed to the easy breaking of the N–H bond on the Co₃Mo₃N surface.     

Catalysts by pyrolysis: Direct observation of transformations during re-pyrolysis of transition metal-nitrogen-carbon materials leading to state-of-the-art platinum group metal-free electrocatalyst

Transition metal-nitrogen-carbon (M-N-C) materials have been the focus of scientists’ efforts to address the rising need for earth-abundant materials solutions for energy technology and decarbonization of the economy. They are viewed as one of the most promising candidates to replace platinum group metal (PGM) catalysts in the fuel cell and energy conversion fields, including the application of oxygen reduction reaction, carbon dioxide reduction reaction, and nitrogen reduction reaction. In the effort to improve M-N-C materials properties and achieve atomic dispersity of the transition metal in the carbonaceous matrix, a re-pyrolysis process has been proposed. This secondary heat treatment process of already obtained primary pyrolysis-derived M-N-C materials has been widely reported to substantially improve the electrochemical performance and operational stability of the catalysts. Here, we report a systematic investigation of this process used on samples of templated M-N-C catalysts to obtain state-of-the-art catalysts via in situ heating X-ray photoelectron spectroscopy (XPS), scanning transmission electron microscopy (STEM), energy-dispersive X-ray spectroscopy (EDS), electron energy loss spectroscopy (EELS), X-ray diffraction (XRD), and X-ray computed tomography (CT) characterization methods. It is found that the re-pyrolysis of M-N-C materials could result in the partial amorphization of the carbonaceous substrate. It causes the rearrangement and transformation of multitudinous N moieties, leading to optimization of their morphological display and association with atomically dispersed transition metal dopants. Ultimately, the re-pyrolysis results in an increase in uniformity of the active Fe-N_x sites distribution without the formation of nano-crystalline phases (metallic or carbide) and with overall preservation of the morphology of the carbonaceous framework achieved during the first formative pyrolysis step of the templated synthesis. These observations provide confirmation that empirically established re-pyrolysis is recommended to be used on all M-N-C materials despite the different synthesis routes to obtain a practical advanced catalytic material.     

Magnetic porous nano-carbon catalysts supported silver nanoparticles derived from chitin and their application in catalytic reduction reactions

The exploitation of recycled carbonaceous catalysts from renewable biomass resources such as chitin is a crucial issue for the development of the sustainable society. In this article, the chitin-based N and O doped carbon microspheres (ChC) were fabricated by a simple dissolution, sol–gel transformation, and the carbonization methods. Subsequently, the novel magnetic Ag-Fe₃O₄@chitin-based carbon microspheres catalyst (MChC) was successfully constructed through the in situ redox reaction. The as-prepared MChC possessed rich micropores with high-surface area, and a narrow size distribution (50–120 μm). The Ag-Fe₃O₄ nanoparticles were immobilized through the interaction with C, N, and O atoms in the pores of MChC. The reduction of 4-nitrophenol was applied to evaluate the catalytic activity of MChC. 4-Nitrophenol (4-NP) could be fully reduced to 4-aminophenol (4-AP) in 5 min with the catalyst MChC-45. Moreover, MChC could be collected in solution with an external magnet in 8 s and remained relatively high-catalytic activity after 10 cycle times. This work provided novel ideas for the fabrication of doped carbon material from biomass and promoted its utilization in nanocatalytic applications.     

Recent advances during CH4 dry reforming for syngas production: A mini review

Given the continuing issues of environment and energy, methane dry reforming for syngas production have sparked interest among researchers, but struggled with the process immaturity owing to catalyst deactivation. This review summarizes the recent advances in the development of efficient and stable catalysts with strong resistance to coking and metal sintering, including the application of novel materials, the assessment of advanced characterizations and the compatibility to improved reaction system. One feasible option is the crystalline oxide catalysts (perovskite, pyrochlore, spinel and LDHs), which feature a fine metal dispersion and surface confinement effect via a metal exsolution strategy and exhibit superior reactivity and stability. Some new materials (h-BN, clays and MOFs) also extend the option because of their unique morphology and microstructure. It also is elaborated that progresses were achieved in advanced characterizations application, leading to success in the establishment of reaction mechanisms and attributions to the formed robust catalysts. In addition, the perspective described the upgrade of reaction system to a higher reaction efficiency and milder reaction conditions. The combination of efficient reaction systems and robust catalysts paves a way for a scaling-up application of the process.