Non-Platinum Group Metal Electrocatalysts toward Efficient Hydrogen Oxidation Reaction

Developing non-platinum group metal (non-PGM) electrocatalysts for the hydrogen oxidation reaction (HOR) represents the efforts towards the more economical use of hydrogen fuel cells and hydrogen energy, which has attracted tremendous attention recently. However, non-PGM electrocatalysts for the HOR are still in their early development stages as compared with the significant advances in those for the oxygen reduction reaction and hydrogen evolution reaction. Herein, this paper summarizes the recent progresses and highlights the key challenges for the rational design of non-PGM electrocatalysts, aiming to promote the development of non-PGM HOR electrocatalysts. Fundamental understandings of the HOR mechanism are firstly reviewed, where theoretical interpretations on the low HOR kinetics in alkaline media, including the hydrogen binding energy theory, the bifunctional mechanism, and the water molecule reorganization, are particularly discussed. Subsequently, progresses of typical non-PGM HOR electrocatalysts in acid and alkaline media are summarized separately. For the HOR under alkaline conditions, the superiorities and challenges of Ni-based catalysts are discussed with a particular focus as they are the most promising non-PGM electrocatalysts. Finally, this paper highlights the challenges and provide perspectives on the future development directions of non-PGM HOR electrocatalysts.     

Embedding carbon dots in Eu3+-doped metal-organic framework for label-free ratiometric fluorescence detection of Fe3+ ions

Fluorescent detection is a new spectroscopic measurement for ions sensing due to the advantages of real-time determination with high selectivity, accuracy, and low cost. However, chemosensors based on fluorescent detection are usually determined by absolute intensity from a monochromatic emission signal, which is easy to be fluctuated by the external environment, especially for Fe³⁺ detection in complex fluids. Herein, we rationally design a dual-emission Eu³⁺: CDs@ZIF-8 to construct a ratiometric fluorescent sensor with self-calibrating ability for Fe³⁺ determination. High efficient carbon dots (CDs) are embedded in europium ions (Eu³⁺)-doped MOF by simple stirring preparation at room temperature. The label-free ratiometric fluorescent probe (I_CDs@ZIF-8/I_Eu) exhibits simultaneous blue and red emission under the same excitation at 365 nm. Remarkably, Eu³⁺: CDs@ZIF-8 displays the superiority of high selectivity to Fe³⁺, which shows ratiometric fluorescence characteristics (I₀/I) in a range of 0-6 μmol\L with a low limit of detection (LOD) of 0.897 μmol\L. Besides, the CDs-MOF nanocomposite holds good aqueous dispersibility and low cytotoxicity, which shows great potential applications in medical aid including biological detection and clinical diagnosis.     

Molecular fingerprint and machine learning to accelerate design of high-performance homochiral metal–organic frameworks

Computational screening was employed to calculate the enantioseparation capabilities of 45 functionalized homochiral metal–organic frameworks (FHMOFs), and machine learning (ML) and molecular fingerprint (MF) techniques were used to find new FHMOFs with high performance. With increasing temperature, the enantioselectivities for (R,S)-1,3-dimethyl-1,2-propadiene are improved. The “glove effect” in the chiral pockets was proposed to explain the correlations between the steric effect of functional groups and performance of FHMOFs. Moreover, the neighborhood component analysis and RDKit/MACCS MFs show the highest predictive effect on enantioselectivities among the four ML classification algorithms with nine MFs that were tested. Based on the importance of MF, 85 new FHMOFs were designed, and a newly designed FHMOF, NO₂-NHOH-FHMOF, with high similarity to the optimal MFs achieved improved chiral separation performance, with enantioselectivities of 85%. The design principles and new chiral pockets obtained by ML and MFs could facilitate the development of new materials for chiral separation.     

Integrating coral-like morphology into cyano-containing carbon nitride towards efficient photocatalytic H2 evolution and Cr(Ⅵ) reduction

The incomplete polymerization of graphite carbon nitride (g-C₃N₄) due to the kinetic problems resulted in its high recombination rate of photo-generated electron-hole pairs. Hence, cyano-containing carbon nitride with coral-like morphology (CCCN) was prepared by the molten salt method with heptazine-based melem as precursor, which presented excellent separation rate of photo-generated electron-hole pairs. SEM exhibited that CCCN owned coral-like morphology which exposed ample active sites and enhanced the capture ability of visible light while FT-IR and XPS demonstrated that cyano groups appearing in coral-like carbon nitride enhanced the separation rate of photo-induced charge carriers. The synergistic effect of coral-like morphology and cyano groups endowed CCCN-15% with superior performance of both the photocatalytic H₂ evolution (4207 μmol h^?1 g^?1) and Cr (Ⅵ) reduction (k = 0.059 min^?1), approximately 16.8 and 6.0 times that of g-C₃N₄, which was comparable among the similar materials. Density functional theory calculation (DFT) revealed that cyano groups decreased the bandgap and strengthened the activation degree of reaction substrate, which enhanced the thermodynamic driving force and the interaction between catalyst and substrate. This work provided a potential strategy for both the renewable energy generation and environmental restoration.     

ZIF-8 derived bimetallic Fe–Ni-Nanoporous carbon for enhanced oxygen reduction reaction

The development of highly efficient nοn-nοble meta? catalysts for (ОRR) in PEMFCs is at the heart of the research, yet their performance is not satisfactory. The Fe–N active sites enclosed in carbon matrix are generally agreed to be the most promising active sites for ORR. In view of this, further effort is made to increase the Fe–N active sites. Here we present the fabrication of novel FeNi bimetallic electrоcatalyst obtained from ZIF, which consists of FeNi nanоallоys incorporated in N-doped carbon (FeNi-NC) featuring carbon nanotubes and porous carbon demonstrates outstanding results for ОRR. The Fe–N and Ni–N active sites synergistically enhance the ORR activity of FeNi-NC catalyst. The FeNi-NC showed remarkable performance in KОH with the half-wave and onset potential of 0.89 V and 0.99 V vs RHE, respectively. This catalyst shows exceptional stability in methanol equivalent to Pt/C commercial. The FeNi-NC retained 71%, while Pt/C commercial retained only 59% of its original current density. The exceptional stability and activity might be associated with the interplay among FeNi active sites and N-doped carbon, the distinct nanо-structure made up of porous carbon and carbon nanotubes with a high graphitization degree.     

A strategic roadmap for large-scale green hydrogen demonstration and commercialisation in China: A review and survey analysis

Hydrogen is gaining increased attention from industries and policymakers in China. However, most of the current demonstration projects in the country have relied on conventional energy sources, including industrial byproduct hydrogen and grey hydrogen produced from fossil fuels. Moreover, strategies and policy frameworks leading to a shift to green or low-carbon hydrogen have neither been explored in-depth nor been identified clearly in the context of China. This study aims at bridging such gaps. Roadmapping techniques enhanced by the Delphi method and SWOT analysis are used to survey hydrogen energy experts from government bodies, industries, and academia to achieve basic agreement on strategically enabling large-scale green hydrogen demonstrations followed by commercialisation in China. The outcome of two rounds of surveys showed that experts' opinions converged on a strategic roadmap with three stages of development. The corresponding policies needed in each stage are evaluated and selected to form a systemic framework.     

Synthesis of hollow Fe,Co, and N-doped carbon catalysts from conducting polymer-metal-organic-frameworks core-shell particles for their application in an oxygen reduction reaction

Oxygen reduction reaction (ORR), one of the key reactions for fuel cells and zinc-air batteries, should be improved for higher performance. Herein, we fabricated hollow Fe, Co, and nitrogen co-doped carbon (H-FeCo-NC) catalyst, which was prepared by carbonization of core-shell particles made of polypyrrole (PPy)-coated polystyrene (PS) spheres as cores and (Zn, Co) bimetallic-zeolitic imidazolate frameworks (ZnCoBZIFs) as shells. PPy was used as a nitrogen and a carbon source. The H-FeCo-NC catalyst had a high surface area of 324.08 m² g^?1 with uniformly distributed Fe and Co species, and excellent ORR performance with the half-wave potential of 0.888 V vs. reversible hydrogen electrode in alkaline media. Furthermore, the H-FeCo-NC catalyst demonstrated exceptional stability, durability, and tolerance to methanol crossover.     

南水北调中线总干渠藻类的生态调度

南水北调中线总干渠无在线调蓄水库,对藻类生态调度过程中出现的问题开展生态调度实现策略和实施方式研究。主要实现策略包括:划定自身的调蓄区,隔离生态调度对下游的影响;采用高效的渠池运行方式,减少生态调度时蓄量的反复调整;综合考虑安全、快速、平稳等需求,设定生态调度实施进程和方式。具体实施方式包括:将总干渠划分为流速调控区、调蓄区和正常运行区,分别实施等体积、控制蓄量和闸前常水位方式运行;将生态调度过程划分为充水阶段和泄水阶段,基于流速调控目标值、持续时长和水位降幅约束条件,确定各阶段时长和各分区的闸门群调控方案等。基于2018年3月输水工况,采用明渠一维非恒定流模型,仿真总干渠上游15个渠池的藻类生态调度过程。结果表明,生态调度可在3.5 d内完成,各渠池的平均流速由0.48 m/s增至0.93 m/s,持续时间超过2 h。在整个生态调度过程中,水位变化平稳,水位变幅符合安全阈值要求,下游渠道的正常运行未受生态调度明显影响。     

Application of artificial neural network method to predict the breakage properties of PGE bearing chromite ore

In the present investigation, systematic grinding experiments were conducted in a laboratory ball mill to determine the breakage properties of low-grade PGE bearing chromite ore. The population balance modeling technique was used to study the breakage parameters such as primary breakage distribution (B_{i, j}) and the specific rates of breakage (S_i). The breakage and selection function values were determined for six feed sizes. The results stated that the breakage follows the first-order grinding kinetics for all the feed sizes. It was observed that the coarser feed sizes exhibit higher selection function values than the finer feed size. Further, an artificial neural network was used to predict breakage characteristics of low-grade PGE bearing chromite ore. The predicted results obtained from the neural network modeling were close to the experimental results with a correlation of determination R² = 0.99 for both product size and selection function.     

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.