Reconstructed Water Oxidation Electrocatalysts: The Impact of Surface Dynamics on Intrinsic Activities

Electroreduction of small molecules such as H₂O, CO₂, and N₂ for producing clean fuels or valuable chemicals provides a sustainable approach to meet the increasing global energy demands and to alleviate the concern on climate change resulting from fossil fuel consumption. On the path to implement this purpose, however, several scientific hurdles remain, one of which is the low energy efficiency due to the sluggish kinetics of the paired oxygen evolution reaction (OER). In response, it is highly desirable to synthesize high-performance and cost-effective OER electrocatalysts. Recent advances have witnessed surface reconstruction engineering as a salient tool to significantly improve the catalytic performance of OER electrocatalysts. In this review, recent progress on the reconstructed OER electrocatalysts and future opportunities are discussed. A brief introduction of the fundamentals of OER and the experimental approaches for generating and characterizing the reconstructed active sites in OER nanocatalysts are given first, followed by an expanded discussion of recent advances on the reconstructed OER electrocatalysts with improved activities, with a particular emphasis on understanding the correlation between surface dynamics and activities. Finally, a prospect for clean future energy communities harnessing surface reconstruction-promoted electrochemical water oxidation will be provided.     

Oxidation State Modulation of Bismuth for Efficient Electrocatalytic Nitrogen Reduction to Ammonia

Electrocatalytic nitrogen reduction reaction (NRR) is a promising strategy for ammonia (NH₃) production under ambient conditions. However, it is severely impeded by the challenging activation of the NN bond and the competing hydrogen evolution reaction (HER), which makes it crucial to design electrocatalysts rationally for efficient NRR. Herein, the rational design of bismuth (Bi) nanoparticles with different oxidation states embedded in carbon nanosheets (Bi@C) as efficient NRR electrocatalysts is reported. The NRR performance of Bi@C improves with the increase of Bi⁰/Bi³⁺ atomic ratios, indicating that the oxidation state of Bi plays a significant role in electrochemical ammonia synthesis. As a result, the Bi@C nanosheets annealed at 900  ° C with the optimal oxidation state of Bi demonstrate the best NRR performance with a high NH₃ yield rate and remarkable Faradaic efficiency of 15.10  ± 0.43% at − 0.4 V versus RHE. Density functional theory calculations reveal that the effective modulation of the oxidation state of Bi can tune the p-filling of active Bi sites and strengthen adsorption of *NNH, which boost the potential-determining step and facilitate the electrocatalytic NRR under ambient conditions. This work may offer valuable insights into the rational material design by modulating oxidation states for efficient electrocatalysis.     

Molecule-confined modification of graphitic C3N4 to design mesopore-dominated Fe-N-C hybrid electrocatalyst for oxygen reduction reaction

To design inexpensive carbon catalysts and enhance their oxygen reduction reaction (ORR) activity is critical for developing efficient energy-conversion systems. In this work, a novel Fe-N-C hybrid electrocatalyst with carbon nanolayers-encapsulated Fe₃O₄ nanoparticles is synthesized successfully by utilizing the molecular-level confinement of graphitic C₃N₄ structures via hemin biomaterial. Benefiting from the Fe-N structure prevalent on the carbon nanosheets and large mesopore-dominated specific surface area, the synthesized catalyst under optimized conditions shows excellent electrocatalytic performance for ORR with an E_ORR at 1.08 V versus reversible hydrogen electrode (RHE) and an E_1/2 at 0.87 V vs. RHE, and outstanding long-term stability, which is superior to commercial Pt/C catalysts (E_ORR at 1.04 V versus RHE and E_1/2 at 0.84 V versus RHE). Moreover, the low hydrogen peroxide yield (<11%) and average electron transfer number (~3.8) indicate a four-electron ORR pathway. Besides, the maximum power density of the home-made Zn-air battery using the obtained catalyst is 97.6 mW cm⁻². This work provides a practical route for the synthesis of cheap and efficient ORR electrocatalysts in metal-air battery systems.     

Effect of ultrasonic waveforms on gas–liquid mass transfer in microreactors

This study aims to investigate the effect of ultrasonic waveforms on the gas–liquid mass transfer process. For a given load power (P), continuous rectangular wave yielded stronger bubble oscillation and higher mass transfer coefficient (k_La) than continuous triangular and sinusoidal wave. For pulsed ultrasound, the k_La decreased monotonically with decreasing duty ratio (D), resulting in weak enhancement at low D (≤33%). For a given average load power (P_A), concentrating the P for a shorter period resulted in a higher k_La due to stronger cavitation behavior. For a given P_A and D, decreasing the pulse period (T) led to an increase in k_La, which reached a constant high level when the T fell below a critical value. By optimizing the D and T, a k_La equivalent to 92% of that under continuous ultrasound was obtained under pulsed ultrasound at a D of 67%, saving 33% in power consumption.     

Fabrication of Co doped MoS2 nanosheets with enlarged interlayer spacing as efficient and pH-Universal bifunctional electrocatalyst for overall water splitting

Exploring inexpensive and active bifunctional electrocatalysts to produce hydrogen and oxygen from water at all pHs is highly desirable. Herein, we report a facile one-step method to prepare vertically aligned Co doped MoS₂ nanosheets with extended interlayer distance on carbon cloth (Co–MoS₂@CC) for full hydrolysis in both alkaline and acidic medium. Co–MoS₂@CC exhibits long-term durability with overpotentials of 56.6 mV and 130 mV for hydrogen generation and 242 mV and 201 mV for oxygen production at 10 mA cm^?2 in basic and acidic conditions, respectively. Moreover, we achieve low voltages of 1.585 V and 1.55 V in basic and acidic conditions respectively for the overall water splitting. We assume that such excellent property of Co–MoS₂@CC may be ascribed to the uncovering of more active sites and high porosity resulted from Co doping, which boosts the conductivity and thus reduces MoS₂ hydrogen adsorption free energy in HER, as well as benefits to catalytic active sites in OER. This one-step doping approach opens up new ways to regulate the intrinsic catalytic activity to catalyze total hydrolysis at all PHs.     

Mathematical model for coal conversion in supercritical water: reacting multiphase flow with conjugate heat transfer

Providing heat for supercritical water gasification (SCWG) of coal by coupling subsequent products oxidation in integrated supercritical water reactor (ISWR) provides an effective method for directional control of temperature field and avoids excessive hot spots caused by uniform heating. An exploratory numerical model incorporating particle-fluid flow dynamics, multispecies transport and thermal coupling between endothermic coal gasification and exothermic product oxidation was established to simulate the reacting multiphase flow process of coal conversion in a novel lab-scale ISWR. An eleven-lump kinetic model was proposed for the prediction of chemical reactions. And the thermal coupling relationship was described by conjugate heat transfer boundary conditions (BC). Detailed physical and chemical field distribution in ISWR were analyzed and influence factors were discussed. The results showed that oxidation of gas products as inner heat source could promote the gasification reaction with only slight or even little maximum temperature increase of the pressure-bearing wall. Coal feeding rate and oxygen supply method significantly affected the field distribution. The multi-injection compressed-air supply method provided a more uniform temperature field but would reduce heat transfer temperature difference. The carbon gasification efficiency (CGE) in the gasification zone could easily reach up to 97% under mild conditions (less than 650 °C).     

Quantitative determination of pore-structure change and permeability estimation under hydrate phase transition by NMR

Quantitatively characterizing the seepage features is critical important for multi-fluid flow in gas hydrate accumulations; however, limited researches concern water permeability during hydrate phase transition. In this work, nuclear magnetic resonance (NMR) measurement is employed to observe the in situ formation and dissociation of tetrahydrofuran (THF) hydrate in porous media. Results indicate that the relative free water and bound water consumption during hydrate phase transition can affect the seepage features of sediments. In addition, we investigate the growth habits of THF hydrate in quartz glass sand and find the growth pattern of the hydrate transforms from suspension to cementation when its saturation exceeds approximately 35%. The Tokyo model shows that the hydrate are heterogeneous distribution of pore-filling and likely to evolve in larger pores; The findings clearly show that NMR is an efficient and direct technique for investigating the seepage characteristics during hydrate phase transition as well as pore fluid distribution in sediments.     

正弦波纹挡板式沉降器内流动特性

采用VOF模型对正弦波纹式入口挡板的重力非均相沉降器内流场进行数值模拟研究。对比了正弦波纹挡板与平挡板的平均流场分布情况，分析了沉降器的轴向流速均一程度（λ₁）随时间演化特性，探究了λ₁和面积加权平均湍流强度（I_a）在沉降器内空间分布特性；引入流场均稳指标USC，研究了冲击间距（L_b/D）对USC的影响。结果表明：正弦波纹挡板作为入口构件可以有效降低返混。在0.84＜L_b/D＜2.17范围内，正弦波纹板沉降器内流场的均一程度整体高于平面挡板；随着L_b/D减小，平挡板沉降器内流场的λ₁基本不变，但正弦波纹挡板沉降器内流场的λ₁降低，且对I_a的影响不明显。对比平挡板，正弦波纹挡板可以有效降低轴向速度的梯度，使返混区面积减小，流场稳定性提高。随着L_b/D增加，USC值呈现多峰值趋势，L_b/D=2.17时正弦波纹板沉降器的USC取得极大值为14.68，较平挡板提高了93.67%。     

Fracture Mode of Martensite-Austenite Constituents Containing Multiphase Steel Controlled by Microstructural and Micromechanical Aspects

The fracture mode in different M-A constituents containing multiphase steels under impact load was examined considering their microstructural and micromechanical aspects. The results showed that a ductile fracture develops in the fine-grained bainitic ferrite/M-A multiphase by microvoids initiation and coalescence, while cleavage develops in the coarse-grained polygonal ferrite/M-A multiphase by microcracks initiation and propagation, due to their diversities in morphologies of microstructural components and microhardness difference between phases.     

好氧发酵过程微界面传质耦合模拟分析

微生物好氧发酵过程是一个多相生化反应体系，空气中的氧在气液两相间的传质速率对生化发酵过程有重要影响。而气泡中氧的传递特性是气泡的形态、运动及体系温度、压力和物性综合影响的结果。通过建立两组分空气气泡上升及其氧传质耦合模型，进而采用数值模拟描述好氧发酵体系中微界面体系的强化效果。利用能量耗散理论评价制造微气泡体系的能耗，以获得高性价比的气泡形态和较高的氧利用率。计算结果表明，在预设的工况下，液面高度一定的反应器内，初始半径大于500 μm的气泡会在短时间内逸出体系，造成物料浪费；而气泡初始半径小于100 μm时，其停留时间、传质效率和氧利用率会显著提升。小气泡的生成需要较大的能耗，需要综合生产成本考虑。在不考虑其他因素影响的情况下，体系中的DO值如果维持在20%~30%，可以获得最大的氧气传质速率。