A review of hydrogen production processes by photocatalytic water splitting – From atomistic catalysis design to optimal reactor engineering

‘Renewable energy is an essential part of our strategy of decarbonization, decentralization, as well as digitalization of energy.’ – Isabelle Kocher.Current climate, health and economic condition of our globe demands the use of renewable energy and the development of novel materials for the efficient generation, storage and transportation of renewable energy. Hydrogen has been recognised as one of the most prominent carriers and green energy source with challenging storage, enabling decarbonization. Photocatalytic H₂ (green hydrogen) production processes are targeting the intensification of separated solar energy harvesting, storage and electrolysis, conventionally yielding O₂/H₂. While catalysis is being investigated extensively, little is done on bridging the gap, related to reactor unit design, optimisation and scaling, be it that of material or of operation. Herein, metals, oxides, perovskites, nitrides, carbides, sulphides, phosphides, 2D structures and heterojunctions are compared in terms of parameters, allowing for efficiency, thermodynamics or kinetics structure–activity relationships, such as the solar-to-hydrogen (STH). Moreover, prominent pilot systems are presented summarily.     

Single-switch boost-buck DC-DC converter for industrial fuel cell and photovoltaics applications

The realization of dc-dc converters performs a vital function in exploiting renewable energy sources such as solar photovoltaic (PV) and fuel cell applications. This paper demonstrates a single-switch unidirectional buck-boost dc-dc converter for continuous power flow control, excluding the hybrid switched-capacitor. The proposed converter utilizes a limited number of passive components, only four diodes and three inductors required, in addition to six capacitors. The converter can operate at a wide input voltage range with continues input current. The converter has experimented under real-time conditions with 660 W PV system. The obtained efficiency ranges from 93% to 98%. Furthermore, the converter has interfaced with 550 W fuel cell operated under different fuel pressure. The realized efficiency ranges from 91% to 97%. The maximum measured inductance current ripple is limited to under 0.70 A in both scenarios, whereas 0.16 V is the maximum output voltage ripple.     

Engineering biphasic hybrid phosphide nanowires as efficient electrocatalyst for hydrogen evolution reaction: Experimental and theoretical insights

Development of highly efficient and cheap electrocatalysts towards the hydrogen evolution reaction (HER) is of great importance for electrochemical water splitting. Herein, hybrid Cu/NiMo-P nanowires on the copper foam were successfully fabricated via a simple two-step method. The hierarchically structured Cu/NiMo-P exhibits large surface areas and rapid electron transfer ability, leading to enhanced catalytic activity. The as-prepared Cu/NiMo-P electrodes need overpotentials of 34 mV and 130 mV to obtain 10 mA cm^?2 for HER in acidic and alkaline solutions, respectively. Density functional theory (DFT) calculations reveal that the Cu/NiMo-P hybrid has a more thermo-neutral hydrogen adsorption free energy and enhanced charge transfer ability as well.     

Construction and analysis of photovoltaic directly coupled conditions in PEM electrolyzer

The Markov model and the PEM electrolyzer system model for directly coupled photovoltaic are combined to construct an efficient and reliable working condition that fits the fluctuation characteristics of solar energy. The working condition is designed through genetic algorithm so that the average coupling efficiency of the system can reach 98.8%. Then, the durability and recovery test are conducted on the basis of the constructed conditions. It is found that the attenuation rate at the current density of 1A/cm² under the photovoltaic fluctuating condition reached 7.8mV/h, which is twice that under the constant current condition. The charge transfer impedance (R_ct) is the main factor leading to the degradation. It is proved by the recovery experiment that the increase of R_ct is related to the pollution of metal ions. After pickling to remove some metal ions, R_ct can be significantly reduced by 46.8% and 65.2%, respectively. After the durability test, the voltammetric charges under the photovoltaic fluctuating condition and the constant current condition are reduced by 48.3% and 19.1% It indicates that the photovoltaic fluctuation condition will accelerate the attenuation of the effective reaction area of MEA, which is irreversible even after pickling. It can be observed from the SEM images that the catalyst layer of MEA has more obvious peeling under the photovoltaic fluctuation condition, which is not conducive to material transmission and destroys the transmission channel of ions and electrons. This result can provide a reliable reference for the coupling design of PEM electrolyzer and renewable energy in the future.     

煤基高能量密度燃料的合成及表征

高能量密度燃料是为新型高性能飞行器提供动力保障的关键,其合成及应用研究具有重要的前瞻性和重大战略意义。煤炭是我国的主体能源和重要原料,通过煤直接转化获取的煤基油,充分保留了煤中特有的环状分子化学结构,具有良好的热安定性和较高的能量密度,被认为是高超音速飞行器的优选燃料。以煤直接液化工艺生产的煤液化石脑油馏分为起始原料,通过富集轻质芳烃、化学合成、催化加氢稳定和产物分离提纯等方法制备煤基高能量密度燃料,并对其产物进行分子结构表征和性能评价。结果表明,煤直接液化生产的石脑油馏分是一种优异的催化重整原料,经催化重整富集轻质芳烃后,其轻质芳烃质量分数高达71.05%。Diels-Alder化学合成主产物是由多个封闭环平面组成且具有空间立体构型的二环或三环烃类物质,质量分数为46.18%,因分子内存在较大的张力能,结构紧凑,其拥有更大的密度和体积热值。煤基高能量密度燃料的密度和体积热值分别为0.8990 g/cm3与38.06 MJ/L,均大大超过现行的国内石油基喷气燃料(RP-3和RP-6)、煤基大比重喷气燃料、美国和俄罗斯军用标准。与单一纯物质合成高能量密度燃料(JP-10和T-10)比较,其密度与体积热值偏小。究其原因主要是轻质芳烃的富集度仅为71.05%,需进一步提高其轻质芳烃质量分数。另外,制备的煤基高能量密度燃料种类复杂,其主产物质量分数仅46.18%,下一步可重点调控合成产物的分子构型和纯化分离。     

WSN低功耗低时延路径式协同计算方法

针对云计算应用于无线传感器网络(Wireless Sensor Network,WSN)时延敏感型业务时存在的高传输时延问题,提出了一种WSN低功耗低时延路径式协同计算方法。该方法基于一种云雾网络架构开展研究,该架构利用汇聚节点组成雾计算层;在数据传输过程中基于雾计算层的计算能力分步骤完成任务计算,降低任务处理时延;由于汇聚节点计算能力较弱,时延降低将导致能耗增加,WSN工作寿命减短,为此提出能耗约束下的任务映射策略,并利用离散二进制粒子群优化(Binary Particle Swarm Optimization,BPSO)算法解决能耗约束下的时延优化问题。仿真结果表明,在相同的能耗约束下,对比其他算法,基于BPSO算法得出的映射方案能有效降低业务处理时延,满足时延敏感型业务的需求。     

Design of Ti4+-doped Li3V2(PO4)3/C fibers for lithium energy storage

In this work, we propose a facile approach to fabricate Ti⁴⁺-doped Li₃V₂(PO₄)₃/C (abbreviated as C-LVTP) nanofibers using an electrospinning route followed by a high temperature treatment. In this designed nanocomposite, the ultrafine LVTP dots are homogeneously dispersed into one-dimensional carbon nanofibers and the Ti⁴⁺ doping does not destroy the crystal structure of monoclinic Li₃V₂(PO₄)₃. Compared to the undoped Li₃V₂(PO₄)₃/C (abbreviated as C-LVP), the as-fabricated C-LVTP fibers present higher reversible capacity, superior high-rate capability as well as better cyclic property. Especially, the C-LVT_7%P cathode delivers not only high capacities of 187.2 and 160.3 mAh g^?1 at 0.5 and 10 C respectively, but also stable cyclic property with the reversible capacity of 135.8 mAh g^?1 at 20 C following 500-cycle spans. The good battery characteristics of C-LVT_7%P can be mainly ascribed to Ti⁴⁺ doping, which can increase the electrical conductivity and Li⁺ diffusion coefficient.     

Hybrid hydrate processes for CO2/H2 mixture purification: A techno-economic analysis

In this work, hydrate based separation technique was combined with membrane separation and amine-absorption separation technologies to design hybrid processes for separation of CO₂/H₂ mixture. Hybrid processes are designed in the presence of different types of hydrate promoters. The conceptual processes have been developed using Aspen HYSYS. Proposed processes were simulated at different flow rates for the feed stream. A comprehensive cost model was developed for economic analysis of novel processes proposed in this study. Based on the results from process simulation and equipment sizing, the amount of total energy consumption, fixed cost, variable cost, and total cost were calculated per unit weight of captured CO₂ for various flow rates of feed stream and in the presence of different hydrate promoters. Results showed that combination of hydrate formation separation technique with membrane separation technology results in a CO₂ capture process with lowest energy consumption and total cost per unit weight of captured CO₂. As split fraction and heat of hydrate formation increases, the share of hydrate formation section in total energy consumption increases. When TBAB is applied as hydrate promoter, due to its higher hydrate separation efficiency, more amount of CO₂ is captured in hydrate formation section and consequently the total cost for process decreases considerably. Hybrid hydrate-membrane process in the presence of TBAB as hydrate promoter with 29.47 US$/ton CO₂ total cost is the best scheme for hybrid hydrate CO₂ capture process. Total cost for this process is lower than total cost for single MDEA-based absorption process as the mature technology for CO₂ capture.     

Role and prospects of green quantum dots in photoelectrochemical hydrogen generation: A review

Eco-friendly quantum dots (QDs) can be termed green QDs which stand as an attractive choice to modify the properties of known semiconductors in the direction of getting efficient photoelectrodes for solar-induced photoelectrochemical (PEC) splitting of water, due to their peculiar properties. Thus, it is of high significance to analyze their merit/demerit as an effective scaffold in PEC cell. QDs are known for their excellent optical properties however, the coupling of green QDs with semiconductor is not only useful in improving absorption characteristics but also promotes charge transfer. This review has undertaken the critical analysis on the worldwide research going on the green QDs modified photoelectrode with respect to their optical, electrical & photoelectrochemical properties, role, usefulness, efficiency, and finally the success in PEC system for hydrogen production. Various methods on the facile synthesis & sensitization techniques of green QDs available in the literature have also been discussed. Further, recent advances on the development of green QDs based photo-electrode, along with major challenges of using green QDs in this field have also been presented.     

Microwave hybrid fast sintering of red clay ceramics

This work aimed to examine the performance of the hybrid sintering of clay ceramic in a microwave furnace, compared to the sintering process in a conventional furnace. The raw materials were subjected to X-ray fluorescence, loss on ignition (LOI), X-ray diffraction, particle size distribution, real specific mass, and thermogravimetric analyses. The red clay ceramic mass was prepared, extruded, pre-sintered in a conventional furnace at 600°C/60 min, and sintered at temperatures between 700 °C and 1100 °C. The sintering conventional (resistive oven) was carried out for 60 min with a heating rate of 10°C/min. In the microwave furnace, the sintering times were 5, 10, and 15 min, with a heating rate of 50°C/min, with a sintering chamber coated with silicon carbide (susceptor). The sintered specimens were characterized according to linear shrinkage, water absorption, apparent porosity, apparent specific mass, X-ray diffraction, Raman spectroscopy analysis, spectroscopy analysis in the ultraviolet and visible regions, microhardness, and scanning electron microscopy. The results showed that microwave sintering promoted an increase in the microhardness and apparent specific mass, and reduction in water absorption and apparent porosity values, due to greater densification in the microstructure. The best results occurred for specimens sintered at 1100°C.