The oxygen production step of a copper-chlorine thermochemical water decomposition cycle for hydrogen production: Energy and exergy analyses

In the copper-chlorine (Cu-Cl) thermochemical cycle water is decomposed into its constituents (oxygen and hydrogen) by a series of chemical reactions. The cycle involves five steps in which three thermally driven chemical reactions and one electrochemical reaction take place. Oxygen is produced during one of the main chemical reactions. In the present study, the O₂ production step is described with its operational and environmental conditions, and energy and exergy analyses are performed. The cycle is assumed driven using nuclear energy. Various parametric studies are carried out on energetic and exergetic aspects of the step, considering variable reaction and reference-environment temperatures. At a constant reference-environment temperature of 25 °C, the exergy destruction of the O₂ production step varies between 4500 and 23,000 kJ/kmol H₂ when the reaction temperature increases from 450 to 1000 °C. At a 500 °C reaction temperature and a 25 °C reference-environment temperature, the exergy destruction for this step is found to be 5300 kJ/kmol H₂. At a reaction temperature of 500 °C and a reference-environment temperature of 25 °C, the exergy efficiency of the step is determined to be 96% and to decrease with increasing reaction temperature and/or reference-environment temperature.     

H2O-splitting thermochemical cycle based on ZnO/Zn-redox: Quenching the effluents from the ZnO dissociation

The production of zinc by thermal dissociation of zinc oxide has been experimentally investigated in the range of 1700-1950 K using a 10-kW solar chemical reactor directly exposed to concentrated solar radiation. The gaseous products Zn(g) and O₂ exiting the reactor underwent rapid cooling by flowing through an annular water-cooled quench unit and by injection of Ar. XRD analysis along with SEM and TEM images of the solid products deposited at the quenching zone revealed the formation of spherical particles of sizes in the 0.1- range, with their surface covered with smaller edged structures, which are characteristic of Zn(g) undergoing condensation followed by Zn(l)/Zn(s) oxidation and coalescence.     

光热驱动多孔氧化铈热化学循环解水制氢非热质平衡模型

热化学循环太阳燃料技术过程所涉及的多孔介质中复杂反应及热质传递过程,尚未建立较为完善的数学模型。以多孔氧化铈热化学循环解水过程为研究对象,将颗粒尺度的氧输运与宏观尺度的热质输运相耦合,提出完整的光热驱动条件下多孔介质非热质平衡模型,实验数据对比验证了动力学及热质输运模型的可靠性,分析了两种尺度(颗粒及床层)下,非热平衡效应、入射辐射热流、反应物浓度对动态过程的影响。入射辐射在床层的体积效应下,轴向的温度梯度使得缺陷反应的热力学平衡控制最大氧空位浓度出现在床层前侧,在缺陷反应的动态过程中,氧化过程相较于还原反应更快,提高多孔载氧体反应器的产物H₂浓度应主要从还原阶段中反应过程及条件出发。可为该类问题的建模和过程设计提供较为完整的理论基础和参考路径。     

光热驱动多孔氧化铈热化学循环解水制氢非热质平衡模型

热化学循环太阳燃料技术过程所涉及的多孔介质中复杂反应及热质传递过程,尚未建立较为完善的数学模型。以多孔氧化铈热化学循环解水过程为研究对象,将颗粒尺度的氧输运与宏观尺度的热质输运相耦合,提出完整的光热驱动条件下多孔介质非热质平衡模型,实验数据对比验证了动力学及热质输运模型的可靠性,分析了两种尺度(颗粒及床层)下,非热平衡效应、入射辐射热流、反应物浓度对动态过程的影响。入射辐射在床层的体积效应下,轴向的温度梯度使得缺陷反应的热力学平衡控制最大氧空位浓度出现在床层前侧,在缺陷反应的动态过程中,氧化过程相较于还原反应更快,提高多孔载氧体反应器的产物H₂浓度应主要从还原阶段中反应过程及条件出发。可为该类问题的建模和过程设计提供较为完整的理论基础和参考路径。     

Effect of TiO2 supporting layer on Fe2O3 photoanode for efficient water splitting

For an electrochemical water splitting system, titanate nanotubular particles with a thickness of ∼700 nm produced by a hydrothermal process were repetitively coated on fluorine-doped tin oxide (FTO) glass via layer-by-layer self-assembly method. The obtained titanate/FTO films were dipped in aqueous Fe solution, followed by heat treatment for crystallization at 500 °C for 10 min in air. The UV–vis absorbance of the Fe-oxide/titanate/FTO film showed a red-shifted spectrum compared with the TiO₂/FTO coated film; this red shift was achieved by the formation of thin hematite-Fe₂O₃ and anatase-TiO₂ phases verified using X-ray diffraction and Raman results. The cyclic voltammetry results of the Fe₂O₃/TiO₂/FTO films showed distinct reversible cycle characteristics with large oxidation–reduction peaks with low onset voltage of I–V characteristics under UV–vis light illumination. The prepared Fe₂O₃/TiO₂/FTO film showed much higher photocurrent densities for more efficient water splitting under UV–vis light illumination than did the Fe₂O₃/FTO film. Its maximum photocurrent was almost 3.5 times higher than that obtained with Fe₂O₃/FTO film because of the easy electron collection in the current collector. The large current collection was due to the existence of a TiO₂ base layer beneath the Fe₂O₃ layer.     

A novel CeO2–xSnO2/Ce2Sn2O7 pyrochlore cycle for enhanced solar thermochemical water splitting

A novel CeO₂–xSnO₂/Ce₂Sn₂O₇ pyrochlore stoichiometric redox cycle with superior H₂ production capacities is identified and corroborated for two‐step solar thermochemical water splitting (STWS). During the first thermal reduction step (1400°C), a reaction between CeO₂ and SnO₂ occurred for all the CeO₂–xSnO₂ (x = 0.05–0.20) solid compounds, forming thermodynamically stable Ce₂Sn₂O₇ pyrochlore rather than metastable CeO_2‐δ. Consequently, substantially higher reduction extents were achieved owing to the reduction of Ce^IV to Ce^III. Moreover, in the subsequent reoxidation with H₂O (800°C), H₂ production capacities increased by a factor of 3.8 as compared to the current benchmark material ceria when x = 0.15, with the regeneration of CeO₂ and SnO₂ and the concomitant reoxidation of Ce^III to Ce^IV. The H₂O‐splitting performance for CeO₂–0.15SnO₂ was reproducible over seven consecutive redox cycles, indicating the material was also robust. © 2017 American Institute of Chemical Engineers AIChE J, 63: 3450–3462, 2017     

Life cycle assessment of ISPRA Mark 9 thermochemical cycle for nuclear hydrogen production

The nuclear energy driven thermochemical cycle is one of the potential water‐splitting processes for producing hydrogen, presumed to be the transportation fuel of the future. A life cycle assessment (LCA) of one such system, which utilizes nuclear energy to drive the ISPRA Mark 9 thermochemical cycle, is presented in this paper. The results of the LCA are presented in terms of the emissions of greenhouse gases (CO₂‐equivalent) and acid gases (SO₂‐equivalent). The contributions of the thermochemical plant to the emissions were determined through the estimation of material and energy requirements for chemical inventory, raw materials consumption and plant fabrication/installation. The greenhouse gas emissions from the system are 2515 g CO₂‐equivalent kg^?1 H₂ produced and acid gas emissions 11.252 g SO₂‐equivalent kg^?1 H₂ produced. A comparison of this hydrogen production route with other routes, including steam reforming of methane and high‐temperature electrolysis, is also presented in the paper. Copyright © 2006 Society of Chemical Industry     

Hydrothermal synthesis of flaky crystallized La2Ti2O7 for producing hydrogen from photocatalytic water splitting

Flaky monoclinic La₂Ti₂O₇ was prepared via a hydrothermal method based on the reaction of Ti(SO₄)₂ and La(NO₃)₃. Relative to the solid-state reaction sample, the flaky La₂Ti₂O₇ showed higher surface areas, much smaller crystal size and more efficient light absorption. All these factors led to the higher photoactivity to produce H₂ from water splitting under UV irradiation.     

Controlled fabrication of Sn/TiO2 nanorods for photoelectrochemical water splitting

In this work, we investigate the controlled fabrication of Sn-doped TiO₂ nanorods (Sn/TiO₂ NRs) for photoelectrochemical water splitting. Sn is incorporated into the rutile TiO₂ nanorods with Sn/Ti molar ratios ranging from 0% to 3% by a simple solvothermal synthesis method. The obtained Sn/TiO₂ NRs are single crystalline with a rutile structure. The concentration of Sn in the final nanorods can be well controlled by adjusting the molar ratio of the precursors. Photoelectrochemical experiments are conducted to explore the photocatalytic activity of Sn/TiO₂ NRs with different doping levels. Under the illumination of solar simulator with the light intensity of 100 mW/cm², our measurements reveal that the photocurrent increases with increasing doping level and reaches the maximum value of 1.01 mA/cm² at −0.4 V versus Ag/AgCl, which corresponds to up to about 50% enhancement compared with the pristine TiO₂ NRs. The Mott-Schottky plots indicate that incorporation of Sn into TiO₂ nanorod can significantly increase the charge carrier density, leading to enhanced conductivity of the nanorod. Furthermore, we demonstrate that Sn/TiO₂ NRs can be a promising candidate for photoanode in photoelectrochemical water splitting because of their excellent chemical stability.     

Preparation of mesoporous In–Nb mixed oxides and its application in photocatalytic water splitting for hydrogen production

A series of mesoporous In–Nb mixed oxides was synthesized using NbCl₅ and In₂O₃ as the starting material and triblock copolymer P123 as template. We investigated the influence of indium content on the synthesis and characteristics of the mesoporous In–Nb mixed oxides, and their photocatalytic activities for water splitting. The materials were characterized by small angle X-ray scattering, powder X-ray diffraction, extended X-ray absorption fine structure, transmission electron microscopy, scanning electron microscopy, energy dispersive spectrometer, N₂ sorption and UV–vis spectroscopy. The surface area of mesoporous In–Nb mixed oxides was greater than 90 m²/g with a wormhole framework. The optimization of synthesis condition of the mesoporus In–Nb oxides catalyst contained a small fraction of highly dispersed indium (In/Nb = 0.13) species intercalated into the framework of mesoporous niobium oxides and exhibited a high photocatalytic activity for water splitting reaction which was about 2.7 times as compared to mesoporous Nb₂O₅ and was about 19 times higher than commercial bulk Nb₂O₅.     

Feasibility of Na-based thermochemical cycles for the capture of CO2 from air—Thermodynamic and thermogravimetric analyses

Three Na-based thermochemical cycles for capturing CO₂ from air are considered: (1) a NaOH/NaHCO₃/Na₂CO₃/Na₂O cycle with 4 reaction steps, (2) a NaOH/NaHCO₃/Na₂CO₃ cycle with 3 reactions steps, and (3) a Na₂CO₃/NaHCO₃ cycle with 2 reaction steps. Depending on the choice of CO₂ sorbent – NaOH or Na₂CO₃ – the cycles are closed by either NaHCO₃ or Na₂CO₃ decomposition, followed by hydrolysis of Na₂CO₃ or Na₂O, respectively. The temperature requirements, energy inputs, and expected products of the reaction steps were determined by thermodynamic equilibrium and energy balance computations. The total thermal energy requirement for Cycles 1, 2, and 3 are 481, 213, and 390 kJ/mol of CO₂ captured, respectively, when heat exchangers are employed to recover the sensible heat of hot streams. Isothermal and dynamic thermogravimetric runs were carried out on the pertinent carbonation, decomposition, and hydrolysis reactions. The extent of the NaOH carbonation with 500 ppm CO₂ in air at 25 °C – applied in Cycles 1 and 2 – reached 9% after 4 h, while that for the Na₂CO₃ carbonation with water-saturated air – applied in Cycle 3 – was 3.5% after 2 h. Thermal decomposition of NaHCO₃ – applied in all three cycles – reached completion after 3 min in the 90–200 °C range, while that of Na₂CO₃ – applied in Cycle 1 – reached completion after 15 min in the 1000–1400 °C range. The significantly slow reaction rates for the carbonation steps and, consequently, the relatively large mass flow rates required, introduce process complications in the scale-up of the reactor technology and impede the application of Na-based sorbents for capturing CO₂ from air.     

Efficient production of hydrogen and multi-walled carbon nanotubes from ethanol over Fe/Al2O3 catalysts

Fe/Al₂O₃ catalysts with different Fe loadings (10-90 mol%) were prepared by hydrothermal method. Ethanol decomposition was studied over these Fe/Al₂O₃ catalysts at temperatures between 500 and 800 °C to produce hydrogen and multi-walled carbon nanotubes (MWCNTs) at the same time. The results showed that the catalytic activity and stability of Fe/Al₂O₃ depended strongly on the Fe loading and reaction temperature. The Fe(30 mol%)/Al₂O₃ and Fe(40 mol%)/Al₂O₃ were both the effective catalyst for ethanol decomposition into hydrogen and MWCNTs at 600 °C. Several reaction pathways were proposed to explain ethanol decomposition to produce hydrogen and carbon (including nanotube) at the same time.     

A hydrogen peroxide sensor based on a horseradish peroxidase/polyaniline/carboxy-functionalized multiwalled carbon nanotube modified gold electrode

We have developed a polyaniline/carboxy-functionalized multiwalled carbon nanotube (PAn/MWCNTCOOH) nanocomposite by blending the emeraldine base form of polyaniline (PAn) and carboxy-functionalized multiwalled carbon nanotubes (MWCNT) in dried dimethyl sulfoxide (DMSO) at room temperature. The conductivity of the resulting PAn/MWCNTCOOH was 3.6 × 10⁻³ S cm⁻¹, mainly as a result of the protonation of the PAn with the carboxyl group and the radical cations of the MWCNT fragments. Horseradish peroxidase (HRP) was immobilized within the PAn/MWCNTCOOH nanocomposite modified Au (PAn/MWCNTCOOH/Au) electrode to form HRP/PAn/MWCNTCOOH/Au for use as a hydrogen peroxide (H₂O₂) sensor. The adsorption between the negatively charged PAn/MWCNTCOOH nanocomposite and the positively charged HRP resulted in a very good sensitivity to H₂O₂ and an increased electrochemically catalytical current during cyclic voltammetry. The HRP/PAn/MWCNTCOOH/Au electrode exhibited a broad linear response range for H₂O₂ concentrations (86 μM–10 mM). This sensor exhibited good sensitivity (194.9 μA mM⁻¹ cm⁻²), a fast response time (2.9 s), and good reproducibility and stability at an applied potential of −0.35 V. The construction of the enzymatic sensor demonstrated the potential application of PAn/MWCNTCOOH nanocomposites for the detection of H₂O₂ with high performance and excellent stability.     

Influence of preparation method on performance of Cu(Zn)(Zr)-alumina catalysts for the hydrogen production via steam reforming of methanol

The selective production of hydrogen via steam reforming of methanol (SRM) was performed using prepared catalysts at atmospheric pressure over a temperature range 200–260^∘C. Reverse water gas shift reaction and methanol decomposition reactions also take place simultaneously with the steam reforming reaction producing carbon monoxide which is highly poisonous to the platinum anode of PEM fuel cell, therefore the detailed study of effect of catalyst preparation method and of different promoters on SRM has been carried out for the minimization of carbon monoxide formation and maximization of hydrogen production. Wet impregnation and co-precipitation methods have been comparatively examined for the preparation of precursors to Cu(Zn)(Al₂O₃) and Cu(Zn)(Zr)(Al₂O₃). The catalyst preparation method affected the methanol conversion, hydrogen yield and carbon monoxide formation significantly. Incorporation of zirconia in Cu(Zn)(Al₂O₃) catalyst enhanced the catalytic activity, hydrogen selectivity and also lower the CO formation. Catalyst Cu(Zn)(Zr)(Al₂O₃) with composition Cu/Zn/Zr/Al:12/4/4/80 prepared by co-precipitation method was the most active catalyst giving methanol conversion up to 97% and CO concentration up to 400 ppm. Catalysts were characterized by atomic absorption spectroscopy (AAS), Brunauer-Emett-Teller (BET) surface area, pore volume, pore size and X-ray powder diffraction (XRPD). The XRPD patterns revealed that the addition of zirconia improves the dispersion of copper which resulted in the better catalytic performance of Cu(Zn)(Zr)(Al₂O₃). The time-on-stream (TOS) catalysts stability test was also conducted for which the Cu(Zn)(Zr)(Al₂O₃) catalyst gave the consistent performance for a long time compared to other catalysts.     

A novel hydrogen peroxide biosensor based on Au-graphene-HRP-chitosan biocomposites

Graphene was prepared successfully by introducing -SO₃⁻ to separate the individual sheets. TEM, EDS and Raman spectroscopy were utilized to characterize the morphology and composition of graphene oxide and graphene. To construct the H₂O₂ biosensor, graphene and horseradish peroxidase (HRP) were co-immobilized into biocompatible polymer chitosan (CS), then a glassy carbon electrode (GCE) was modified by the biocomposite, followed by electrodeposition of Au nanoparticles on the surface to fabricate Au/graphene/HRP/CS/GCE. Cyclic voltammetry demonstrated that the direct electron transfer of HRP was realized, and the biosensor had an excellent performance in terms of electrocatalytic reduction towards H₂O₂. The biosensor showed high sensitivity and fast response upon the addition of H₂O₂, under the conditions of pH 6.5, potential −0.3 V. The time to reach the stable-state current was less than 3 s, and the linear range to H₂O₂ was from 5 × 10⁻⁶ M to 5.13 × 10⁻³ M with a detection limit of 1.7 × 10⁻⁶ M (S/N = 3). Moreover, the biosensor exhibited good reproducibility and long-term stability.     

Reduction and oxidation properties of Fe2O3/ZrO2 oxygen carrier for hydrogen production

Fe₂O₃ is a promising oxygen carrier for hydrogen production in the chemical-looping process. A set of kinetic studies on reduction with CH₄, CO and H₂ respectively, oxidation with water and oxygen containing Ar for chemical-looping hydrogen production was conducted. Fe₂O₃ (20 wt.%)/ZrO₂ was prepared by a co-precipitation method. The main variables in the TGA (thermogravimetric analyzer) experiment were temperatures and gas concentrations. The reaction kinetics parameters were estimated based on the experimental data. In the reduction by CH₄, CO and H₂, the reaction rate changed near FeO. Changes in the reaction rate due to phase transformation were observed at low temperature and low gas concentration during the reduction by CH₄, but the phenomenon was not remarkable for the reduction by CO and H₂. The reduction rate achieved using CO and H₂ was relatively faster than achieved using CH₄. The Hancock and Sharp method of comparing the kinetics of isothermal solid-state reactions was applied. A phase boundary controlled model (contacting sphere) was applied to the reduction of Fe₂O₃ to FeO by CH₄, and a different phase boundary controlled model (contacting infinite slab) was fit well to the reduction of FeO to Fe by CH₄. The reduction of Fe₂O₃ to Fe by CO and H₂ can be described by the former phase boundary controlled model (contacting sphere). This phase boundary controlled model (contacting sphere) also fit well for the oxidation of Fe to Fe₃O₄ by water and FeO to Fe₂O₃ by oxygen containing Ar. These kinetics data could be used to design chemical-looping hydrogen production systems.     

碘硫循环制氢中HI浓缩分离工艺的研究进展

综述了碘硫循环制氢中用于HI浓缩分离的3种主要技术路线,即磷酸萃取精馏、反应精馏以及电解电渗析预浓缩-精馏的研究进展,对各路线的过程原理、操作流程、能量利用效率等方面进行了讨论,在此基础上对比了其各自的优点和不足之处,并对其应用前景进行了展望。其中,磷酸萃取精馏开发最早,相对成熟,但操作流程复杂,运行效率需进一步提升;反应精馏流程有望以高集成度取得高效率,但所需条件非常苛刻,其设备开发、工艺实验等工作亟待展开;近年来发展较快的电解电渗析预浓缩-精馏工艺由于具有操作简单,条件温和,浓缩效率高等优点而具有较好的应用前景,其进一步工艺放大、模块化以及与精馏的高效协同等都是未来研究的重点和难点。     

Preparation and electrochemical studies of metal–carbon composite catalysts for small-scale electrosynthesis of H2O2

Numerous transition metal–carbon composite catalysts (M = V, Zn, Ni, Sn, Ce, Ba, Fe, Cu) have been synthesized and tested for electroreduction of O₂ to H₂O₂, The activity and selectivity of all synthesized catalysts for electrosynthesis of H₂O₂ were determined by the rotating ring-disk electrode method in acidic and neutral electrolytes. The Co-based catalysts in general showed the highest activity towards H₂O₂ formation. Experiments with different loading contents of Co showed that the activation overpotential losses of oxygen reduction to H₂O₂ reduces as loading increases to about 4 wt% Co. Addition of Co beyond this level did not seem to impact the overpotential losses. The cobalt-based catalysts, were spray-coated onto 120 μm thick Toray^® graphite substrates, and were studied in bulk electrolysis cells for up to 100 h at potentiostatic conditions (0.25 V vs. RHE) in pH 0, 3, and 7 electrolytes. At (25 °C and 1 bar) with a catalysts loading of about and using dissolved O₂ in 0.5 M H₂SO₄, typical H₂O₂ electrosynthesis rates of about were reached with current efficiencies of about 85 ± 5% at 0.25 V (vs. RHE).