Pt nanoclusters modified porous g-C_(3)N_(4)nanosheets to significantly enhance hydrogen production by photocatalytic water reforming of methanol

For the use of green hydrogen energy,it is crucial to have efficient photocatalytic activity for hydrogen generation by water reforming of methanol under mild conditions.Much attention has been paid to gC_(3)N_(4)as a promising photocatalyst for the generation of hydrogen.To improve the separation of photogenerated charge,porous nanosheet g-C_(3)N_(4)was modified with Pt nanoclusters(Pt/g-C_(3)N_(4))through impregnation and following photo-induced reduction.This catalyst showed excellent photocatalytic activity of water reforming of methanol fo r hydrogen production with a 17.12 mmol·g^(-1)·h^(-1)rate at room temperature,which was 311 times higher than that of the unmodified g-C_(3)N_(4).The strong interactions of Pt-N in Pt/g-C_(3)N_(4)constructed effective electron transfer channels to promote the separation of photogenerated electrons and holes effectively.In addition,in-situ infrared spectroscopy was used to investigate the intermediates of the hydrogen production reaction,which proved that methanol and water eventually turn into H_(2)and CO_(2)via formaldehyde and formate.This study provides insights for understanding the photocatalytic hydrogen production in the water reforming of methanol.

Trends and advances in the development of coal fly ash-based materials for application in hydrogen-rich gas production:A review

Coal fly ash(FA),a valuable industrial solid residue generated from coal combustion,is composed of various metal oxides and has a high thermal stability.Given that the coal-based energy will continue to account for a significant portion of global electricity generation in the coming years,the lack of effective management strategies exacerbates the threat of FA wastes to the surrounding environment and human health.For a sustainable development,green and renewable hydrogen economy and CO_(2)capture efforts provide appealing opportunities to valorize FA as catalysts and/or sorbents due to their appealing physicochemical properties.Hydrogen applications along with carbon neutrality are potential strategies to mitigate climate change crisis,but high processing costs(catalysts/sorbents)are challenging to realize this purpose.In this context,the utilization of FA not only enhances industrial competitiveness(by reducing manufacturing costs),but also provides ecologically friendly approaches to minimizing this solid waste.This state-of-the-art review highlights a wide-ranging outlook on the valorization of FA as catalysts and sorbents for hydrogen-rich gas production via conventional/intensified processes(CO_(2)/H_(2)O reforming,ammonia decomposition,hydride hydrolysis).The fundamental physicochemical characterizations and hazards/utilization of FA,which significantly affect the FA's utilization in various fields,are first introduced.The influence of several factors(like FA types and catalysis/sorption operation conditions)on the activity performance of FA-based materials is then discussed in detail.This critical review aims to open the window to further innovative ideas regarding the application of different FA residues in other catalytic and sorption processes.

Renewable Methanol Production Using Captured Carbon Dioxide and Hydrogen Generated through Water-Splitting

The global warming issues associated with fossil fuels have forced the world to shift towards environment-friendly alternatives. The studies on the capture and storage of CO2 have gained significant research attention, and to attract the world towards CO2 capturing and storing, it is necessary to find suitable applications for this captured CO2. Methanol is one of the products which can be produced by utilizing the captured CO2 and hydrogen that can be produced by water splitting. Keeping in view both these green fuel production processes, this study proposes a combined application of both these technologies for the production of methanol, which is an important chemical used in manufacturing industries. This review paper presents a brief study of both carbon capture and hydrogen production technologies. It also provides research trends, economic aspects, and methods of incorporating both these technologies to produce methanol. Additionally, the prospects of the approach in Oman have also been presented.

High-efficient solar-driven hydrogen production by full-spectrum synergistic photo-thermo-catalytic methanol steam reforming with in-situ photoreduced Pt-CuO_(x) catalyst

Synergy between the intrinsic photon and thermal effects from full-spectrum sunlight for H_(2) production is considered to be central to further improve solar-driven H_(2) production.To that end,the photo-thermocatalyst that demonstrates both photoelectronic and photothermal conversion capabilities have drawn much attention recently.Here,we propose a novel synergistic full-spectrum photo-thermo-catalysis technique for high-efficient H_(2) production by solar-driven methanol steam reforming(MSR),along with the Pt-Cu Oxphoto-thermo-catalyst featuring Pt-Cu/Cu_(2)O/CuO heterojunctions by Pt-mediated in-situ photoreduction of Cu O.The results show that the H_(2) production performance rises superlinearly with increasing light intensity.The optimal H_(2) production rate of 1.6 mol g^(-1) h^(-1) with the corresponding solar-to-hydrogen conversion efficiency of 7%and the CO selectivity of 5%is achieved under 15×sun full-spectrum irradiance(1×sun=1 k W m^(-2))at 180°C,which is much more efficient than the previously-reported Cu-based thermo-catalysts for MSR normally operating at 250~350°C.These attractive performances result from the optimized reaction kinetics in terms of intensified intermediate adsorption and accelerated carrier transfer by long-wave photothermal effect,and reduced activation barrier by short-wave photoelectronic effect,due to the broadened full-spectrum absorbability of catalyst.This work has brought us into the innovative technology of full-spectrum synergistic photothermo-catalysis,which is envisioned to expand the application fields of high-efficient solar fuel production.

Coordination Effect-Promoted Durable Ni(OH)_(2) for Energy-Saving Hydrogen Evolution from Water/ Methanol Co-Electrocatalysis

Electrocatalytic water splitting is a viable technique for generating hydrogen but is precluded from the sluggish kinetics of oxygen evolution reactions(OER).Small molecule oxidation reactions with lower working potentials,such as methanol oxidation reactions,are good alternatives to OER with faster kinetics.However,the typically employed Ni-based electrocatalysts have poor activity and stability.Herein,a novel three-dimensional(3D)-networking Modoped Ni(OH)_(2) with ultralow Ni-Ni coordination is synthesized,which exhibits a high MOR activity of 100 mA cm^(−2) at 1.39 V,delivering 28 mV dec^(−1) for the Tafel slope.Meanwhile,hydrogen evolution with value-added formate co-generation is boosted with a current density of more than 500 mA cm^(−2) at a cell voltage of 2.00 V for 50 h,showing excellent stability in an industrial alkaline concentration(6 M KOH).Mechanistic studies based on density functional the-ory and X-ray absorption spectroscopy showed that the improved performance is mainly attributed to the ultralow Ni-Ni coordination,3D-networking structures and Mo dopants,which improve the catalytic activity,increase the active site density and strengthen the Ni(OH)_(2)3D-networking structures,respectively.This study paves a new way for designing electrocatalysts with enhanced activity and durability for industrial energy-saving hydrogen production.

Effect of supercritical water on the stability and activity of alkaline carbonate catalysts in coal gasification

The stability and activity of alkaline carbonate catalysts in supercritical water coal gasification has been investigated using density functional theory method. Our calculations present that the adsorption of Na2CO3 on coal are more stable than that of K2CO3, but the stability of Na2CO3 is strongly reduced as the cluster gets larger. In supercritical water system, the dispersion and stability of Na2CO3 catalyst on coal support is strongly improved. During coal gasification process, Na2CO3 transforms with supercritical water into NaOH and NaHCO3, which is beneficial for hydrogen production. The transformation process has been studied via thermodynamics and kinetics ways. The selectively catalytic mechanism of NaOH and the intermediate form of sodium-based catalyst in water-gas shift reaction for higher hydrogen production has also been investigated. Furthermore, NaOH can transform back to Na2CO3 after catalyzing the water-gas shift reaction. Thus, the cooperative effects between supercritical water and Na2CO3 catalyst form a benignant circle which greatly enhances the reaction rate of coal gasification and promotes the production of hydrogen.

Low temperature hydrogen production from water and methanol over Pt/α-MoC catalysts

Subject Code:B03 With the support by the National Natural Science Foundation of China,a collaborative study by the research groups led by Prof.Ma Ding(马丁)from Peking University,Prof.Zhou Wu(周武)from the University of Chinese Academy of Sciences,Prof.Wen Xiaodong(温晓东)from the Institute of

Systematic physicochemical characterization,carbon balance and cost of production analyses of activated carbons derived from(Co)-HTC of coal discards and sewage sludge for hydrogen storage applications

Hydrothermal carbonization(HTC)technologies for producing value-added carbonaceous material(hydrochar)from coal waste and sewage sludge(SS)waste might be a long-term recycling strategy for hydrogen storage applications,cutting disposal costs and solving waste disposal difficulties.In this study,hydrochars(HC)with high carbon content were produced using a combination of optimal HTC(HTC and Co-HTC)and chemical activation of coal tailings(CT),coal slurry(CS),and a mixture of coal discard and sewage sludge(CB).At 850℃and 800℃,respectively,with a KOH/HC ratio of 4:1 and a residence time of 135 min,activated carbons(ACs)with the highest Brunauer–Emmett–Teller specific surface(S_(BET))of 2299.25 m^(2)g^(−1)and 2243.57 m^(2)g^(−1)were obtained.The hydrogen adsorption capability of the produced ACs was further studied using gas adsorption isotherms at 77 K.At 35 bars,the values of hydrogen adsorbed onto AC-HCT(AC obtained from HTC of CT),AC-HCS(AC obtained from HTC of CS),and AC-HCB(AC obtained from HTC of the blending of coal discard(CD)and SS)were approximately 6.12%,6.8%,and 6.57%in weight,respectively.Furthermore,the cost of producing synthetic ACs for hydrogen storage is equivalent to the cost of commercial carbons.Furthermore,the high proportion of carbon retained(>70%)in ACs synthesized by HTC from CD and SS precursors should restrict their potential carbon emissions.

Pre-combustion mercury removal with co-production of hydrogen via coal electrolysis

Pre-combustion mercury removal via coal electrolysis was performed and investigated on a bench-scale coal electrolytic cell(CEC)systemically,and factorial design was used to determine the effect of different operating conditions(coal particle size,operating temperature,operating cell voltage,and flow rate of slurry)on the percentage of mercury removal,percentage of ash removal,and dry heating value change.The results showed that the operating cell voltage,as well as the interaction between operating cell voltage and coal particle size,are significant factors in the percentage of mercury removal.There is no significant factor in the percentage of ash removal and the dry heating value change,but the coal could be purified while keeping the dry heating value almost constant after electrolysis.A co-product of hydrogen could be produced during coal electrolysis with 50%lower energy consumption compared with water electrolysis.Meanwhile,a mechanism for mercury removal in coal was proposed.The facts indicate that coal electrolysis is a promising method for precombustion mercury removal.

Study on Performance of Laminated Porous Metal Fiber Sintered Felt as Catalyst Support for Methanol Steam Reforming Microreactor

In this study, the laminated porous metal fiber sintered felt(PMFSF) functioning as catalyst support was used in a cylindrical methanol steam reforming(MSR) microreactor for hydrogen production. The PMFSF was fabricated by the low temperature solid-phase sintering method using metal fibers such as copper fibers and aluminum fibers which are obtained by the multi-tooth cutting method. The two-layer impregnation method was employed to coat Cu/Zn/Al/Zr catalyst on the PMFSF. The effect of fiber material, uniform porosity and gradient porosity on the performance of methano steam reforming microreactor was studied by varying the gas hourly space velocity(GHSV) and reaction temperature. Our results showed that the loading strength of porous copper fiber sintered felt(PCFSF) was better than porous aluminum fiber sintered felt(PAFSF). Under the same reaction conditions, the PCFSF showed higher methanol conversion and more H_2 output than PAFSF. Moreover, the gradient porosity(Type 5: 90%×80%×70%) of PMFSF used as the catalyst support in microreactor demonstrated a best reaction performance for hydrogen production.

Study on Transition Metal Catalysts for Hydrogen Production from Coal Pyrolysis

In this paper,13 kinds of transition metals are studied as catalysts for the hydrogen production from coal pyrolysis, and relationships between the catalytic activity of a transition metal and its outer electron configuration,d% of transition metals and geometric configuration are summarized.Experimental results show that the same group of transition metals show good similarity for hydrogen production from coal pyrolysis;the d%of transition metals which have activity for hydrogen production from coal pyrolysis is between 40%-50%;all transition metals which have catalytic activity possess either a face-centered cubic or a hexagonal crystal structure.Therefore,it is important to choose a transition metal with an appropriate d%and crystal structure as the catalyst for hydrogen production from coal pyrolysis.

Methanol Steam Reforming over Na-Doped ZnO-Al2O3 Catalysts

In this study, the catalyst composition in binary ZnO-Al2O3 catalyst was initially evaluated and optimized for methanol steam reforming. Then different Na contents were loaded by an incipient wetness impregnation method onto the optimized ZnAl catalyst. It was found that the activity was greatly enhanced by the modification of Na, which depended on the Na content in the catalyst. The methanol conversion was 96% on a 0.1 Na/0.4 ZnAl catalyst (GHSV = 14,040 h-1, S/C = 1.4, 350°C), which was much higher with respect to a Na-free 0.4 ZnAl catalyst (74%). The remarkable improvement of activity was attributed to a weakening of the C-H bonds and clear of hydroxyl group by the Na dopant leading to an accelerated dehydrogenation of the reaction intermediates formed on ZnAl2O4 spinel surface and thus the overall reaction.

固体氧化物电解槽辅助煤电机组深度调峰技术可行性研究

常规的煤电机组灵活性改造方案,难以消除频繁快速变负荷对热力系统造成的潜在寿命折损与设备安全风险。为提高煤电机组参与深度调峰的长期安全性与经济性,以某国产超超临界二次再热1000 MW燃煤机组为应用对象,提出了基于氢储能系统的煤电机组“健康调峰”技术路线,并论证了调峰煤电制氢的间接碳减排意义。在此基础上,分析比较了不同制氢工艺与煤电厂生产条件的匹配程度,认为固体氧化物电解槽(SOEC)制氢为综合最优方案,据此给出了SOEC耦合煤电调峰的原理性设计方案,最后以年度负荷曲线对新方案进行了财务分析。计算结果表明,示例机组自第6年起每年可获得1.07亿元/年的净利润,每年减少碳排放281.92 t,同时获得设备延寿、降耗减碳等其他收益。相关结论对于指导调峰煤电机组的健康安全运行具有参考意义。

深部煤炭地下气化制氢先进能效分析

深部煤炭地下气化制氢不仅可以利用我国丰富的深部煤炭资源,将传统采煤方法难以开采或开采不经济的深部煤层转化为氢气,而且有望成为一种理想的煤基低成本制氢路线。基于位于加拿大天鹅山的世界上唯一千米级深部煤炭地下气化试验数据,结合Aspen Plus过程模拟,以先进[火用]为先进能效指标,对深部煤炭地下气化制氢能量利用情况进行分析。与商业化的Lurgi地面煤气化制氢路线作对比,以产出单位质量氢气的积累[火用]消耗为指标,比较了2种制氢路线的能量消耗水平。结果表明,在氢气生产能力为12亿Nm^(3)/a情形下,深部煤炭地下气化制氢从原料到产品的总[火用]损失为451.79 MW。先进[火用]分析可以有效量化气化过程可以避免的[火用]损失,其中39.9%为不可避免[火用]损失。甲烷重整单元的内部可避免[火用]损E_(dest,k)^(AV,EN)和外部可避免[火用]损E_(dest,k)^(AV,EX)分别为96.63和81.58 MW,具有最大能效提升空间,如能利用转化气、烟道气的热量副产蒸汽,可将其内部可避免[火用]损失减少38.5%。地下气化单元的E_(dest,k)^(AV,EN)和E_(dest,k)^(AV,EX)分别为4.38和62.73 MW,表明降低其[火用]损失的重点应放在提高其他单元的能量效率,从而降低外部可避免[火用]损。其余单元改进空间均比较小可不予考虑。以积累[火用]消耗量为标准衡量能量消耗水平时,产出1 kg氢气,深部煤炭地下气化制氢的积累[火用]消耗为376.1 MJ,仅为Lurgi地面煤气化制氢的83.6%,表明深部煤炭地下气化制氢能够显著降低能量消耗水平。敏感性分析显示,2者积累[火用]消耗的差距随着生产规模的扩大而增加。研究结果可为深部煤炭地下气化制氢的过程优化及技术可行性定量化提供科学依据。

电解煤浆制氢过程中煤阶及矿物的影响与煤结构演化研究进展

电解煤浆制氢(CSE)是一种在温和条件下实现电化学制氢与煤炭低碳清洁利用的新技术。电解煤浆制氢的理论分解电压仅为0.21V,实际消耗的能量约为电解水制氢的1/3~1/2,具有能耗低、污染小,可与煤基精细化学品制备、煤岩显微组分分离等过程集成的优点,但煤转化率低、煤浆电解机理不清晰等问题仍具有极大挑战性。本文讨论了CSE机理研究现状,概述了煤阶及矿物质对CSE的电氧化活性的影响,总结了CSE过程中煤表面元素、官能团结构、煤碳骨架结构在阳极区电化学氧化的变化规律,讨论了阴极区电化学还原对煤表面润湿性、Zeta电位等煤表面性质的影响,以及阴极区添加煤浆的电还原制氢及其耦合技术,以期为CSE制氢与煤低碳清洁利用提供理论支撑。此外,本文还展望了CSE的发展方向,提出了高性能CSE电极催化材料开发及煤氧化-还原反应调控机理研究是该技术获得突破的关键。

液相放电等离子体分解甲醇制氢:电极配置的优化

利用液相阵列电极滑动弧放电等离子体分解甲醇来优化现有制氢技术,系统研究了不同电极配置对制氢性能的影响。获得最优极配数量,发现同放电功率下4针电极最大氢气流速达到1188.54 ml/min,相对于单针提高了118%。此外,在液相放电中阵列针-环结构相比阵列针-孔板结构具有更高的氢气产能和能量产率。在阵列针-环电极配置工况,滑动弧放电等离子体分解甲醇表现出最佳制氢性能,能量产率69.75 g/kWh,能量效率71.12%,优于现有大多数制氢方案。

风化煤暗发酵生物制氢与关键代谢途径分析

风化煤热值低、利用方式单一且污染环境,为拓宽风化煤的利用途径,实现资源利用和环境保护,对风化煤进行暗发酵制取生物氢气。选取山西晋城和太原、内蒙古乌海三个矿区的自然风化煤,以煤层矿井水作为菌种来源,通过生物产氢试验、GC-MS、三维荧光和宏基因组学等测试手段揭示风化煤生物制氢可行性及关键代谢产物和途径。结果表明:不同矿区风化煤可以被转化为生物氢气,其中乌海风化煤产氢量最大(10.26 mL/g),远高于晋城风化煤产氢量(5.22 mL/g)。风化煤产氢系统偏酸性环境,pH和COD质量浓度具有一定的规律性变化,随着发酵的进行部分有机物得到利用产生乙酸和氢气。风化煤产氢过程中液相有机物主要以酸类(乙酸、丙酸、正戊酸和丁酸)和醇类(2,3-丁二醇,糖醇和(S)-1,2-丙二醇)为主,可溶性有机质以腐殖酸和色氨酸蛋白类有机质为主,且随着发酵的进行,多种有机质被消耗利用。风化煤制氢过程中微生物主要以Pseudomonadota门和Citrobacter属为主,且主要通过分解和利用有机酸(乙酸、丙酸、丁酸、乳酸)产生氢气。风化煤制氢过程中,乙酸代谢途径以糖酵解途径为主,有机质被细菌分解生成丙酮酸后再被产氢细菌利用,其中丙氨酸激酶和醛酮酸脱氢酶在细胞代谢生成氢气过程中发挥着重要作用。研究结果揭示了风化煤产氢的潜力机制,为风化煤有效利用提供了理论参考。

甲醇液相重整制氢研究进展

围绕甲醇液相重整制氢技术展开,介绍了甲醇液相重整反应机理,对比了不同甲醇重整制氢技术,讨论了不同工艺下的适用场景。总结发现了工艺温度在250~350℃的水蒸汽重整技术更适合在分布式加氢站中采用,液相重整技术在氢燃料电池体系中更具应用潜力。针对液相重整技术低温､高选择性的工艺特点,对液相重整制氢使用的催化剂进行了综述和展望。

光热协同甲醇水蒸气重整制氢实验和微观机理研究

针对太阳能光热化学甲醇重整制氢中光热耦合效应及微观机理尚不清楚的问题,采用光热化学和热化学反应对比的研究方式,与微观实验相结合,研究了光热化学甲醇重整中光和热的耦合效应,探究了光和热在微观产物转化中的反应路径。研究结果表明:在较低温度下,光对氢气产率的提升具有促进作用,当其与热化学达到相同氢气产率时,光热化学反应温度降低,造成这种现象的原因是光促进了水的分解、吸附态HCOO*的生成以及碳酸盐的分解,其中水在反应中的作用通过不同水醇比的实验得到了进一步验证;随着温度的升高,固定辐照度下光的促进作用逐渐降低,这是因为光对碳酸盐物质分解的促进作用随温度升高而减弱。研究阐明了光和热的耦合效应,分析了对应的微观机理,为理解光热协同机理提供了理论基础。

延川南2#煤层地下气化制氢工艺研究

为评价延川南2#煤层地下气化的产氢潜力,在查明煤的工业、元素分析等数据基础上,通过物理模拟实验研究了氧气浓度对气化温度和H2产率的影响,并利用AspenPlus软件建立煤炭地下气化预测模型进行模拟验证,在此基础上,利用上述模型研究氧煤比和汽氧比对H2产率的影响作用。通过物理模拟与数值模拟结果得出,水蒸气在煤炭地下气化过程中起主要作用,能够有效提高H2产率,延川南地区进行煤炭地下气化时,可优选富氧-水蒸气作为气化剂,且氧气浓度为80%最为适宜。