Hydrogen production

制氢
  • 文章类型: Journal Article
    用于制氢的阴离子交换膜水电解(AEMWE)结合了质子交换膜水电解和碱性水电解的优点。已经采取了几种策略来提高AEMWE的性能并获得具有高氢氧根离子电导率的膜,低气体渗透,和高耐久性。在这项工作中,已经开发了用聚[2,2'-(对氧二亚苯基)-5,5'-苯并咪唑](PBIO)聚合物纤维增强的AEM。将通过静电纺丝制备的PBIO的纤维网浸渍到聚(亚苯基)mTPN离聚物中。通过在增强物和离聚物之间形成强的表面相互作用以及通过增强物在膜厚度上的膨胀来增强膜。氢氧离子电导率,热稳定性,尺寸肿胀,机械性能,并将增强膜的氢交叉与未增强膜的特性进行了比较。将PBIO纳米纤维增强物掺入膜中可减少氢交叉并改善拉伸性能,不影响氢氧化物的导电性。PBIO增强的mTPN膜在无PGM的5cm2AEMWE单电池中使用NiFe氧化物阳极和NiMo阴极催化剂进行评估,在50°C的电池温度下,并且将IMKOH进料至阳极。在260小时的测试期间,电池的性能不断提高,在1.0Acm-2时达到2.06V。
    Anion exchange membrane water electrolysis (AEMWE) for hydrogen production combines the advantages of proton exchange membrane water electrolysis and alkaline water electrolysis. Several strategies have been adopted to improve the performance of AEMWE and to obtain membranes with high hydroxide ion conductivity, low gas permeation, and high durability. In this work AEMs reinforced with poly[2,2\'-(p-oxydiphenylene)-5,5\'-benzimidazole] (PBIO) polymer fibres have been developed. A fibre web of PBIO prepared by electrospinning was impregnated into the poly(terphenylene) mTPN ionomer. The membranes are strengthened by the formation of a strong surface interaction between the reinforcement and the ionomer and by the expansion of the reinforcement over the membrane thickness. The hydroxide ion conductivity, thermal stability, dimensional swelling, mechanical properties, and hydrogen crossover of the reinforced membranes were compared with the characteristics of the non-reinforced counterpart. The incorporation of PBIO nanofibre reinforcement into the membrane reduced hydrogen crossover and improved tensile properties, without affecting hydroxide conductivity. PBIO-reinforced mTPN membrane was assessed in a PGM-free 5 cm2 AEMWE single cell using NiFe oxide anode and NiMo cathode catalysts, at a cell temperature of 50 °C and with 1 M KOH fed to the anode. The performance of the cell increased continuously over the 260 hours test period, reaching 2.06 V at 1.0 A cm-2.
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  • 文章类型: Journal Article
    化粪池是最常用的分散式废水处理系统,用于现场应用中的家庭废水处理。在不同的化粪池配置下,各种污染物的去除率较低。将微生物电解槽(MEC)集成到化粪池或基于生物膜的反应器中可以是用于家庭废水处理和能源生产的绿色和可持续技术。在这项研究中,将50升化粪池转换为50升MEC,再加上基于生物膜的反应器,用于同时处理家庭废水和制氢。基于生物膜的反应器通过厌氧填充床生物膜反应器(APBBR)和好氧移动床生物膜反应器(aeMBBR)集成。通过施加0.7V和1.0V的电压,在不同的有机负载率(OLR)下评估了MEC/APBBR/aeMBBR。结果表明,OLR从0.2增加到0.44kgCOD/m3d不会影响有机物的去除。随着OLR增加至0.44kgCOD/m3d,养分和固体去除率下降。全球化学需氧量(COD)的去除,生化需氧量(BOD),总氮(TN),氨态氮(NH4+),总磷(TP)和总悬浮固体(TSS)去除率为81%至84%,84%到85%,53%到68%,88%到98%,分别为11%至30%和76%至88%,是在这项研究中获得的。MEC中产生的电流密度从0到0.41A/m2有助于增加氢气产生和污染物去除。在MEC中获得的最大体积制氢速率为0.007L/L。d(0.072L/d)。将MEC集成到基于生物膜的反应器中,施加1.0V的电压会在MEC内产生不同的生物电化学氮和磷转化,允许同时反硝化硝化过程和除磷。
    The septic tank is the most commonly used decentralized wastewater treatment systems for household wastewater treatment in on-site applications. The removal rate of various pollutants is lower in different septic tank configurations. The integration of a microbial electrolysis cells (MEC) into septic tank or biofilm-based reactors can be a green and sustainable technology for household wastewater treatment and energy production. In this study, a 50-L septic tank was converted into a 50-L MEC coupled with biofilm-based reactor for simultaneous household wastewater treatment and hydrogen production. The biofilm-based reactor was integrated by an anaerobic packed-bed biofilm reactor (APBBR) and an aerobic moving bed biofilm reactor (aeMBBR). The MEC/APBBR/aeMBBR was evaluated at different organic loading rates (OLRs) by applying voltage of 0.7 and 1.0 V. Result showed that the increase of OLRs from 0.2 to 0.44 kg COD/m3 d did not affect organic matter removals. Nutrient and solids removal decreased with increasing OLR up to 0.44 kg COD/m3 d. Global removal of chemical oxygen demand (COD), biochemical oxygen demand (BOD), total nitrogen (TN), ammoniacal nitrogen (NH4+), total phosphorus (TP) and total suspended solids (TSS) removal ranged from 81 to 84%, 84 to 85%, 53 to 68%, 88 to 98%, 11 to 30% and 76 to 88% respectively, was obtained in this study. The current density generated in the MEC from 0 to 0.41 A/m2 contributed to an increase in hydrogen production and pollutants removal. The maximum volumetric hydrogen production rate obtained in the MEC was 0.007 L/L.d (0.072 L/d). The integration of the MEC into biofilm-based reactors applying a voltage of 1.0 V generated different bioelectrochemical nitrogen and phosphorus transformations within the MEC, allowing a simultaneous denitrification-nitrification process with phosphorus removal.
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  • 文章类型: Journal Article
    在能源短缺的大背景下,氢能作为绿色清洁能源备受关注。为了探索高效的制氢途径,我们设计了一种碳基核壳光热辅助光催化体系(Carbon@ZnIn2S4,记为C@ZIS)的复合光催化剂。精心设计的催化剂C@ZIS复合材料即使在不存在贵金属Pt助催化剂的情况下也表现出2.97mmolg-1h-1的光催化氢沉淀速率。将基于碳的核-壳光催化剂结合到光催化反应中通过在反应溶液中引发光热效应而显著影响反应的活性。物理化学实验结果表明,C@ZIS复合体系中的碳球可以提供更多的活性位点,从而加速电子转移和分离效率,从而提高了光催化活性。该研究提出了一种有效的设计概念,用于开发有效的碳基核壳光热辅助光催化剂,这有望促进太阳能到氢能的有效转化。
    Against the backdrop of energy shortage, hydrogen energy has attracted much attention as a green and clean energy source. In order to explore efficient hydrogen production pathways, we designed a composite photocatalyst with carbon-based core-shell photothermal-assisted photocatalytic system (Carbon@ZnIn2S4, denoted as C@ZIS). The well-designed catalyst C@ZIS composites demonstrated a photocatalytic hydrogen precipitation rate of 2.97 mmol g-1 h-1 even in the absence of the noble metal Pt co-catalyst. The incorporation of carbon-based core-shell photocatalysts into a photocatalytic reaction significantly affects the activity of the reaction by triggering a photothermal effect in the reaction solution. The results of the physicochemical experiments demonstrated that the carbon spheres in C@ZIS composite system could provide a greater number of active sites, thereby accelerating the electron transfer and separation efficiency, and thus enhancing the photocatalytic activity. The study presents an efficacious design concept for the development of efficacious carbon-based core-shell photothermal-assisted photocatalysts, which is anticipated to facilitate the efficient conversion of solar energy to hydrogen energy.
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  • 文章类型: Journal Article
    污染物的光催化降解与氢气(H2)释放已成为解决环境和能源危机的有希望的解决方案。然而,光激发电子和空穴的快速复合限制了光催化活性。在这里,通过用ZnIn2S4取代C-TiO2中的氧位点,设计了S方案异质结碳掺杂的TiO2/ZnIn2S4(C-TiO2/ZnIn2S4)。在可见光照射下,最佳C-TiO2/ZnIn2S4对微囊藻毒素-LR(MC-LR)的降解效率较高(88.6%),与原始C-TiO2(72.9%)和ZnIn2S4(66.8%)相比。此外,C-TiO2/ZnIn2S4的H2产率达到1526.9μmol·g-1·h-1,分别是C-TiO2和ZnIn2S4的3.83倍和2.87倍。实验和理论研究表明,C-TiO2/ZnIn2S4异质结中存在内部电场(IEF),加速光生电荷对的分离,从而提高MC-LR降解和H2产生的光催化效率。这项工作突出了开发用于废水处理和H2生成的高性能光催化剂的新视角。
    Photocatalytic degradation of pollutants coupled with hydrogen (H2) evolution has emerged as a promising solution for environmental and energy crises. However, the fast recombination of photoexcited electrons and holes limits photocatalytic activities. Herein, an S-scheme heterojunction carbon doped-TiO2/ZnIn2S4 (C-TiO2/ZnIn2S4) was designed by substituting oxygen sites within C-TiO2 by ZnIn2S4. Under visible light irradiation, the optimal C-TiO2/ZnIn2S4 exhibits a higher degradation efficiency (88.6%) of microcystin-LR (MC-LR), compared to pristine C-TiO2 (72.9%) and ZnIn2S4 (66.8%). Furthermore, the H2 yield of the C-TiO2/ZnIn2S4 reaches 1526.9 μmol g-1 h-1, which is 3.83 times and 2.87 times that of the C-TiO2 and ZnIn2S4, respectively. Experimental and theoretical investigations reveal that an internal electric field (IEF) informed in the C-TiO2/ZnIn2S4 heterojunction, accelerates the separation of photogenerated charge pairs, thereby enhancing photocatalytic efficiency of MC-LR degradation and H2 production. This work highlights a new perspective on the development of high-performance photocatalysts for wastewater treatment and H2 generation.
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  • 文章类型: Journal Article
    开发用于甲烷干重整(DRM)的具有成本效益和高性能的催化剂系统对于可持续生产氢气(H2)至关重要。在这里,我们研究了在Ni基催化剂中使用铁(Fe)作为促进剂和主要的氧化铝载体来改善其DRM性能。发现添加铁作为启动子会添加可还原的铁物种以及可还原的NiO物种,增强碱性并诱导可氧化碳的沉积。通过掺入1重量%。%Fe一5Ni/10ZrAl催化剂,观察到更高的CO2相互作用和可还原的“与载体具有强相互作用的NiO物种”的形成,这导致了420分钟的流上时间(TOS)中80%的H2产率。进一步将Fe含量增加至2wt%导致形成另外的可还原的氧化铁物质,并且H2产率显著增加至84%。尽管Fe促进的催化剂严重失重,由于CH4分解速率和碳沉积物扩散速率之间的适当平衡,因此保持了高H2产率。最后,掺入3重量。%Fe加入5Ni/10ZrAl催化剂导致最高的CO2相互作用,可还原NiO物种的广泛存在,最小的石墨沉积物和87%的H2产率。我们的发现表明,铁促进的氧化锆-氧化铝负载的Ni催化剂可以是通过DRM生产H2的廉价且优异的催化体系。
    Developing cost-effective and high-performance catalyst systems for dry reforming of methane (DRM) is crucial for producing hydrogen (H2) sustainably. Herein, we investigate using iron (Fe) as a promoter and major alumina support in Ni-based catalysts to improve their DRM performance. The addition of iron as a promotor was found to add reducible iron species along with reducible NiO species, enhance the basicity and induce the deposition of oxidizable carbon. By incorporating 1 wt.% Fe into a 5Ni/10ZrAl catalyst, a higher CO2 interaction and formation of reducible \"NiO-species having strong interaction with support\" was observed, which led to an ∼80% H2 yield in 420 min of Time on Stream (TOS). Further increasing the Fe content to 2wt% led to the formation of additional reducible iron oxide species and a noticeable rise in H2 yield up to 84%. Despite the severe weight loss on Fe-promoted catalysts, high H2 yield was maintained due to the proper balance between the rate of CH4 decomposition and the rate of carbon deposit diffusion. Finally, incorporating 3 wt.% Fe into the 5Ni/10ZrAl catalyst resulted in the highest CO2 interaction, wide presence of reducible NiO-species, minimum graphitic deposit and an 87% H2 yield. Our findings suggest that iron-promoted zirconia-alumina-supported Ni catalysts can be a cheap and excellent catalytic system for H2 production via DRM.
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  • 文章类型: Journal Article
    氢-乙醇联产可以显著提高玉米秸秆(CS)的能量转化效率。在这项研究中,以CS为原料,研究了一步和两步光发酵产氢(PFHP)和乙醇生产的联产特性。此外,分析了实验的气液特性。计算了氢-乙醇联产的动力学,并对氢气和乙醇的经济性进行了分析。实验结果表明,当CS浓度为25g/L时,两步氢-乙醇联产的制氢性能最好。总氢气产量为350.08mL,氢气产率为70.02mL/g,是一步法的2.45倍。氢-乙醇联产效率为17.79%,与氢发酵相比,效率是氢发酵的2.76倍。研究结果为CS的优质利用提供了技术参考。
    Hydrogen-ethanol co-production can significantly improve the energy conversion efficiency of corn stalk (CS). In this study, with CS as the raw material, the co-production characteristics of one-step and two-step photo-fermentation hydrogen production (PFHP) and ethanol production were investigated. In addition, the gas and liquid characteristics of the experiment were analyzed. The kinetics of hydrogen-ethanol co-production was calculated, and the economics of hydrogen and ethanol were analyzed. Results of the experiments indicated that the two-step hydrogen-ethanol co-production had the best hydrogen production performance when the concentration of CS was 25 g/L. The total hydrogen production was 350.08 mL, and the hydrogen yield was 70.02 mL/g, which was 2.45 times higher than that of the one-step method. The efficiency of hydrogen-ethanol co-production was 17.79 %, which was 2.76 times more efficient than hydrogen compared to fermentation with hydrogen. The result provides technical reference for the high-quality utilization of CS.
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  • 文章类型: Journal Article
    光催化已成为一种有前途且环境可持续的解决方案,可通过乙醇光反应产生高纯度氢气。人们普遍认为,添加助催化剂,尤其是贵金属,显著增强了半导体的催化活性。然而,贵金属如Pt的高成本可能会限制这一新兴技术的实际应用。在这里,我们评估了通过在预形成的半导体纳米颗粒之间创建适当的界面来减少贵金属负载的可能性。商业二氧化钛(P25)由于其商业可用性而被选为半导体,促进我们结果的直接验证和佐证。选择Pt作为助催化剂是因为用于乙醇光重整的最有效的光催化剂之一仍然基于P25与Pt的组合使用。我们报告说,当使用非常低的Pt负载量(≤0.05wt%)时,诱导聚集体的产生显着改善了产生的总氢气。我们开发了一种开创性的反应器,旨在在液相中纳米颗粒悬浮液的真实操作条件下进行光致发光研究。这种方法使我们能够从P25附聚物中获得平均光致发光发射,这是不可能通过使用标准固体样品支架获得的。多亏了这些设备,我们可以得出的结论是,活性的这种显着改善主要是由于形成了有利于聚集体颗粒之间电荷转移的界面。据此,团聚体的二氧化钛纳米颗粒充当天线以收集太阳光的光子并产生将被转移到位于相同团聚体中的铂纳米颗粒的光激发电子。相比之下,具有低Pt负载量的原始P25将具有大量没有铂的二氧化钛纳米颗粒,因此,inactive.该结果在用于实际未来光催化反应器的固定化光催化系统的情况下尤其相关,因为半导体的固定将产生与我们的方法产生的相互作用相似的相互作用。因此,最初的半导体固定和随后的助催化剂的光沉积成为显著降低助催化剂含量的有希望的方法。
    Photocatalysis has emerged as a promising and environmentally sustainable solution to produce high-purity hydrogen through ethanol photoreforming. It is commonly accepted that adding co-catalysts, especially noble metals, significantly enhances the catalytic activity of semiconductors. However, the high cost of noble metals such as Pt may limit the real application of this emerging technology. Here we evaluate the possibility of reducing the noble metal loading by creating the appropriate interface between pre-formed semiconductor nanoparticles. Commercial titania (P25) was selected as the semiconductor due to its commercial availability, facilitating the straightforward validation and corroboration of our results. Pt was selected as co-catalyst because one of the most efficient photocatalysts for the ethanol photo-reforming is still based on the use of P25 in combination with Pt. We report that the creation of induced aggregates dramatically improves the total hydrogen produced when very low loadings (≤0.05 wt%) of Pt are used. We have developed a pioneering reactor designed for conducting photoluminescence studies under authentic operational conditions of nanoparticle suspensions in the liquid phase. This approach allows us to obtain the average photoluminescence emission from the P25 agglomerates what it would be impossible to obtain by using standard solid samples holders. Thanks to this equipment, we can conclude that this remarkable improvement of the activity is mainly due to creation of an interface that favors the charge transfer between the particles of the aggregates. According to this, the titania nanoparticles of the agglomerates act as an antenna to collect the photons of the sun-light and produce the photo-excited electrons that will be transferred to the platinum nanoparticles located in the same agglomeration. In contrast, raw P25 with low loadings of Pt would have a high number of titania nanoparticles without platinum, and therefore, inactive. This result would be especially relevant in the case of immobilized photocatalytic systems for real future photocatalytic reactors because the immobilization of the semiconductors would generate similar interactions to the one created by our method. Consequently, the initial semiconductor immobilization followed by the subsequent photo-deposition of the co-catalyst emerges as a promising approach for a substantial reduction of the co-catalyst content.
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  • 文章类型: Journal Article
    开发了Mo-Ni/C催化剂,并根据乙醇的分解来生产多壁碳纳米管(MWCNT)和氢气进行了评估。催化剂使用不同摩尔比的Mo:Ni(1:9、2:8和3:7),其中Mo充当掺杂剂以提高MWCNT产率,并且Ni充当MWCNT形成的主要活性相。在测试的比率中,2:8的Mo:Ni比表现出最佳的性能,产生86%的氢气和高质量的MWCNTs。除了氢,该过程还产生了CO,CH4和CO2。气相色谱(GC)用于分析Mo:Ni比例对气体产量和选择性的影响,虽然使用SEM评估了所得MWCNT的质量,拉曼光谱,和TEM分析。
    A Mo-Ni/C catalyst was developed and assessed in terms of the decomposition of ethanol to produce multi-wall carbon nanotubes (MWCNTs) and hydrogen. The catalyst utilized different molar ratios of Mo:Ni (1:9, 2:8, and 3:7), with Mo acting as a dopant to enhance the MWCNT yield and Ni acting as the primary active phase for MWCNT formation. Among the tested ratios, the 2:8 Mo:Ni ratio exhibited the optimal performance, yielding 86% hydrogen and high-quality MWCNTs. In addition to hydrogen, the process also generated CO, CH4, and CO2. Gas chromatography (GC) was employed to analyze the influence of the Mo:Ni ratio on gas production and selectivity, while the quality of the resulting MWCNTs was evaluated using SEM, Raman spectroscopy, and TEM analyses.
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  • 文章类型: Journal Article
    通过光催化产生氢气是解决环境问题和能源危机的一项令人着迷的技术。然而,追求成本效益,稳定,和有效的光催化剂在能源转换领域仍然是一个重大的挑战。在这里,我们设计了新型的InVO4/Ti3C2MXene(IVTC)异质结构,采用酸蚀刻产生具有手风琴状形态的Ti3C2MXene,使用水热技术生产正交InVO4纳米颗粒(NPs),并通过自组装方法将它们整合在一起。场发射扫描电子显微镜和HRTEM分析均显示InVO4NP的一致分布,在两个表面和Ti3C2MXene片之间的平均尺寸为43.4nm。Ti3C2MXene纳米片和InVO4之间的紧密界面抑制了载流子复合并促进了电荷转移,从而促进光催化H2的产生。在可见光照射下,在含有优化的10%的InVO4负载量的IVTC异质结构中,氢释放速率增强,与原始InVO4NP相比,表现出超过3倍的增加,在四个周期内保持效率。这项研究提出了一种有希望的方法,用于设计和创建具有优异的可见光驱动的光催化活性的高效异质结构,以析出H2。
    The generation of hydrogen through photocatalysis is a fascinating technology for addressing environmental concerns and the energy crisis. Nevertheless, the quest for cost-effective, stable, and efficient photocatalysts in the realm of energy conversion remains a significant challenge. Herein, we designed novel InVO4/Ti3C2 MXene (IVTC) heterostructures by employing acid etching to produce Ti3C2 MXene with an accordion-like morphology, using the hydrothermal technique for the production of orthorhombic InVO4 nanoparticles (NPs), and integrating them through a self-assembly approach. Both field-emission scanning electron microscopy and HRTEM analyses revealed a consistent distribution of InVO4 NPs with an average size of 43.4 nm on both surfaces and between the sheets of Ti3C2 MXene. The intimate interface between the Ti3C2 MXene nanosheet and InVO4 suppressed carrier recombination and promoted charge transfer, thereby boosting photocatalytic H2 production. Under visible light exposure, the rate of hydrogen evolution is enhanced in IVTC heterostructures containing an optimized 10% loading of InVO4, exhibiting over a 3-fold increase compared to pristine InVO4 NPs, maintaining efficiency across four cycles. This research presents a promising method for designing and creating high-efficiency heterostructures possessing excellent visible-light-driven photocatalytic activity for H2 evolution.
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  • 文章类型: Journal Article
    高熵材料(HEMs)由于其多样化和迷人的物理化学性质而受到广泛关注。然而,微调HEM的形态特性仍然是一个巨大的挑战,限制其潜在的应用。为了解决这个问题,我们提出了一个快速的,低能耗二乙烯三胺(DETA)辅助微波水热法合成一系列二维高熵硒化物(HESes)。随后,所获得的HES用于光催化水分解。值得注意的是优化的HES,Cd0.9Zn1.2Mn0.4Cu1.8Cr1.2Se4.5,显示出氢的输出速率为16.08mmolh-1g-1,量子效率约为在420nm单色LED照射下30%。结果表明,这些HES的光催化性能不仅源于扩大的比表面积和提高的光生电荷载流子利用效率,而且还源于促进Cd-Hads键的形成,受多种主元素对Cd的影响。这些发现为为各种应用量身定制的HEM设计提供了指导。
    High-entropy materials (HEMs) have garnered extensive attention owing to their diverse and captivating physicochemical properties. Yet, fine-tuning morphological properties of HEMs remains a formidable challenge, constraining their potential applications. To address this, we present a rapid, low-energy consumption diethylenetriamine (DETA)-assisted microwave hydrothermal method for synthesizing a series of two-dimensional high-entropy selenides (HESes). Subsequently, the obtained HESes are harnessed for photocatalytic water splitting. Noteworthy is the optimized HESes, Cd0.9Zn1.2Mn0.4Cu1.8Cr1.2Se4.5, showcasing an output rate of hydrogen of 16.08 mmol h-1 g-1 and a quantum efficiency of ca. 30% under 420 nm monochromatic LED irradiation. It is revealed that the photocatalytic performance of these HESes stems not only from the enlarged specific surface area and enhanced photogenerated charge carrier utilization efficiency but also from the promoted formation of the Cd-Hads bond, influenced by multiple principal elements on the Cd. These findings provide a guide for the design of HEMs tailored for various applications.
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