WO2025236249A1 - 基于流动式光催化反应的日光下原位合成过氧化氢的方法 - Google Patents

基于流动式光催化反应的日光下原位合成过氧化氢的方法

Info

Publication number
WO2025236249A1
WO2025236249A1 PCT/CN2024/093762 CN2024093762W WO2025236249A1 WO 2025236249 A1 WO2025236249 A1 WO 2025236249A1 CN 2024093762 W CN2024093762 W CN 2024093762W WO 2025236249 A1 WO2025236249 A1 WO 2025236249A1
Authority
WO
WIPO (PCT)
Prior art keywords
water
flow
photocatalytic
hydrogen peroxide
bismuth vanadate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/CN2024/093762
Other languages
English (en)
French (fr)
Inventor
褚驰恒
郑小汕
潘振华
于万超
谭孟溪
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zju Anqing Yangtze Delta Future Industry Institute
Zhejiang University
Original Assignee
Zju Anqing Yangtze Delta Future Industry Institute
Zhejiang University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zju Anqing Yangtze Delta Future Industry Institute, Zhejiang University filed Critical Zju Anqing Yangtze Delta Future Industry Institute
Priority to PCT/CN2024/093762 priority Critical patent/WO2025236249A1/zh
Publication of WO2025236249A1 publication Critical patent/WO2025236249A1/zh
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
    • C01B15/01—Hydrogen peroxide
    • C01B15/027—Preparation from water

Definitions

  • This invention belongs to the field of particulate photocatalysis technology and relates to a system for capturing and utilizing solar energy through artificial photosynthesis technology, which has important value in the field of green chemical and fuel synthesis.
  • it relates to a method for in-situ synthesis of hydrogen peroxide under sunlight based on a flow-type photocatalytic reaction.
  • PC Particulate photocatalysis
  • Particulate photocatalysts and their integration with cocatalyst components can be obtained through simple synthetic routes (such as solid-phase, melt, and solution methods for photocatalysts; impregnation and photodeposition for cocatalysts) without the need for expensive vacuum deposition techniques. Furthermore, these synthetic routes do not require the high-purity precursors and reagents used in the photovoltaic industry. These characteristics make PC systems advantageous for low-cost and large-scale preparation. In addition, particulate photocatalysts have high specific surface areas (e.g., BiVO4 is approximately 5 m2/g) for surface reactions, enabling operating photocurrents on the scale of 10 ⁇ 6 ⁇ A cm ⁇ 2 . These operating conditions can reduce the inactivation of reaction sites and give the PC system a longer lifespan.
  • BiVO4 is approximately 5 m2/g
  • H2O2 generation has attracted increasing attention. Compared to water splitting, H2O2 generation offers advantages in scalable production and on-demand utilization. The Gibbs free energy barrier for H2O2 generation is only half that of water splitting, making the reaction thermodynamically favorable for non-sacrificial synthesis. Furthermore, aqueous H2O2 is the only product, thus avoiding concerns about product separation and safety issues. Moreover, as a liquid solar fuel, H2O2 has an energy density comparable to H2 gas but with greater storage and transport capabilities. Most importantly, the commercial value of H2O2 is an order of magnitude lower than that of H2 based on per-molar price, resulting in lower solar conversion efficiencies required for economical production.
  • H2O2 - based PC generation systems are primarily powder suspensions. This suspension design is unsuitable for large-scale H2O2 photosynthesis because 1) maximizing light capture in the particulate suspension is not repeatable, and 2) separating the H2O2 product from the particulate suspension requires additional processing, thus increasing energy consumption and cost. To date, developing scalable PC systems remains a major challenge hindering the practical application of H2O2 photosynthesis .
  • the purpose of this invention is to provide a method for in-situ synthesis of hydrogen peroxide under sunlight based on a flow-type photocatalytic reaction.
  • This invention enables the conversion of water and oxygen into high-value-added hydrogen peroxide under outdoor sunlight conditions.
  • This application achieves a breakthrough by preparing a flexible and lightweight photocatalytic membrane, which not only facilitates the design of reaction devices but also enables the separation of the catalyst and product, significantly reducing the production cost of hydrogen peroxide.
  • this application allows for the preparation of hydrogen peroxide at different concentrations by adjusting the flow rate, making it suitable for various application scenarios and achieving more significant results in environmental remediation, demonstrating strong practicality and widespread application value.
  • This application provides a method for in-situ synthesis of hydrogen peroxide under sunlight based on a flow-type photocatalytic reaction, comprising the following steps:
  • CoOx and Pd cocatalysts were loaded at the oxidation and reduction ends of the bismuth vanadate photocatalyst, respectively.
  • the flow-type photocatalytic reaction device includes a bottom plate, a water tank, and a cover plate from bottom to top.
  • the water tank is provided with an inlet and an outlet.
  • the photocatalytic membrane is placed between the bottom plate and the water tank.
  • step (1) specifically involves: dispersing the bismuth vanadate photocatalyst in a 0.5-1.0 mM sodium iodate aqueous solution, adding 0.2-0.4 wt% cobalt nitrate relative to the weight of the bismuth vanadate photocatalyst, and selectively depositing the CoOx cocatalyst onto the oxidation end sites of the bismuth vanadate photocatalyst under visible light irradiation; after washing and recovering the catalyst, placing it in clean water, adding 0.3-0.6 wt% sodium tetrachloropalladium relative to the weight of the catalyst, and selectively depositing the Pd cocatalyst onto the reduction end sites of the bismuth vanadate photocatalyst under visible light irradiation.
  • step (2) specifically involves: thoroughly stirring 100-300 mg of bismuth vanadate photocatalyst, 1700-2000 mg of polyvinylidene fluoride and 8-10 g of dimethylformamide at 60-65°C to obtain a uniform membrane precursor solution; centrifuging the membrane precursor solution at a speed of 4000-5000 rpm to remove air bubbles; scraping a uniform 200-300 micrometer thick layer of membrane precursor solution onto a clean glass slide using a film scraper, placing it in clean water to stand until the dimethylformamide solvent has fully diffused and evaporated to obtain a photocatalytic membrane.
  • step (3) hydrogen peroxide solutions of different concentrations are obtained by adjusting the flow rate of water in the flow-type photocatalytic reactor.
  • this application provides a simple photocatalytic reaction device for converting solar energy into chemical energy, which can utilize sunlight to convert water and oxygen into hydrogen peroxide.
  • the developed photocatalytic membrane preparation process avoids the additional energy consumption and cost caused by catalyst and product separation, and the membrane synthesis process is scalable and easily scalable.
  • This reactor features a directionally designed water tank, allowing control of the reaction time between water and the catalytic membrane by adjusting the water flow rate, thus producing hydrogen peroxide of varying concentrations and making it suitable for diverse applications.
  • this reactor requires no sophisticated control equipment and can be used immediately in sunny locations, making it suitable for various chemical production and environmental remediation processes.
  • FIG. 1 is a flowchart illustrating a photocatalytic membrane preparation method according to an exemplary embodiment: a is a precursor liquid formed by the catalyst and the polyvinylidene fluoride membrane in the solvent dimethylformamide; b is a picture of the membrane scraping process; c is the phase transition process of the membrane; d is a picture of the finished membrane and its flexibility; e is a scanning electron microscope image of the photocatalytic membrane.
  • Figure 2 is a schematic diagram of the photoreactor and its photocatalytic performance.
  • Figure a shows the reactor structure;
  • Figure b shows the photocatalytic hydrogen peroxide generation performance at different flow rates.
  • Figure 3 shows the outdoor experimental performance, where a is a photograph of a one-square-meter flowable photoreactor; b shows the increase in yield as the area of the photocatalyst increases; c shows the generation of hydrogen peroxide under different light intensities at different times of the day; and d shows the photoreactor's activity stability experiment over one month.
  • Figure 4 shows a sample case of using the photoreactor to produce hydrogen peroxide in situ for soil remediation
  • a is a schematic diagram of the process of accelerating the natural purification of soil with in situ photosynthetic hydrogen peroxide
  • b is the concentration change under different conditions
  • c is the removal effect of pollutants in the soil after being added to the soil.
  • first, second, third, etc. may be used in this application to describe various information, this information should not be limited to these terms. These terms are only used to distinguish information of the same type from one another.
  • first information may also be referred to as second information, and similarly, second information may also be referred to as first information.
  • word “if” as used herein can be interpreted as "when,””when,” or “in response to.” "Should be determined”.
  • This application provides a method for in-situ synthesis of hydrogen peroxide under sunlight, comprising the following steps:
  • CoOx and Pd cocatalysts were loaded at the oxidation and reduction ends of the bismuth vanadate photocatalyst, respectively.
  • a bismuth vanadate photocatalyst is dispersed in a 1.0 mM sodium iodate aqueous solution, and 0.3 wt% cobalt nitrate solution is added. Under visible light irradiation, the CoOx cocatalyst is selectively deposited on the oxidation end sites. After the catalyst is washed and recovered, it is placed in water, and 0.4 wt% sodium tetrachloropalladium solution is added. Under visible light irradiation, the Pd cocatalyst is selectively deposited on the reduction sites.
  • the proportion of photocatalyst added and the thickness of the film have a significant impact on the performance of the photocatalytic membrane. For example, reducing the amount of photocatalyst used will lead to insufficient catalytic performance, while excessive catalyst will result in catalyst waste.
  • the thickness of the catalytic membrane also affects performance. To this end, the applicant has conducted performance experiments on photocatalytic membranes with different proportions and thicknesses. The catalytic membrane with a catalyst proportion of 2% and a thickness of 200 micrometers showed the best performance. Therefore, subsequent embodiments will all be based on this proportion.
  • the flow-type photocatalytic reaction device includes a bottom plate, a water tank, and a cover plate from bottom to top.
  • the water tank is provided with an inlet and an outlet.
  • the photocatalytic membrane is placed between the bottom plate and the water tank.
  • the reactor includes a base plate, a cover plate, an inlet, an outlet, and a water tank.
  • the photocatalytic membrane is placed on the base plate and below the water tank, and the reactor is fixed with screws to form a flow-through photoreactor.
  • water is introduced through the inlet, and the water flows directionally under the influence of the water tank, ultimately yielding a hydrogen peroxide solution at the outlet.
  • the reaction time between the water and the photocatalytic membrane can be controlled by adjusting the water flow rate, thus obtaining hydrogen peroxide of different concentrations.
  • Figure 3 illustrates the scalable production of the reactor.
  • the reactor material is high light transmittance.
  • the acrylic cover allows light with a wavelength greater than 400 nm to pass through. Cutting off the ultraviolet light region helps reduce the decomposition of H2O2 .
  • Performance tests under natural sunlight showed that the H2O2 generation rate increased linearly with the increase of the BiVO4 panel area ( Figure 3b). Therefore, when the panel area increased from 625 cm2 to 1 m2 , the STC remained constant at ⁇ 0.087%.
  • the H2O2 generation rate is related to light intensity. For example, in a day's reaction (Figure 3c), H2O2 generation first increases after sunrise (7:00), peaks at 12:00, and then declines until sunset (17:30). The STC shows an inverse trend with light intensity because the AQY is lower under high light intensity, a common phenomenon in large-scale outdoor trials.
  • This application further investigated the long-term stability of the photocatalytic panel reactor from October 12, 2022 to November 12, 2022 (30°17′46′′N, 120°05′31′′E, Hangzhou, China). The H2O2 generation rate correlated well with light intensity (d in Figure 3).
  • the STC showed little change on sunny days, but increased slightly on cloudy days with low light intensity, indicating stable solar-chemical conversion performance of the photocatalyst sheet and the array panel reactor.
  • the XRD, UV-vis, and XPS spectra of the photocatalyst sheet showed consistent performance.
  • ICP analysis of the reactant solution revealed no significant elemental dissolution during the reaction.
  • This application also utilizes this method to accelerate the natural evolutionary process of soil.
  • photosynthetic H2O2 is used to initiate a Fenton-like reaction with reducing substances in the soil (such as Fe(II)) to generate ⁇ OH in the soil.
  • reducing substances in the soil such as Fe(II)
  • Fe(II) reducing substances in the soil
  • a natural diurnal rhythm was simulated, i.e., 8 hours of on-site H2O2 photosynthesis and Fenton reagent activation were carried out during the day (Figure 4b), followed by 16 hours of soil microbial regeneration of the Fenton reagent at night.
  • the degradation rate of phenol exceeded 95%.
  • only slight phenol degradation was observed without the injection of H2O2 ( Figure 4c).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

提供基于流动式光催化反应的日光下原位合成过氧化氢的方法，包括以下步骤：在钒酸铋光催化剂的氧化端和还原端分别负载CoOx助催化剂和Pd助催化剂；将钒酸铋光催化剂与聚偏氟乙烯在二甲基甲酰胺溶液中充分混合均匀，然后通过刮膜机在玻璃片上刮出200微米厚的混合物前驱液，随后将玻璃片置于清水中，通过相转变得出柔性的光催化膜；将光催化膜置于流动式光催化反应装置中，将反应器固定后，置于日光条件下，将水通入反应器，在出水口获得过氧化氢溶液，其中流动式光催化反应装置包括自下而上的底板、水槽、盖板，水槽设置有进水口、出水口，光催化膜设置于底板和水槽之间。

Description

基于流动式光催化反应的日光下原位合成过氧化氢的方法 技术领域
本发明属于颗粒光催化技术领域，涉及一种通过人工光合作用技术捕获和利用太阳能的系统，在绿色化学品和燃料合成领域具有重要价值，尤其涉及基于流动式光催化反应的日光下原位合成过氧化氢的方法。
背景技术
通过人工光合作用技术来捕获和利用太阳能在绿色合成高附加值化学品和燃料方面具有重要价值。先前基于光电催化的研究已经在太阳能转换方面取得了显著成就，实现了超过10％的太阳能转化为氢气和超过2％的太阳能转化为过氧化氢(H2O2)的转化效率。然而，光电催化在人工光合作用中的应用面临着可扩展性差和高成本的挑战。颗粒光催化(PC)被认为是最简单的人工光合作用方法，因为它在装置制备、操作和维护方面具有优势。通过简便的合成途径(如固相、熔融、溶液法等用于光催化剂；浸渍、光沉积等用于助催化剂)，可以获得颗粒光催化剂及其与助催化剂组分的集成，而无需使用昂贵的真空沉积技术。此外，这些合成途径不需要光伏工业中使用的高纯度前体和试剂。这些特点使得PC系统有利于低成本和大规模制备。此外，颗粒光催化剂具有高比表面积(例如BiVO4约为5平方米/克)，用于表面反应，可实现10-μA cm-2尺度的操作光电流。这种操作条件可以减轻反应位点的失活，并使PC系统具有较长的寿命。
在各种PC反应中，H2O2生成引起了越来越多的关注。与水分解相比，H2O2生成在可扩展生产和按需利用方面具有优势。H2O2生成的吉布斯自由能障碍仅为水分解的一半，使得这个反应在热力学上有利于实现非牺牲合成。此外，H2O2水溶液是唯一的产物，因此可以避免产物分离和安全问题的关注。此外，作为液体太阳能燃料，H2O2具有与H2气体相当的能量密度，但具有更高的储存和运输能力。最重要的是，根据每摩尔价格计算，H2O2的商业价值比H2低一个数量级，使得实现经济生产所需的太阳能转换效率更低。出于这些原因，过去十年中对光催化H2O2生成的研究取得了显著进展。然而，目前可用的H2O2生成PC系统主要是粉末悬浮液。这种悬浮设计不适用于大规模的H2O2光合作用，因为1)在颗粒悬浮液中最大化光捕获不可重复，2)从颗粒悬浮液中分离H2O2产品需要额外的处理，从而增加了能耗和成本。迄今为止，开发可扩展的PC系统仍然是阻碍H2O2光合作用实际应用的主要挑战。
发明内容
本发明的目的在于提供一种基于流动式光催化反应的日光下原位合成过氧化氢的方法， 可实现在户外日光条件下将水和氧气转化生产高附加值的过氧化氢。本申请突破性地制备了柔性轻便的光催化膜，不仅易于设计反应装置，同时实现了催化剂与产物之间的分离，大大降低了过氧化氢生产成本。本申请还可以通过调节流速得到不同浓度的过氧化氢，适用于不同使用场景，并在环境修复中取得更显著的成果，具有很强的实用性和推广价值。
本申请提供一种基于流动式光催化反应的日光下原位合成过氧化氢的方法，包括以下步骤：
(1)在钒酸铋光催化剂的氧化端和还原端分别负载CoOx助催化剂和Pd助催化剂；
(2)将钒酸铋光催化剂与聚偏氟乙烯在二甲基甲酰胺溶液中充分混合均匀，然后通过刮膜机在玻璃片上刮出200微米厚的混合物前驱液，随后将玻璃片置于清水中，通过相转变得出柔性的光催化膜；
(3)将光催化膜置于流动式光催化反应装置中，将反应器固定后，置于日光条件下，将水通入反应器，在出水口获得过氧化氢溶液，其中所述流动式光催化反应装置包括自下而上的底板、水槽、盖板，所述水槽设置有进水口、出水口，所述光催化摸设置于底板和水槽之间。
进一步地，所述步骤(1)具体为：将钒酸铋光催化剂分散在0.5-1.0mM碘酸钠水溶液中，加入相比于钒酸铋光催化剂重量0.2-0.4wt％的硝酸钴，在可见光照射下，将CoOx助催化剂选择性沉积于钒酸铋光催化剂的氧化端位点上；将催化剂洗净回收后，置于清水中，加入相比于催化剂重量0.3-0.6wt％的四氯钯酸钠，在可见光照射下，将Pd助催化剂选择性沉积于钒酸铋光催化剂的还原端位点上。
进一步地，在沉积助催化剂过程中，所有操作均在无氧环境下进行。
进一步地，所述步骤(2)具体为：将100-300mg的钒酸铋光催化剂、1700-2000mg的聚偏氟乙烯和8-10g的二甲基甲酰胺在60-65°的条件下充分搅拌，得到均匀的膜前驱体液；将该膜前驱体液通过离心机在4000-5000rpm的转速下，将气泡排除；用刮膜机在干净的玻璃片上刮出一层均匀的200-300微米厚的膜前驱体液，置于清水中静止，待二甲基甲酰胺溶剂充分扩散挥发，得到光催化膜。
进一步地，在步骤(3)中，通过对所述流动式光催化反应装置中水流的流速进行调节，得到不同浓度的过氧化氢溶液。
本申请的实施例提供的技术方案可以包括以下有益效果：
由上述实施例可知，本申请提供了一种简便的太阳能转化为化学能的光反应装置，可以利用太阳光将水和氧气转化生成过氧化氢。其中开发的光催化膜制备工艺可以避免了催化剂与产物分离带来的而外能耗和成本，而且该膜的合成工艺可拓展，易实现规模化制备。另外， 该反应器具有定向设计的水槽，可以通过控制水流速度来控制水与催化膜的反应时间，从而得到不同浓度的过氧化氢，可以适用于不同的应用场景。值得一提的是，该反应器不需要精密的控制仪器，可以在日光充足的地方随产随用，适用于各种化工产生与环境修复过程。
应当理解的是，以上的一般描述和后文的细节描述仅是示例性和解释性的，并不能限制本申请。
附图说明
此处的附图被并入说明书中并构成本说明书的一部分，示出了符合本申请的实施例，并与说明书一起用于解释本申请的原理。
图1是根据一示例性实施例示出的光催化膜制备方法流程图：a为催化剂与聚偏氟乙烯膜在溶剂二甲基甲酰胺下形成的前驱体液；b为刮膜过程图片；c为膜的相变过程；d为膜的成品图及其柔软特性；e则是光催化膜的扫描电镜图。
图2是光反应器的结构示意图仪器光催化新能。其中a为反应器结构示意图；b为不同流速下光催化过氧化氢生成性能。
图3户外实验性能图，其中a为一平方米大的流动式光反应器的照片；b为产量随着光催化器面积的增大而增加；c为一天内不同时间段不同光照强度下过氧化氢的生成情况；d为一个月的光反应器活性稳定性实验。
图4是利用该光反应器原位产过氧化氢用于土壤修复的样本案例；a是原位光合成过氧化氢加速土壤自然净化过程示意图；b是不同流俗下的浓度变化；c是加入到土壤后土壤中污染物的去除效果。
具体实施方式
这里将详细地对示例性实施例进行说明，其示例表示在附图中。下面的描述涉及附图时，除非另有表示，不同附图中的相同数字表示相同或相似的要素。以下示例性实施例中所描述的实施方式并不代表与本申请相一致的所有实施方式。
在本申请使用的术语是仅仅出于描述特定实施例的目的，而非旨在限制本申请。在本申请和所附权利要求书中所使用的单数形式的“一种”、“所述”和“该”也旨在包括多数形式，除非上下文清楚地表示其他含义。还应当理解，本文中使用的术语“和/或”是指并包含一个或多个相关联的列出项目的任何或所有可能组合。
应当理解，尽管在本申请可能采用术语第一、第二、第三等来描述各种信息，但这些信息不应限于这些术语。这些术语仅用来将同一类型的信息彼此区分开。例如，在不脱离本申请范围的情况下，第一信息也可以被称为第二信息，类似地，第二信息也可以被称为第一信息。取决于语境，如在此所使用的词语“如果”可以被解释成为“在……时”或“当……时”或“响 应于确定”。
本申请提供一种日光下原位合成过氧化氢的方法，包括以下步骤：
(1)在钒酸铋光催化剂的氧化端和还原端分别负载CoOx助催化剂和Pd助催化剂；
在一实施例中，将钒酸铋光催化剂分散在1.0mM碘酸钠水溶液中，加入0.3wt％的硝酸钴溶液，在可见光照射下，将CoOx助催化剂选择性沉积于氧化端位点上；将催化剂洗净回收后，置于清水中，加入0.4wt％的四氯钯酸钠溶液，在可见光照射下，将Pd助催化剂选择性沉积于还原位点上。
(2)将钒酸铋光催化剂与聚偏氟乙烯在二甲基甲酰胺溶液中充分混合均匀，然后通过刮膜机在玻璃片上刮出200微米厚的混合物前驱液，随后将玻璃片置于清水中，通过相转变得出柔性的光催化膜；
如图1所示，将200mg的光催化剂，1700mg的聚偏氟乙烯和8.1g的二甲基甲酰胺在60°的条件下搅拌12小时，然后得到均匀的膜前驱体液。该膜前驱体液通过离心机在4000rpm的转速下，将气泡排除。随后用刮膜机在干净的玻璃片上刮出一层均匀的200微米厚的膜前驱体液，然后置于清水中静止，待二甲基甲酰胺溶剂的扩散挥发，便得到柔韧的光催化膜。最后，通过扫描电镜对光催化膜表面进行观测，发现光催化剂被膜基底牢牢包裹在膜的表面。
在具体实施中，光催化剂添加比例与刮膜厚度会对光催化膜性能有较大影响，例如减少光催化剂的使用，会导致催化性能的不足，当过多的催化剂则会导致催化剂的浪费，还有催化膜的膜厚也对性能有所影响。为此申请人已进行了不同比例与厚度的光催化膜性能实验，在催化剂比例为2％与200微米厚的催化膜性能最佳，因此后续实施例均以此比例进行。
(3)将光催化膜置于流动式光催化反应装置中，将反应器固定后，置于日光条件下，将水通入反应器，在出水口获得过氧化氢溶液，其中所述流动式光催化反应装置包括自下而上的底板、水槽、盖板，所述水槽设置有进水口、出水口，所述光催化摸设置于底板和水槽之间。
如图2中的a所示，该反应器包括底板、盖板、进水口、出水口、水槽。将光催化膜置于底板之上水槽之下，通过螺丝将反应器固定后，组成流动式光反应器。在日光条件下，在进水口处通入水，水在水槽的作用下定向流动，最终在出口处获得过氧化氢溶液。如图2中的b所示，通过控制水流的速度可以控制水与光催化膜反应的时间，从而得到不同浓度的过氧化氢。
图3则展示了该反应器的可规模化生产，我们将面板反应器扩大到25cm×25cm，并进一步开发了由16个光反应器组成的1平米的阵列面板(图3中的a)。反应器材料为高透光 的亚克力，允许λ>400nm的光通过盖板。切断紫外光区有利于减少H2O2的分解。自然阳光照射下的性能测试表明，H2O2生成率随BiVO4面板面积的增加呈线性增加(图3中的b)。因此，当面板面积从625cm2扩大到1m2时，STC保持恒定在～0.087％。这种稳定的性能在多个光反应器中清楚地证明了BiVO4光催化剂片的易于规模化的潜力。H2O2的生成速率与光照强度有关。例如，在一天的反应中(图3中的c)，H2O2生成在日出后(7:00)首先增加，在12:00达到峰值，然后下降到日落(17:30)。STC随光强的变化趋势相反，因为在高光强下AQY较低，这是大规模户外试验中常见的现象。本申请进一步研究了2022年10月12日至2022年11月12日(30°17′46″N,120°05′31″E，中国杭州)光催化面板反应堆的长期稳定性。H2O2生成速率与光照强度相关良好(图3中的d)。更重要的是，STC在晴天变化不大，而在低光照强度的阴天略有增加，这表明光催化剂片材和阵列板反应器的太阳能-化学转化性能稳定。反应1个月后，光催化剂片材的XRD谱、UV-vis光谱、XPS光谱表现一致。此外，根据反应物溶液的ICP分析，在反应过程中没有观察到明显的元素溶。这些结果表明光催化膜具有显著的稳定性。
本申请还利用了该方法加速土壤的自然进化过程。具体地，如图4中的a所示，利用光合作用的H2O2与土壤中还原性物质(如Fe(II))引发芬顿类反应，在土壤中产生·OH。为了完成H2O2活化和Fenton试剂再生以实现可持续羟基自由基生产的循环，模拟自然昼夜节律，即在白天进行8小时的现场H2O2光合作用(图4中的b)和Fenton试剂活化，然后在夜间进行16小时的土壤微生物对Fenton试剂的再生。经过5个昼夜氧化还原循环后，苯酚的降解率超过95％。与之形成鲜明对比的是，在没有注入H2O2的情况下，只观察到轻微的苯酚降解(<12％)(图4中的c)。这些结果表明，引入现场绿色合成H2O2可以大大加快土壤的自然净化过程。
本领域技术人员在考虑说明书及实践这里公开的内容后，将容易想到本申请的其它实施方案。本申请旨在涵盖本申请的任何变型、用途或者适应性变化，这些变型、用途或者适应性变化遵循本申请的一般性原理并包括本申请未公开的本技术领域中的公知常识或惯用技术手段。
应当理解的是，本申请并不局限于上面已经描述并在附图中示出的精确结构，并且可以在不脱离其范围进行各种修改和改变。

Claims (5)

  1. 一种基于流动式光催化反应的日光下原位合成过氧化氢的方法，其特征在于，包括以下步骤：
    (1)在钒酸铋光催化剂的氧化端和还原端分别负载CoOx助催化剂和Pd助催化剂；
    (2)将钒酸铋光催化剂与聚偏氟乙烯在二甲基甲酰胺溶液中充分混合均匀，然后通过刮膜机在玻璃片上刮出200微米厚的混合物前驱液，随后将玻璃片置于清水中，通过相转变得出柔性的光催化膜；
    (3)将光催化膜置于流动式光催化反应装置中，将反应器固定后，置于日光条件下，将水通入反应器，在出水口获得过氧化氢溶液，其中所述流动式光催化反应装置包括自下而上的底板、水槽、盖板，所述水槽设置有进水口、出水口，所述光催化摸设置于底板和水槽之间。
  2. 根据权利要求1所述的方法，其特征在于，所述步骤(1)具体为：将钒酸铋光催化剂分散在0.5-1.0mM碘酸钠水溶液中，加入相比于钒酸铋光催化剂重量0.2-0.4wt％的硝酸钴，在可见光照射下，将CoOx助催化剂选择性沉积于钒酸铋光催化剂的氧化端位点上；将催化剂洗净回收后，置于清水中，加入相比于催化剂重量0.3-0.6wt％的四氯钯酸钠，在可见光照射下，将Pd助催化剂选择性沉积于钒酸铋光催化剂的还原端位点上。
  3. 根据权利要求2所述的方法，其特征在于，在沉积助催化剂过程中，所有操作均在无氧环境下进行。
  4. 根据权利要求1所述的方法，其特征在于，所述步骤(2)具体为：将100-300mg的钒酸铋光催化剂、1700-2000mg的聚偏氟乙烯和8-10g的二甲基甲酰胺在60-65°的条件下充分搅拌，得到均匀的膜前驱体液；将该膜前驱体液通过离心机在4000-5000rpm的转速下，将气泡排除；用刮膜机在干净的玻璃片上刮出一层均匀的200-300微米厚的膜前驱体液，置于清水中静止，待二甲基甲酰胺溶剂充分扩散挥发，得到光催化膜。
  5. 根据权利要求1所述的方法，其特征在于，在步骤(3)中，通过对所述流动式光催化反应装置中水流的流速进行调节，得到不同浓度的过氧化氢溶液。
PCT/CN2024/093762 2024-05-16 2024-05-16 基于流动式光催化反应的日光下原位合成过氧化氢的方法 Pending WO2025236249A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/CN2024/093762 WO2025236249A1 (zh) 2024-05-16 2024-05-16 基于流动式光催化反应的日光下原位合成过氧化氢的方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2024/093762 WO2025236249A1 (zh) 2024-05-16 2024-05-16 基于流动式光催化反应的日光下原位合成过氧化氢的方法

Publications (1)

Publication Number Publication Date
WO2025236249A1 true WO2025236249A1 (zh) 2025-11-20

Family

ID=97719294

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2024/093762 Pending WO2025236249A1 (zh) 2024-05-16 2024-05-16 基于流动式光催化反应的日光下原位合成过氧化氢的方法

Country Status (1)

Country Link
WO (1) WO2025236249A1 (zh)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1806915A (zh) * 2006-02-23 2006-07-26 上海交通大学 氧化钴负载的钒酸铋复合光催化剂及其制备方法
CN112316936A (zh) * 2020-11-23 2021-02-05 华中科技大学 一种BiVO4界面光催化剂、制备方法及其应用
CN114405506A (zh) * 2022-01-21 2022-04-29 武汉理工大学 一种双金属PdAu助剂选择性修饰钒酸铋光催化剂及其制备方法和应用
CN114405552A (zh) * 2022-02-15 2022-04-29 肇庆学院 一种用于助催化芬顿反应的双功能纤维膜及其制备方法
CN114534665A (zh) * 2022-02-23 2022-05-27 苏州大学张家港工业技术研究院 一种可拓展的流动管式光催化反应装置及方法
CN115025784A (zh) * 2022-06-16 2022-09-09 南京理工大学 一种CoOx/BiVO4纳米片及其制备方法和应用
CN115947383A (zh) * 2022-12-28 2023-04-11 青岛科技大学 氧化钴负载钒酸铋纳米片压电催化剂及其制备方法和应用
KR20240015806A (ko) * 2022-07-27 2024-02-06 주식회사 늘푸른광촉매 비스무트 바나데이트의 소나무 구조에 팔라듐 나노입자가 데코레이션된 설파메톡사졸 광분해용 광촉매 및 그 제조방법

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1806915A (zh) * 2006-02-23 2006-07-26 上海交通大学 氧化钴负载的钒酸铋复合光催化剂及其制备方法
CN112316936A (zh) * 2020-11-23 2021-02-05 华中科技大学 一种BiVO4界面光催化剂、制备方法及其应用
CN114405506A (zh) * 2022-01-21 2022-04-29 武汉理工大学 一种双金属PdAu助剂选择性修饰钒酸铋光催化剂及其制备方法和应用
CN114405552A (zh) * 2022-02-15 2022-04-29 肇庆学院 一种用于助催化芬顿反应的双功能纤维膜及其制备方法
CN114534665A (zh) * 2022-02-23 2022-05-27 苏州大学张家港工业技术研究院 一种可拓展的流动管式光催化反应装置及方法
CN115025784A (zh) * 2022-06-16 2022-09-09 南京理工大学 一种CoOx/BiVO4纳米片及其制备方法和应用
KR20240015806A (ko) * 2022-07-27 2024-02-06 주식회사 늘푸른광촉매 비스무트 바나데이트의 소나무 구조에 팔라듐 나노입자가 데코레이션된 설파메톡사졸 광분해용 광촉매 및 그 제조방법
CN115947383A (zh) * 2022-12-28 2023-04-11 青岛科技大学 氧化钴负载钒酸铋纳米片压电催化剂及其制备方法和应用

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
LIU TIAN, PAN ZHENHUA, VEQUIZO JUNIE JHON M., KATO KOSAKU, WU BINBIN, YAMAKATA AKIRA, KATAYAMA KENJI, CHEN BAOLIANG, CHU CHIHENG, : "Overall photosynthesis of H2O2 by an inorganic semiconductor", NATURE COMMUNICATIONS, NATURE PUBLISHING GROUP, UK, vol. 13, no. 1, UK, XP093373734, ISSN: 2041-1723, DOI: 10.1038/s41467-022-28686-x *

Similar Documents

Publication Publication Date Title
Qi et al. Photocatalytic H2 generation via CoP quantum-dot-modified g-C3N4 synthesized by electroless plating
Ding et al. Hydrogen and potassium acetate co-production from electrochemical reforming of ethanol at ultrathin cobalt sulfide nanosheets on nickel foam
Read et al. Atomic plane-selective deposition of gold nanoparticles on metal oxide crystals exploiting preferential adsorption of additives
Wang et al. Self-supporting triphase photocatalytic CO2 reduction to CH3OH on controllable core–shell structure with tunable interfacial wettability
Bratovčić et al. Design and development of photocatalytic systems for reduction of CO2 into valuable chemicals and fuels
Yang et al. Boosting photocatalytic overall water splitting on direct Z-scheme BiOBr/ZnIn2S4 heterostructure by atomic-level interfacial charge transport modulation
Huang et al. Dual-doping promotes the carbon dioxide electroreduction activity of MoS2 nanosheet array
CN102744087B (zh) 一种片状纳米氯氧化铋薄膜光催化剂的电化学制备方法
Zhang et al. Solar-assisted-self-healing N-doped MXene quantum dots-based membrane with protein resistance for seawater desalination
CN115970765B (zh) 具有3d三相界面的仿生可漂浮光催化材料、制备方法及其在光催化氮还原合成氨中的应用
CN104588040A (zh) 一种光催化剂及其制备方法
CN107602474A (zh) 一种模板法制备具有特定取向的金属有机骨架薄膜的方法
Nandy et al. Effects of Se Incorporation in La5Ti2CuS5O7 by annealing on physical properties and photocatalytic H2 evolution activity
Sun et al. Design of dual Z-scheme heterojunction Ag/AgI@ Bi2O2CO3/3DOM TiO2 composite materials with solar-driven photocatalytic degradation and hydrogen production
CN105836807A (zh) 一种二维薄片自组装多级结构氧化钨及其制备方法和应用
CN117101729A (zh) 一种用于污水治理的光催化复合改性均相液的制备方法
Raza et al. Engineered 2D metal oxides for photocatalysis as environmental remediation: a theoretical perspective
Wang et al. Recent developments in immobilized photocatalyst for hydrogen production
Wang et al. Bioinspired material for high-performance photocatalytic systems
Qureshy et al. Experimental investigation of a new photoelectrochemical cell design featuring a unique photocathode configuration for solar hydrogen production
Peng et al. Grain-boundary-enriched copper electrocatalysts for efficient carbon dioxide reduction to multi-carbon products
Xu et al. Effect of the proton transfer pathway on selective photoreforming of lignin models for target products enabled by sulfur vacancy engineering on chalcogenide nanosheets
CN113856760A (zh) 一种MOF-NO2限域下的TiO2纳米复合光催化剂及其制备方法
CN110699704B (zh) 一种自支撑型硫化银催化二氧化碳还原电极材料的制备方法、产品及应用
CN118513086B (zh) 一种光热-热释电-光催化复合薄膜催化剂体系及其制备方法和应用

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 24938273

Country of ref document: EP

Kind code of ref document: A1