Study on VOCs/ synergistic treatment process based on adsorption/ in-situ catalytic oxidation 基于吸附/原位催化氧化的挥发性有机化合物/ 协同处理工艺研究
Jiahao Cheng , Xiaoqing Sun , Xingxing Cheng , Zhiqiang Wang Jiahao Cheng , Xiaoqing Sun , Xingxing Cheng , Zhiqiang Wang a School of Energy and Power Engineering, Shandong University, Jinan 250061, China a 山东大学能源与动力工程学院，中国济南 250061 National Engineering Laboratory for Reducing Emissions from Coal Combustion, Jinan 250061, China 燃煤减排国家工程实验室，中国济南 250061
A B S T R A C T The mechanism of synergistic treatment of VOCs and is poorly understood, it urgently needed to study the co-adsorption/in-situ catalytic oxidation mechanism. In this study, we proposed an integrated VOCs/ treatment (i-VNT) process for the adsorption/in-situ catalytic of using metal doped . The results showed that the adsorption capacity on different adsorbents in co-adsorption process appeared different degrees of reduction, especially the maximum reduction for is of , respectively. The "inhibition zone" existed in the synergistic catalytic process in as the competition for reactive oxygen species, while in , the avoided the excessive oxidation of . Finally, the adsorption intermediates, changes of surface functional groups and reaction mechanism were clarified using in situ FTIR in real time. This current research offered efficient and stable catalysts for the co-adsorption/in-situ catalytic oxidation destruction, and provided a promising strategy for the next step in the synergistic treatment of multiple pollutants in open application scenarios A B S T R A C T VOCs 和 的协同处理机理尚不清楚，迫切需要研究共吸附/原位催化氧化机理。在这项研究中，我们利用掺杂金属的 ，提出了一种吸附/原位催化 的 VOCs/ 综合处理（i-VNT）工艺。结果表明，在共吸附过程中，不同吸附剂上的吸附容量出现了不同程度的还原，尤其是 的最大还原量分别为 。在协同催化过程中， 存在 "抑制区"，作为活性氧的竞争区，而在 中， 则避免了 的过度氧化。最后，利用原位傅立叶变换红外光谱实时阐明了吸附中间产物、表面官能团的变化和反应机理。目前的研究为共吸附/原位催化氧化破坏提供了高效稳定的催化剂，并为下一步在开放应用场景中协同处理多种污染物提供了可行的策略。
1. Introduction 1.导言
Both volatile organic compounds (VOCs) and ammonia are common pollutants in the industry, with wide emissions from chemical factories, catalyst preparation, material fabrication, agricultural activities, and coal-fired sources etc. [1,2]. In the study by Amon et al. [3], emissions of and from a commercial straw flow system for fattening pigs in Upper Austria were and per pig place per year without daily manure removal. In addition, the downstream industries related to agriculture, such as rendering and dairy industry, production operations emit a significant, but as yet poorly quantified, VOC load [4]. The release of VOCs and into the open space can lead to noticeable odors and potential damage of health, such as stratospheric ozone depletion, irritation to human organ, etc. [5,6,7]. There is a great demand for the treatment of VOCs and in both indoor working spaces and open areas. 挥发性有机化合物（VOCs）和氨 是工业中常见的污染物，广泛排放于化工厂、催化剂制备、材料制造、农业活动和燃煤源等。[1,2].在 Amon 等人的研究中[3]，在不每天清除粪便的情况下，上奥地利育肥猪商业秸秆流系统每年每头猪排放的 和 分别为 和 。此外，与农业相关的下游产业，如熏蒸和乳制品工业，在生产过程中也会排放大量的挥发性有机化合物，但目前尚未对其进行量化[4]。挥发性有机化合物和 释放到开放空间会产生明显的气味和潜在的健康损害，如平流层臭氧损耗、对人体器官的刺激等[5,6,7]。[5,6,7].对室内工作空间和露天场所的挥发性有机化合物和 的处理需求很大。
VOCs have garnered significant attention due to stringent environment regulations . Many different methods, such as adsorption, condensation and selective catalytic reduction, have been extensively and widely employed in their mitigation [10]. Among these methods, a widely used one to abate VOCs is adsorption-catalytic oxidation [11]. 由于严格的环境法规 ，挥发性有机化合物引起了人们的极大关注。许多不同的方法，如吸附法、冷凝法和选择性催化还原法，已被广泛应用于减少挥发性有机化合物[10]。在这些方法中，吸附-催化氧化法是一种被广泛使用的减少挥发性有机化合物的方法[11]。
The adsorbent could be activated carbon or zeolites, while the catalysts typically consist of noble metals [12]. For instance, Hou et al., [13] used glycine modification to enhance the nitrogen-containing functional groups on the surface of activated carbon, resulting in an increased toluene adsorption capacity of . However, activated carbon's poor structural stability led Liu et al., [14] to used mesoporecoated zeolites to prepare molecular sieves with a core-shell structure, thus improving the adsorbents' hydrophobicity and masstransfer properties. Kim et al., [15] also improved the adsorbent's hydrophobicity and mass-transfer performance by creating an open-pore structure zeolite to accelerate the adsorbent's mass transfer capabilities. 吸附剂可以是活性炭或沸石，而催化剂通常由贵金属组成 [12]。例如，Hou 等人[13] 利用甘氨酸改性来增强活性炭表面的含氮官能团，从而将甲苯的吸附容量提高到 。然而，由于活性炭的结构稳定性较差，Liu 等人[14] 利用介孔涂层 沸石制备了具有核壳结构的分子筛，从而改善了吸附剂的疏水性和吸附性能。Kim 等人，[15] 还通过创造一种开孔结构的沸石来提高吸附剂的疏水性和传质性能，从而加速吸附剂的传质能力。
However, the control of has not received much attention at present due to fewer regulations being issued. Few treatment investigations have focused on adsorption, biological purification and catalytic decomposition. One ideal technology that can be applied is the selective oxidation of [16,17]. Common active components in catalysts include , and . For example, the catalyst prepared by Lee et al., [18] exhibits a high oxygen storage capacity and a large number of oxygen vacancies due to the high dispersion of , which improves the catalytic activity and selectivity. Qu et al., [19] loaded Ag on different carriers and found that Ag particles 然而，由于颁布的法规较少，目前对 的控制还没有引起足够的重视。很少有 处理研究集中在吸附、生物净化和催化分解方面。一种可以应用的理想技术是对 进行选择性氧化[16,17]。 催化剂中常见的活性成分包括 和 。例如，Lee 等人制备的 催化剂，[18] 由于 的高分散性，表现出较高的储氧能力和大量的氧空位，从而提高了催化活性和 的选择性。Qu 等人，[19] 在不同的载体上负载 Ag，发现 Ag 颗粒
Received 13 December 2023; Received in revised form 17 January 2024; Accepted 25 January 2024 2023 年 12 月 13 日收到；2024 年 1 月 17 日收到修订稿；2024 年 1 月 25 日接受
Fig. 1. Schematic diagram of synergistic degradation of VOCs by adsorption/in-situ catalytic oxidation. 图 1.通过吸附/原位催化氧化协同降解 VOCs 的示意图 。
on carriers were smaller in size and more dispersed and had good low temperature characteristics selectivity at . 载体上的粒度更小、更分散，具有良好的低温特性 选择性， 。
It is interesting that can also be adsorbed onto many absorbents and catalytically oxidized into harmless via . Although the exact reaction mechanisms are not clear, mainstream research suggests that they may all follow the Eley-Rideal mechanism. Therefore, it would be of great interest if could be eliminated simultaneously with VOCs in the same reaction using the same absorbents/catalysts. Competition between the two for active sites as well as reactive oxygen species is bound to occur during the reaction, however, to the best of our knowledge, no prior research has been reported on the catalyst for simultaneous removal of VOCs and . Therefore, it urgently needed to study the co-adsorption/in-situ catalytic oxidation mechanism, and in this work, we aim to develop catalysts for these dual purposes. 有趣的是， 也可以吸附在许多吸收剂上，并通过 催化氧化成无害的 。虽然确切的反应机制尚不清楚，但主流研究表明，它们可能都遵循 Eley-Rideal 机制。因此，如果能使用相同的吸收剂/催化剂，在相同的反应中同时消除 和挥发性有机化合物，将是非常有意义的。在反应过程中，二者对活性位点和活性氧的竞争必然会发生，然而，据我们所知，之前还没有关于同时去除 VOCs 和 的催化剂的研究报告。因此，迫切需要对共吸附/原位催化氧化机理进行研究，在这项工作中，我们的目标是开发出具有上述双重用途的催化剂。
To make this VOCs/ abatement process more convenient and suitable for factories and workshops, an integrated VOCs/ treatment (i-VNT) process of synergistic adsorption-oxidation was further proposed, as depicted in Fig. 1. This process integrates both VOCs adsorption-oxidation processes, as well as adsorption-oxidation processes, into one reactor using only one kind of catalyst which serves as both the VOCs adsorbent and the VOCs oxidation catalyst. During the adsorption phase, ventilation is working and the surrounding air at room temperature is introduced into the reactor, where VOCs are adsorbed onto the catalyst. Once the catalyst becomes saturated, ventilation is halted, and the catalyst is heated within a sealed environment. VOCs and are then catalytically oxidized at an elevated temperature. The simultaneous removal of VOCs and , coupled with the integrated adsorption and oxidation processes, allows for a compact and easily deployable reactor suitable for various locations within factory premises, including both indoor workshops and open areas. This approach holds great promise for significantly improving air quality in industrial settings. 为了使这种 VOCs/ 减排工艺更方便、更适用于工厂和车间，进一步提出了一种 VOCs/ 协同吸附-氧化综合处理（i-VNT）工艺，如图 1 所示。该工艺将 VOCs 吸附-氧化过程和 吸附-氧化过程整合到一个反应器中，只使用一种催化剂，这种催化剂既是 VOCs 吸附剂，又是 VOCs 氧化催化剂。在吸附阶段，通风设备开始工作，室温下的周围空气被引入反应器，VOCs 被吸附在催化剂上。催化剂饱和后，通风停止，催化剂在密封环境中加热。然后，VOC 和 在高温下进行催化氧化。同时去除挥发性有机化合物和 ，再加上一体化的吸附和氧化过程，使得反应器结构紧凑，易于部署，适用于工厂内的各种场所，包括室内车间和开放区域。这种方法有望显著改善工业环境中的空气质量。
The objective of this work is to develop catalysts that could serve both as VOCs/ absorbents and VOCs/ oxidation catalysts. Pxylene will be used as a model VOCs molecule. Transition metal particles doped on will be synthesized, owing to their reported excellent VOCs and adsorption capabilities [20,21]. Various metal oxides and ), which are cost-effective and known to provide ample oxidation sites , will be impregnated onto the support to serve as oxidation catalysts. The developed catalysts will then be applied in the proposed i-VNT process to assess their performance under various conditions. The reaction mechanism of this process will also be explored. 这项工作的目的是开发既可用作 VOCs/ 吸收剂又可用作 VOCs/ 氧化催化剂的催化剂。对二甲苯将被用作 VOCs 分子模型。由于 上掺杂的过渡金属颗粒具有出色的 VOCs 和 吸附能力，因此将在 上合成过渡金属颗粒 [20,21]。各种金属氧化物 和 ）将被浸渍到载体上，作为氧化催化剂，这些金属氧化物具有成本效益，而且已知可提供充足的氧化位点 。开发的催化剂随后将应用于拟议的 i-VNT 工艺，以评估其在各种条件下的性能。此外，还将探索该工艺的反应机理。
2. Experimental 2.实验
2.1. Catalyst preparation 2.1.催化剂制备
Metal doped catalysts were prepared using impregnation techniques. Specifically, , and ( , Macklin) were completely dissolved in deionized water as precursor salts and added to the powered . The total amount of metal doped was controlled at (if bimetallic co-doped was performed, the molar ratio was 1:1). Subsequently, the catalysts were placed in a water bath at and heated while being stirred to evaporate the surface water. Afterwards, they were transferred to a drying oven at for and finally placed in a muffle furnace at for . The prepared catalysts were labeled as , respectively. 掺杂金属的催化剂采用浸渍技术制备。具体来说， , 和 ( , Macklin) 作为前驱盐完全溶解在去离子水中，然后加入到通电的 中。掺杂金属的总量控制在 （如果进行双金属共掺杂，摩尔比为 1:1）。随后，将催化剂放入 的水浴中，边搅拌边加热，以蒸发表面水分。之后，将催化剂转移到 的干燥箱中进行 ，最后放入 的马弗炉中进行 。制备的催化剂分别标记为 , 。
2.2. Activity test 2.2.活动测试
All the catalyst adsorption and regeneration tests were conducted in a fixed bed reactor system comprising a VOCs generation system, gas distribution system, fixed-bed reactor and gas analysis system. 所有催化剂吸附和再生试验都是在固定床反应器系统中进行的，该系统包括 VOCs 生成系统、气体分配系统、固定床反应器和气体分析系统。
(c)
(d)
Fig. 2. (a) The curves of adsorbed amount versus time of single adsorption and combined adsorption at , , and ; (b) The curves of adsorbed amount versus time of single adsorption and combined adsorption at , and ; (c) Breakthrough curves of , and combined adsorption; (d) Comparison of adsorption capacity of different adsorbents at different temperatures. (Conditions: of adsorbents, , as balanced gas, and total gas flow ). 图 2. (a) 在 、 和 的单一吸附和组合吸附的吸附量随时间的变化曲线；(b) 在 和 的单一吸附和组合吸附的吸附量随时间的变化曲线；(c) 、 和组合吸附的突破曲线；(d) 不同吸附剂在不同温度下的吸附容量比较。(条件：吸附剂为 ， ， 为平衡气体，气体总流量为 ）。
Schematic diagrams of the setup can be found in the Fig. S. 1 in Supplementary Material. In each experiment, the adsorbent was placed into a quartz column with an inner diameter of , and the temperature was controlled using a furnace. To simulate an actual open site, air was chosen as the carrier gas, and the feed components (liquid o-xylene) rate was controlled using a syringe dosing pump (LSP01-1A) into the vaporization chamber, where the temperature was maintained at , significantly higher than the boiling point of solvent. The experiments were carried out with a concentration of of (oxylene), of , and a temperature of 200 to . The degraded gaseous components, including and , were analyzed in a real-time using a gas analyzer (PV6001-VOC-EX, Hunan Rike, China), a gas chromatograph (G901A, Huifen Instruments, China) and Fourier Infrared Spectroscopy (FT-IR). 实验装置示意图见补充材料中的图 S. 1。在每次实验中，都将吸附剂放入内径为 的石英柱中，并使用熔炉控制温度。为模拟实际的露天场所，选择空气作为载气，并使用注射器定量泵（LSP01-1A）控制进入汽化室的进料组分（液态邻二甲苯）的速率，汽化室的温度保持在 ，明显高于溶剂的沸点。实验的浓度为 of （二甲苯）， of ，温度为 200 至 。使用气体分析仪（PV6001-VOC-EX，中国湖南日科）、气相色谱仪（G901A，中国汇文仪器）和傅立叶红外光谱仪（FT-IR）对降解的气体成分（包括 和 ）进行实时分析。
2.3. Adsorbent characterization 2.3.吸附剂特征
The specific surface area and total pore volume were determined by adsorption-desorption at using specific surface analyzer (Quanta chrome Autosorb 1C, USA, and V-Sorb 4800P, CIQTEK, China) on granular samples that had been degassed at for . The modified adsorbents were characterized using a programmed chemisorption instrument (PCA-1200), and the outlet gas signals from the micro fixed bed reactor were detected by a thermal conductivity detector (TCD). Temperature programmed desorption (TPD) were performed to investigate desorption properties. All the tests were carried out at a gas flow rate of . The saturated catalyst was initially purged with for at room temperature and then heated up to at a rate of . Hydrogen temperature programmed reduction ( -TPR) was characterized for the investigation of oxidizing properties. The fresh catalysts were first purged with at for to remove surface water, cooled to , and then exposed to a / He reducing gas and heated to at a rate of . Oxygen temperature programmed oxidation ( ) were investigated to analyze the oxidizing process during the regeneration phase. The adsorbed saturated catalyst was oxidized under atmosphere, and the process was heated to at a rate of to observe the signal values at different temperatures. and -TPR were carried out on the setup in Section 2.2. After saturating the pretreated samples with adsorbent, the temperature was increased to 800 at a rate of , and the concentration of was simultaneously detected and recorded by a detector. 使用比表面分析仪（Quanta chrome Autosorb 1C，美国；V-Sorb 4800P，CIQTEK，中国）对在 进行脱气处理的粒状样品在 进行吸附-解吸，测定其比表面积 和总孔容积 。使用程序化学吸附仪（PCA-1200）对改性吸附剂进行表征，并使用热导检测器（TCD）检测微型固定床反应器的出口气体信号。为了研究解吸特性，还进行了温度编程解吸（TPD）试验。所有测试都是在 的气体流速下进行的。饱和催化剂最初在室温下用 对 进行吹扫，然后以 的速率加热至 。氢气温度编程还原 ( -TPR)被用于研究氧化特性。新鲜催化剂首先在 用 冲洗 以去除表面水分，冷却至 ，然后接触 / He 还原气体并以 的速率加热至 。氧温程控氧化 ( ) 研究分析了再生阶段的氧化过程。吸附饱和的催化剂在 的气氛下进行氧化，并以 的速率加热到 ，以观察不同温度下的信号值。 和 -TPR 是在第 2.2 节的装置上进行的。在吸附剂饱和预处理样品后，以 的速率将温度升至 800 ，同时用检测器检测并记录 的浓度。
To investigate the structure and composition of the crystalline phase of the adsorbent, X-ray diffraction (XRD) patterns were obtained using Rigaku Smart Lab X-ray diffractometer in the range of with the scanning speed of . X-ray photoelectron spectra (XPS) were detected on an ESCALAB 250xi equipped with an AI excitation source, in which the binding energy was scanned over a range of 0 to with the scanning step is . To compare the oxidation of in different flow rates, the Fourier Transform Infrared (FT-IR) with an accuracy of were used for real-time detection of , and . In situ FT-IR was employed to study the changes of chemical functional groups on the catalyst's surface under the two modes of ventilation regeneration and enclosed regeneration. In situ diffuse reflectance spectra at wavelengths of were recorded. The samples were initially raised from room temperature to 为了研究吸附剂晶相的结构和组成，使用 Rigaku Smart Lab X 射线衍射仪获得了 X 射线衍射（XRD）图样，扫描范围为 ，扫描速度为 。X 射线光电子能谱（XPS）是在配有 AI 激发源的 ESCALAB 250xi 上检测的，其中结合能的扫描范围为 0 至 ，扫描步长为 。为了比较 在不同流速下的氧化情况，使用精度为 的傅立叶变换红外（FT-IR）对 和 进行实时检测。原位傅立叶变换红外光谱用于研究通风再生和封闭再生两种模式下催化剂表面化学官能团的变化。原位漫反射光谱的波长为 。样品最初从室温升至
Fig. 3. Characteristics of synergistic catalytic oxidation of metallic supported : (a) Synergistic catalytic oxidation characteristics on ; (b) 图 3. 金属支撑的 的协同催化氧化特性：（a） 的协同催化氧化特性；（b） 的协同催化氧化特性。
characteristics on . (Conditions: of adsorbents, balance and total gas flow ). 上的特性。（条件：吸附剂 、 平衡和气体总流量 ）。
, and the backgrounds were collected at different temperatures and then cooled to room temperature. Subsequently, the configured experimental gas configuration (total flow rate equilibrium gas) was passed through the sample, and the spectra were collected under different experimental conditions. 在不同温度下采集背景光谱，然后冷却至室温。随后，将配置好的实验气体（总流量 平衡气体）通过样品，并在不同的实验条件下采集光谱。
3. Results and discussion 3.结果和讨论
3.1. Adsorption and catalytic performance 3.1.吸附和催化性能
3.1.1. Performance of co-adsorption 3.1.1. 共吸附的性能
The adsorption experiments of , and the combined and on metal doped at , and were investigated, and the curves of the adsorption amounts versus time of were shown in Fig. 2 (a) and Fig. 2 (b). Temperature showed a significant effect on the adsorption capacity, especially for , that was in virtue of the lower boiling point and molecular polarity, resulting in weaker intermolecular forces with the adsorbent. At the initial stage of adsorption, the effect of temperature was not obvious, and the three curves nearly overlapped. Although, the increase of temperature accelerated the migration rate of molecules to the support's surface, it inhibited the adsorption rate of adsorbent, resulting in the decrease of adsorption amount. In the process of the single adsorption process, the adsorption amounts curves showed a similar tendency, with nearly saturated after , while reached an adsorption limit at 50 min. Interestingly, the first stabilization time in the combined adsorption process was also around , denoting that co-adsorption cause little effect on adsorption, it can be said that the material was the first to lose its ability to adsorb , but can still continue to adsorb . By contrast, co-adsorption showed a clear impact on the adsorption of , the most intuitive feature on Fig. 2 (c) was the appearance of a "transiently stable plane" at the dimensionless concentration of 0.12 after and kept for , then rapidly increased to the initial concentration, corresponding to a decrease of adsorbed amount of . Because of that, the adsorption rate changed obviously, corresponding to the significant change in the slope of the curve in the enlarged picture in Fig. 2 (b). The almost similar adsorption breakthrough time indicated the little interference with the adsorption of large molecules of and small molecules of on the adsorbents. It was also presumed that and occupy different sites during adsorption. 研究了 以及 和 对掺杂金属的 在 和 的吸附实验， 的吸附量随时间的变化曲线如图 2 (a) 和图 2 (b) 所示。温度对吸附量的影响很大，尤其是对 而言，这是因为 的沸点较低，分子极性较强，与吸附剂的分子间作用力较弱。在吸附初期，温度的影响并不明显，三条曲线几乎重合。温度的升高虽然加快了分子向载体表面迁移的速率，但却抑制了吸附剂的吸附速率，导致吸附量减少。在单次吸附过程中，吸附量曲线表现出相似的趋势， ，在 后接近饱和，而 在 50 分钟时达到吸附极限。有趣的是，联合吸附过程中的首次稳定时间也在 左右，说明联合吸附对 的吸附影响不大，可以说该材料最先失去了吸附 的能力，但仍能继续吸附 。相比之下，共吸附对 的吸附有明显的影响，图 2（c）中最直观的特征是 后，在无量纲浓度为 0.12 时出现一个 "瞬时稳定平面"，并保持到 ，然后迅速增加到初始浓度，这与 的吸附量减少相对应。因此，吸附速率发生了明显变化，这与图 2（b）放大图中曲线斜率的显著变化相对应。几乎相近的吸附突破时间表明，大分子 和小分子 在吸附剂上的吸附干扰很小。此外，还推测 和 在吸附过程中占据了不同的位点。
The final adsorption capacities of the single substance adsorption and synergistic adsorption process of the three adsorbents are depicted in Fig. 2 (d). The adsorption capacities of several adsorbents are approximately the same, which is due to the similar molecular diameters of the loaded and ions, enabling to form mutual solvents with each other. Overall, demonstrated the best adsorption performance. As the adsorption temperature increases, a decrease in the adsorption capacity occurs. In the case of , for example, the synergistic adsorption induced a decrease in the adsorption of and a decrease in the adsorption of . This is due to the fact that the activation energies of adsorption of and on carriers were , respectively, which suggests that the adsorption of is more likely to occur. More detailed calculations and graphs can be found in Fig. S. 2 in Supplementary Material. 图 2（d）显示了三种吸附剂的单一物质吸附和协同吸附过程的最终吸附容量。几种吸附剂的吸附容量大致相同，这是因为所吸附的 和 离子的分子直径相近，可以相互形成溶剂。总体而言， 的吸附性能最好。随着吸附温度的升高，吸附容量会下降。以 为例，协同吸附导致 的吸附量下降， 的吸附量下降， 的吸附量下降， 的吸附量下降。这是由于 和 在 载体上的吸附活化能分别为 ，这表明 的吸附更有可能发生。更详细的计算和图表见补充材料中的图 S. 2。
3.1.2. Synergistic catalytic oxidation properties of 3.1.2.3.1.2.
Metal-doping was chosen to reduce the required cooling time owing to a lower required catalytic reduction temperature. The concerted catalytic oxidation characteristic curve of metal doped was displayed in Fig. 3. In Fig. 3 (a), the selective of decreased with 选择掺杂金属是为了降低催化还原温度，从而减少所需的冷却时间。 掺杂金属的 的协同催化氧化特性曲线如图 3 所示。在图 3 (a)中， 的选择性随着温度的升高而降低。
Fig. 4. In-situ catalytic oxidation characteristic under different regeneration gas flow. 图 4.不同再生气体流量下的原位催化氧化特性。
the increase of temperature. Below , little bit NO and nearly no were generated in the products, while temperature reached to 300 , the concentration began to jump. In addition, in the range of , with the increase in temperature, there was a trend that the TVOC concentration remained unchanged or slightly increased, but a small amount of and in the by-product was detected, which meant that was involved in the oxidation reaction. Therefore, it was speculated that competes with for active oxygen species and inhibited the degrade reaction of , resulting in a decrease in the total reaction rate. Afterwards, the competition between and was not obvious after because the reactive oxygen content in the system increased to a sufficient content that both of them can participate in the oxidation reaction, resulting in the increase of the total conversion rate . The reaction mechanism can be further investigated by FT-IR characterization. Whilst Fig. 3 (b) and Fig. 3 (c) showed a similar curve profile of total VOC (TVOC), , that is, the degrade efficiency of TVOC trended to decrease first and then increase, indicating the inhibitory effect on . In contrast, can achieve complete catalysis at , verifying that and Mn bimetallic doping helped to improve the catalytic activity of the material. Nevertheless, the enhanced oxidation performance leaded to excessive oxidation of , meanwhile, the and concentrations were 107 and , respectively, with a poor selectivity. Either, the catalytic activity of did not improve significantly and the selectivity decreased substantially, with and concentrations of 378 and at , respectively. All the results demonstrated the poor beneficial effect on synergistic catalytic of bimetallic doping. Therefore, was optimized as the active component in virtue of the lower completed conversion temperature and higher selectivity, which had a significant selectivity of at . 温度升高。在 以下，产品中产生少量 NO，几乎没有 ，而温度达到 300 时， 浓度开始跃升。此外，在 的范围内，随着温度的升高，TVOC 的浓度有保持不变或略有升高的趋势，但在副产品中检测到了少量的 和 ，这意味着 参与了氧化反应。因此，推测 与 竞争活性氧，抑制了 的降解反应，导致总反应速率下降。之后， 之后， 和 之间的竞争并不明显，因为体系中的活性氧含量增加到足够多，两者都能参与氧化反应，导致总转化率增加 。反应机理可通过傅立叶变换红外特性进一步研究。图 3 (b) 和图 3 (c) 显示了总挥发性有机化合物（TVOC）的相似曲线轮廓， ，即 TVOC 的降解效率呈先降低后升高的趋势，这表明了 的抑制作用。相比之下， ， ，验证了 和锰双金属掺杂有助于提高材料的催化活性。然而，氧化性能的提高导致了 的过度氧化，同时， 和 的浓度分别为 107 和 ，选择性较差。另外， 的催化活性也没有显著提高，选择性大幅降低， 和 的浓度分别为 378 和 ， 。所有这些结果都表明，双金属掺杂对协同催化的有利影响很小。因此，凭借较低的完成转化温度和较高的 选择性，对 作为活性组分进行了优化， ，其 选择性明显高于 。
In order to compare the interaction between and during the synergistic catalytic oxidation reaction, single-substance catalysis experiments were investigated on and results were shown in Fig. 3 (d). The catalysts for oxidation occurred at around and catalytic efficiency reached to at , subsequently, the concentrations of by-products increased dramatically with the increase of temperature, especially for . Although could be completely degraded at , according to the -balance, the selectivity was , so the optimized temperature for catalyzed was still . By contrast, the 's catalytic oxidation required a higher temperature, with a catalytic efficiency of only at and complete degradation at . Due to the inconsistent react temperature window, it appeared that a contradiction between the selectivity and conversion rate in the synergistic catalytic oxidation process according to the C-balance. Both and can achieve complete degradation below when single-catalysis, while in the synergistic catalytic oxidation, complete conversion temperature ( ) shifted to , proving the compete for the reactive oxygen species. In the range of reacted with the reactive oxygen species in preference and the inhibition effect appeared but disappeared only after . On the other hand, in Fig. 3 (a), the generation temperatures of and at synergistic catalytic oxidation were 245 and , respectively, which were higher than those at single catalysis, indicating that could avoid excessive oxidation of , which was conducive to improving selectivity. 为了比较 和 在协同催化氧化反应过程中的相互作用，对 进行了单物质催化实验研究，结果如图 3 (d)所示。 的催化氧化发生在 左右，在 时催化效率达到 ，随后，随着温度的升高，副产物的浓度急剧增加，尤其是 。虽然 在 时可以完全降解，但根据 - 平衡， 的选择性为 ，因此 催化的最佳温度仍为 。相比之下， 的催化氧化需要更高的温度，在 时催化效率仅为 ，而在 时可完全降解。由于反应温度窗口不一致，根据 C 平衡，协同催化氧化过程中的选择性和转化率之间出现了矛盾。单催化时， 和 都能在 以下实现完全降解，而在协同催化氧化过程中，完全转化温度（ ）转移到了 ，证明了活性氧的竞争。在 的范围内，优先与活性氧发生反应，抑制作用出现，但在 之后才消失。另一方面，在图 3 (a) 中，协同催化氧化时 和 的生成温度分别为 245 和 ，高于单一催化时的生成温度，说明 可以避免 的过度氧化，有利于提高 的选择性。
3.2. Performance of process 3.2. 流程的性能
3.2.1. Effect on regeneration gas parameters 3.2.1.对再生气体参数的影响
3.2.1.1. Gas flow analysis. The reaction processes were evaluated by testing the concentrations of and at the reactor outlet under regeneration gas flow rates of and , and the results are depicted in Fig. 4 (a-d). It can be 3.2.1.1.气体流量分析。在 和 的再生气体流速下，通过测试反应器出口处 和 的浓度来评估反应过程，结果如图 4（a-d）所示。可以看出
Fig. 5. In-situ catalytic oxidation characteristic under different oxygen content. 图 5.不同氧含量下的原位催化氧化特性。
observed that the slope of the concentration curve in the three groups of experiments is steeper than the slope of the concentration curve, and the inflection point occurs earlier. This is because when the regeneration gas is first introduced, due to the enrichment effect during the adsorption stage is present at a high concentration level, while the concentration of is relatively insufficient, leading to the incomplete oxidation of into . With the continuous supply of the regeneration gas, the in the system becomes sufficient for a complete reaction. As a result, the concentration gradually decreases, while begins to rise. The significant change in concentration in the initial stage indicates that it is primarily leaving the system in the form of desorption at this time and is not participating in the catalytic reaction. 观察到三组实验中 浓度曲线的斜率比 浓度曲线的斜率陡峭，且拐点出现较早。这是因为刚开始引入再生气体时，由于吸附阶段的富集效应， 的浓度水平较高，而 的浓度相对不足，导致 未完全氧化成 。随着再生气体的持续供应，系统中的 变得足以完全反应。因此， 的浓度逐渐下降，而 开始上升。初始阶段 浓度的显著变化表明，此时它主要以解吸附的形式离开系统，并没有参与催化反应。
At a flow rate of , the concentration increased without any inflection point, and the concentration increased as well. When the gas flow rate was increased to , it was observed that both and concentrations underwent a process of increasing and then decreasing, with the turning points occurring at approximately and , respectively. When the flow rate reached exhibited a decreasing trend around , and the regeneration process could be completed in with aeration. This indicates that increasing the flow rate can facilitate the rapid removal of reaction products from the catalyst, shorten the regeneration stage time, and thus improve cycle efficiency. However, excessively high space velocity reduces the contact time between air and , hindering deep catalysis, causing physical-adsorbed toluene to escape, and leading to the formation of more by-product CO. Therefore, a gas flow rate of is considered a reasonable choice for the regeneration process. 当流速为 时， 浓度增加，但没有出现拐点， 浓度也有所增加。当气体流速增加到 时，发现 和 的浓度都经历了一个先增加后减少的过程，转折点分别出现在 和 附近。当流速达到 时，在 附近呈现下降趋势，再生过程可在 通过曝气完成。这表明，提高流速可以促进催化剂中反应产物的快速清除，缩短再生阶段的时间，从而提高循环效率。但是，过高的空间流速会减少空气与 的接触时间，阻碍催化剂的深度催化，导致物理吸附的甲苯逸出，并形成更多的副产物 CO。因此，在再生过程中，合理的气体流速为 。
3.2.1.2. Oxygen content analysis. To control the total flow of regeneration gas with the same catalyst filling amount, the concentration of was regulated by changing the volume ratio of air and . Four concentration conditions, namely , and , were selected. The results are shown in Fig. 5 (a-b). When the regeneration gas was initially introduced, the concentrations of and increased dramatically, with a subsequent rise and fall process as the reaction progressed. The curve's slope at oxygen concentration was the steepest, resulting in the fastest reaction rate, followed by the concentration. In contrast, the reaction under the oxygen concentration condition exhibited a flatter progress, and the amounts of generated products was lower. Although the concentration curve showed a higher peak at concentration, the overall product yield was lower compared to the case with oxygen concentration. Therefore, an increase in oxygen concentration improves and selectivity and reduces the generation of by-products. 3.2.1.2.氧含量分析。为了控制相同催化剂装填量下再生气体的总流量，通过改变空气和 的体积比来调节 的浓度。选择了四种浓度条件，即 、和 。结果如图 5（a-b）所示。最初引入再生气体时， 和 的浓度急剧上升，随后随着反应的进行，浓度呈上升和下降过程。 氧浓度下的曲线斜率最陡，反应速度最快，其次是 浓度下。相比之下，在 氧浓度条件下的反应过程较为平缓，生成物的数量也较少。虽然 浓度曲线在 浓度时出现了一个较高的峰值，但与 氧浓度的情况相比，总体产物产量较低。因此，增加氧气浓度可以提高 和 的选择性，减少副产物的生成。
3.2.1.3. Regeneration temperature analysis. Four temperatures, namely , and , were selected near . The in-situ catalytic oxidation characteristics at different regeneration temperatures are shown in Fig. 6 (a-b). A comparison of the four temperatures revealed that at , the and concentration curve slopes were the steepest, indicating the fastest catalytic reaction rate under those working conditions. When the regeneration temperature 3.2.1.3.再生温度分析。在 附近选择了四个温度，即 和 。不同再生温度下的原位催化氧化特性如图 6（a-b）所示。对四个温度进行比较后发现，在 时， 和 的浓度曲线斜率最大，表明在该工作条件下催化反应速率最快。当再生温度
Fig. 6. In-situ catalytic oxidation characteristic under different regeneration temperature. 图 6.不同再生温度下的原位催化氧化特性。
was lower than the material's , very little and were generated, and the pollutants could only desorb from the material's surface, without reaching deep treatment. At and , the time required for complete degradation was and , respectively, demonstrating that increasing the regeneration temperature can shorten the in-situ catalytic oxidation reaction time, which is conducive to rapid cycling. However, practical applications need to consider the energy consumption issue comprehensively. 当再生温度低于材料的 时，产生的 和 非常少，污染物只能从材料表面解吸，无法进入深层处理。在 和 时，完全降解所需的时间分别为 和 ，这说明提高再生温度可以缩短原位催化氧化反应时间，有利于快速循环。然而，实际应用需要综合考虑能耗问题。
3.2.2. Characteristic of regeneration performance 3.2.2.再生性能特点
Regeneration tests are essential for assessing the durability of the material. Two types of regeneration experiments, aeration regeneration and enclosed regeneration experiments, were performed. Fig. S. 3 showed the synergistic removal of by adsorption/in-situ catalytic oxidation of in an aeration environment. The adsorption breakthrough times were found to be 52,51 and 50 min for the three adsorption breakthrough times, respectively. This indicates that the material's adsorption performance does not deteriorate after insitu catalytic oxidation. However, a key issue is that an enrichment peak with a dimensionless concentration of appears at the initial stage of desorption. Such a high enrichment concentration is not suitable for direct emission. Therefore, a novel enclosed regeneration approach is proposed in this paper. 再生试验对于评估材料的耐久性至关重要。我们进行了两种类型的再生实验，即曝气再生实验和封闭再生实验。图 3 显示了 在曝气环境中通过吸附/原位催化氧化协同去除 的情况。在三种吸附突破时间中， 的吸附突破时间分别为 52、51 和 50 分钟。这表明材料的吸附性能在原位催化氧化后并没有恶化。然而，一个关键问题是，在解吸的初始阶段出现了一个富集峰，其无量纲浓度为 。如此高的富集浓度不适合直接排放。因此，本文提出了一种新型封闭再生方法。
The enclosed regeneration test was conducted under the same experimental conditions. The difference is that after the saturated adsorption, a high concentration of oxygen was introduced into the reactor. Subsequently, the upper and lower valves of the reactor were closed to create a confined space, and the temperature was then increased to achieve regeneration. The results are presented in Fig. 7. The confined space allows the detached substances to remain and react with the high-concentration oxygen for an extended period. After two cycles, the breakthrough times decreased to for and 40 min for , indicating the incomplete regeneration of the catalysts. Therefore, a fourth aeration regeneration was carried out, restoring the breakthrough time to , the detailed adsorbed amount can be seen in the Fig. S. 4. The purging effect of oxygen facilitated the breakdown of deposited by-products and their removal from the material's surface, confirming the reversibility of the decrease in adsorption performance during enclosed regeneration. Therefore, in the proposed i-VNT process, 封闭再生试验是在相同的实验条件下进行的。不同的是，饱和吸附后，高浓度氧气被引入反应器。随后，关闭反应器的上下阀门，形成密闭空间，然后升高温度以实现再生。结果如图 7 所示。密闭空间允许脱落物质长时间停留并与高浓度氧气发生反应。经过两个循环后， 的突破时间降至 ， 的突破时间降至 40 分钟，表明催化剂再生不完全。因此，进行了第四次曝气再生，使突破时间恢复到 ，详细的吸附量见图 S.4。氧气的净化作用促进了沉积副产物的分解和从材料表面的清除，证实了封闭再生过程中吸附性能下降的可逆性。因此，在拟议的 i- VNT 工艺中、
(c)
(d)
Fig. 8. Characterization analysis: (a) XRD spectra of catalysts supported on different metals; (b) and -TPD spectra of metal doped ; (c) TPR spectra on metal doped ; (f) He-TPD and -TPO spectra of . 图 8 表征分析表征分析：（a）不同金属支撑的 催化剂的 XRD 光谱；（b）掺杂金属的 和 -TPD 光谱 ；（c）掺杂金属的 TPR 光谱 ；（f） 的 He-TPD 和 -TPO 光谱。
a combined regeneration method of enclosed regeneration plus aeration regeneration is expected to be used. In an actual rotary reactor, the initial distribution ratio of enclosed regeneration to aeration regeneration can be set as . 预计将采用封闭再生加曝气再生的组合再生方法。在实际的旋转式反应器中，封闭再生与曝气再生的初始分配比例可设定为 。
3.3. Catalyst characterization and reaction mechanism 3.3.催化剂特性和反应机理
3.3.1. Characterization 3.3.1.特征描述
The adsorption-desorption isotherm of metal-doped is presented in Fig. S.5, exhibiting the typical characteristics of a type IV pattern. This indicates the mesoporous nature of the material and the adsorption of the adsorbent in a monolayer with capillary condensation. The specific surface areas of the three catalysts were similar, with values centered around , and the average pore sizes were also centered around . These excellent surface properties ensured the superior adsorption performance of the materials. 掺金属 的 吸附-解吸等温线见图 S.5，表现出典型的 IV 型模式特征。这表明材料具有介孔性质，吸附剂以毛细管凝结的单层形式被吸附。三种催化剂的比表面积相似，都集中在 左右，平均孔径也集中在 左右。这些优异的表面特性确保了材料的卓越吸附性能。
The structure and composition of the crystalline phases of the material was characterized by XRD, and the patterns of metal doped were given in the Fig. 8 (a). According to the spectra, two distinct cubic crystal shapes of were observed, where , and (PDF#04-0880), and , (PDF#50-00741). For the sample of , the diffraction peak at and were attribute to the reflection of . After the doping of metal , the diffraction of was found to disappear but without the appearance of new peaks of . Another week diffraction peak at was assigned to the tetrahedral crystal type solid solution that corresponded to (321) crystal plane. Moreover, the intensity of diffraction peaks got weakened at and , it was speculated that may have interacted with to cover part of its crystalline phase, or the formation of third mixed crystalline phase structure of , which was due to eutectic expands and reacts by heating up [30]. In addition, for the sample of , no diffraction peaks ascribed to and were detected, which may be due to the well dispersion of the metal oxide or that the oxide grew on in an epitaxial manner [31,32]. Scherer's formula was used for the calculation of crystallite sizes of nanoscale as no interference from and metals in the diffraction peaks at for all the samples. Accordingly, it was calculated that the size of were and , respectively, indicating that the doped metal did not change the structure of the original tetragonal and without any agglomeration (Fig. 9). 图 8 (a)给出了掺杂金属的 的图样。光谱显示， 有两种不同的立方晶体形状，分别是 , 和 (PDF#04-0880) 以及 , (PDF#50-00741)。对于 样品， 和 处的衍射峰归因于 的反射。在掺入金属 后，发现 的衍射峰消失了，但没有出现 的新峰。 处的另一周衍射峰被认为是与 (321) 晶面相对应的四面体晶体类型 固溶体。此外， 在 和 处的衍射峰强度减弱，推测 可能与 发生了相互作用，覆盖了其部分晶相，或形成了 的第三种混合晶相结构，这是由于共晶膨胀并在加热时发生反应所致[30]。此外，对于 样品，未检测到归属于 和 的衍射峰，这可能是由于金属氧化物分散良好，或 氧化物以外延方式生长在 上 [31,32]。由于在 处的衍射峰中没有 和 金属的干扰，因此使用舍勒公式计算了纳米级 的晶粒大小。据此计算出 的尺寸分别为 和 ，表明掺杂的金属并没有改变原有四方 的结构，也没有发生任何团聚现象（图 9）。
To evaluate the effect of acidity on the adsorption and activation process of the reactants, -TPD experiments of metal doped were carried out. The acidic strength of the material can be determined by the position and the size of the peak area, and the results were shown in the Fig. 8 (b). The broad desorption peaks below were assigned to the desorption of the physisorbed and the dissociation of from the weak acid sites [33,34]. Another strong peak showed in on corresponding to the medium acidic sites, assigned to the desorption from the Brønsted acid site. Compared to the pure carrier (in Fig. S. 9 in Supplementary Materials), the intensity of strong peaks weakened after metal doping, as the high peak values shifted toward low-temperature and medium-temperature regions, which indicated the enhanced adsorption of on the strong Lewis acid site. On the one hand, the increased peak intensities derived from the opening pore size and the enhancing the specific surface area of the substrate caused by the doped metal. On the other hand, the presence of metal generating new active sites. In general, both the increased number and intensity of acidic sites were beneficial for the adsorption and the activation of , resulting in an excellent activity in the entire temperature range [35]. The toluene-TPD experiment was performed to investigate the adsorption capacity, and the spectrum were also given in Fig. 8 (b). The desorption process of toluene is much simpler and the desorption peaks are mainly concentrated around , which implies that only one type of benzene adsorption site exists on the surface of the material. In this case, most of the xylene was desorbed in the form of physical desorption because its interaction force with the adsorbent surface was very weak. However, the fluctuations occur above , which was due to the reaction between the lattice oxygen species of metal oxides and the chemisorbed xylenes [36]. The high intensity of the desorption peak is favorable for the material to adsorb more toluene, thus increasing the reaction rate. And the XPS analysis can be found in S1 Text section in Supplementary material. 为了评估酸性对反应物吸附和活化过程的影响，对掺杂金属的 进行了 -TPD 实验。材料的酸性强度可以通过峰面积的位置和大小来确定，结果如图 8 (b)所示。 以下的宽解吸峰被认为是物理吸附 的解吸和 从弱酸位点解离 [33,34]。另一个强峰出现在 上的 中，与中酸性位点相对应，是 从勃氏酸位点解吸的结果。与纯 载体相比（见补充材料中的图 S. 9），掺杂金属后强峰强度减弱，高峰值向低温和中温区转移，这表明 在强路易斯酸位点上的吸附增强。一方面，峰强度的增加源于掺杂金属导致的孔径增大和基底比表面积的增加。另一方面，金属的存在产生了新的活性位点。总的来说，酸性位点数量和强度的增加都有利于 的吸附和活化，从而使 在整个温度范围内都具有出色的活性 [35]。图 8 (b)给出了甲苯-TPD 实验的吸附容量和光谱。甲苯的解吸过程要简单得多，解吸峰主要集中在 附近，这意味着材料表面只存在一种苯吸附位点。在这种情况下，由于二甲苯与吸附剂表面的相互作用力非常弱，因此大部分二甲苯都是以物理解吸的形式解吸的。然而，波动发生在 以上，这是由于金属氧化物的晶格氧物种与化学吸附的二甲苯之间发生了反应[36]。高强度的解吸峰有利于材料吸附更多的甲苯，从而提高反应速率。XPS 分析见补充材料 S1 文字部分。
The oxidation performance of been doping metals were interrogated using -TPR and profiles were shown in Fig. 8 (c). A wide asymmetrical reduction area at and was observed of sample, indicating the multiple oxide states of species resulting in a large consumption of [37]. Particularly, consumption peaks below related to the transition from to , and the main peaks at and were due to the reduction of to . Furthermore, the dramatic increase in at was presumed to be the reduction of to , and the released heat in the reaction can further promote the conversion of to [38]. However, the reduction peak shifted to a higher temperature region by adding metal , causing the difficulty of reduction on catalysts. The high temperature consumption peak corresponded to the conversion of to , illustrating the little contribution of Mn to the catalyst. Similarly, the reduction peak moved to a higher temperature of , and three peaks appeared, among which, the peak around assigned to the reduction of to and . By contrast, the reduction of occurred after and was due to the poor dispersion of the bimetal, the appearance of large particles of crystals or agglomeration of small particles of crystals blocking the contact with , therefore, more time and higher temperature was needed to the reduction. Overall, the lowest reduction temperature of among the three catalysts was attributed to the better dispersion of species on the support, which is consistent with the XRD characterization results. 使用 -TPR 对 掺杂金属后的氧化性能进行了检测，图 8（c）显示了其曲线。 样品在 和 处观察到一个宽的非对称还原区，这表明 物种的多重氧化态导致了 的大量消耗[37]。尤其是 在 以下的消耗峰值与 向 过渡有关，而 和 处的主要峰值是由于 向 的还原。此外， 处的急剧增加被认为是 还原到 的过程，反应中释放的热量可进一步促进 向 的转化 [38]。然而，通过添加金属 ，还原峰转移到了温度更高的区域，造成了催化剂上还原的困难。高温消耗峰对应于 到 的转化，说明锰对催化剂的贡献很小。同样，还原峰移动到温度更高的 处，出现了三个峰，其中 附近的峰是 还原成 和 的峰。相比之下， 的还原发生在 之后，原因是双金属的分散性较差，出现了大颗粒的 晶体或小颗粒晶体的聚集阻塞了与 的接触，因此还原需要更多的时间和更高的温度。总体而言，三种催化剂中 的还原温度最低，这是因为 物种在载体上的分散性较好，这与 XRD 表征结果一致。
The results of He-TPD in Fig. 8 (d) showed that the desorption occurred from and ended at as the change of signal value in the curve. While in the results of -TPO, the desorption was only physisorption of when the temperature below , after which, both physisorption and chemisorption occurred. It was worth noting that the value started to rise when the temperature rose to in virtue of the generation of and , etc., indicating the occurrence of the oxidation of . The signal value reached summit at , which was also the most intense temperature point for catalytic oxidation. Subsequently, the signal value decreased, suggesting the gradually consumption for on the catalyst. Both the results demonstrated that in the in-situ catalytic oxidation stage, if the set regeneration temperature was too low or the oxidational gas was introduced before , the pollutants would leave the catalyst surface in the form of desorption, which led an incompleteness of the oxidation degradation and a secondary pollution. Since the flow rate selected in the test was min, which was much higher than the selected in the TPD and TPO experiments, a shift of the reaction process to the low temperature region would occur. For example, can be completely taken out of the system at under . 图 8 (d)中 He-TPD 的结果表明，从 开始出现解吸，到 结束，这与曲线中信号值的变化有关。而在 -TPO 的结果中，当温度低于 时，解吸只发生在 的物理吸附上，之后，物理吸附和化学吸附都发生了。值得注意的是，当温度上升到 时，由于产生了 和 等，信号值开始上升，表明 发生了氧化。信号值在 达到顶峰，这也是催化氧化作用最强烈的温度点。随后，信号值下降，表明 在催化剂上的消耗逐渐减少。这两个结果都表明，在原位催化氧化阶段，如果设定的再生温度过低或在 之前引入氧化气体，污染物会以解吸的形式离开催化剂表面，从而导致氧化降解不完全和二次污染。由于试验中选择的流速为 min，远高于 TPD 和 TPO 试验中选择的流速，因此反应过程会转移到低温区域。例如，在 下， ， 可以完全从系统中取出。
The real time changes of surface functional groups during the synergistic reaction using in situ FTIR provide useful information about the comparison of different catalytic efficiencies, formation of the selectivity and reaction pathways for catalytic oxidation of and . The in situ FTIR spectra of the synergistic adsorption-oxidation reaction on were given in Fig. 10 (a), and the spectra of the single substance adsorption process were given in Fig. S. (10-11) in Supplementary Material. The wide peak at the range of and were associated with the vibration of , which were all from , then, the peak at were associated with the 利用原位傅立叶变换红外光谱分析了协同反应过程中表面官能团的实时变化，为比较 和 催化氧化的不同催化效率、选择性的形成和反应途径提供了有用的信息。 上协同吸附-氧化反应的原位傅立叶变换红外光谱见图 10 (a)，单一物质吸附过程的光谱见补充材料中的图 S. (10-11)。 和 范围内的宽峰与 的振动有关，这些振动都来自 ，然后， 范围内的峰与
action of at the Brønsted acid site to form . After an increasing of temperature to , different peaks were observed, including the vibration peak in and the and peak in 2926 and , suggesting the preliminary oxidation while generation of peak ( ), which was due to the result of the reaction of with adsorbed oxygen or lattice oxygen from the catalyst, part of the can be further oxidized to , also, since the reaction between the adsorbed and hydroxyl group, an inverted peak at 3000-3500 cm appeared [39]. Peaks at and 1521 were associated with the chelated bidentate nitrate and carboxylic acid group, respectively. It was obviously that, throughout the whole temperature range, vibrational peaks ), bridged bidentate nitrate ( ) and vibrational peaks ( ) can be observed. With the increasing of temperature from 200 to , the weakening of the coordination of and the generation of carboxylate peaks can be observed, indicating that the occupies the Lewis acid site at this time and hindered the adsorption of . At the range of , it can be seen that the intensity of peak decreased, while the intensity of carboxylic acid peak increased. On one hand, it indicated that the presence of inhibited the deep oxidation of , which corresponding to the results of the decrease in total conversion with increasing temperature appeared in the catalyst efficient test. On the other hand, it was speculated that the amide can be generated from the reaction between chelated bidentate nitrate and the by-products generated from , and it further forms carboxylic acid and , resulting in the increasing of carboxylic acid peak intensity. In addition, the process of amide formation consumed a lot of hydrogen and oxygen ions inside the catalyst, which can promote the formation of more oxygen vacancies and further accelerate the reaction. The group was a by-product of the oxidation of . Ye et al., [17] found that the presence of and can promote the dehydrogenation of on the benzene ring to produce benzyl alcohol, which facilitated the further oxidation of . Also, no peaks of adsorbed , adsorbed and gaseous (1368/1404, 966, ) were observed in the spectra [40], and together with the consistent presence of nitrate peaks, it was presumed that was easily oxidized to adsorbed , which reacted with adsorbed to form subsequently, and eventually reacted to water and . Due to the inactivity 在布氏酸位点的作用下形成 。温度升高到 后，观察到不同的峰值，包括 中的 振荡峰，2926 和 中的 和 峰，表明初步氧化，同时产生 峰 ( )、这是由于 与催化剂中吸附的氧或晶格氧反应的结果，部分 可进一步氧化为 ，同时，由于吸附的 与羟基反应，在 3000-3500 cm 处出现了一个倒置峰 [39]。 和 1521 处的峰分别与螯合的二叉硝酸基和羧酸基有关。很明显，在整个温度范围内，都可以观察到 振荡峰 ）、桥接的双叉硝酸酯（ ）和 振荡峰（ ）。随着温度从 200 升高到 ，可以观察到 的配位减弱和羧酸盐峰的产生，说明此时 占据了路易斯酸位点，阻碍了 的吸附。在 的范围内，可以看到 峰的强度下降，而羧酸峰的强度上升。一方面，这表明 的存在抑制了 的深度氧化，这与催化剂效率测试中出现的总转化率随温度升高而降低的结果相对应。另一方面，推测酰胺 可由螯合双齿硝酸盐与 生成的副产物反应生成，并进一步形成羧酸和 ，导致羧酸峰强度增加。此外，酰胺的形成过程消耗了催化剂内部大量的氢离子和氧离子，可促进形成更多的氧空位，进一步加快反应速度。 基团是 氧化反应的副产物。Ye 等人[17] 发现， 和 的存在可促进 在苯环上脱氢生成苯甲醇，从而促进 的进一步氧化。 此外，光谱中没有观察到吸附的 、吸附的 和气态的 (1368/1404, 966, ) 的峰值[40]，再加上硝酸盐峰值的一致存在，推测 很容易被氧化成吸附的 ，随后与吸附的 反应生成 ，并最终反应生成水和 。由于不活动
Fig. 10. Synergistic catalytic reaction path based on . 图 10.基于 的协同催化反应路径。
Fig. 11. Adsorption fitting curve of and and mixture at different temperatures. 图 11. 和 以及 混合物在不同温度下的吸附拟合曲线。
of couple with the strong adsorption for on the catalyst surface, the formation of was low. 由于 与 在催化剂表面的吸附力很强，因此 的生成量很低。
Leading research clarified three reaction pathways for catalytic oxidation, including mechanism, intermediate mechanism and iSCR reaction mechanism. Thus, combined with FT-IR mechanistic analysis, the effects for the presence of on the oxidation of might follow two routes: (a) competition with for reactive oxygen species, which leaded to the deposition of aldehydes, carboxylic acids, and carbonates on the catalyst surface, and thus, requiring higher complete conversion temperature; (b) promoted the dehydrogenation of on the benzene ring to generate benzyl alcohol to facilitate oxidation. Comparison on the effects of single and synergistic catalytic oxidation also revealed the competition for reactive oxygen, which can avoid excessive oxidation of to and , since the and generation temperatures correspond to and when was catalyzed alone, while in synergistic catalytic oxidation were and , respectively. So, it can be said that firstly dehydrogenation to generate and , followed by reaction with oxygen to generate or , and the products can also react with each other. Take for example, on which and can react to form and then be converted to and , in addition, the acidic sites on the surface can also provide a strong adsorption effect on , thus reducing the generation of and . By contrast, on CuMn and , the dehydrogenation of and the ring opening of will be inhibited, and only by increasing the temperature can promote the complete conversion, but in turn, it led to a direct reaction of with gaseous causing a decrease in selectivity. That is why there was a mutual inhibition of total conversion and selectivity. Also, the by-products of and can react with each other to form amides, and then to and carboxylates, which is also a path to avoid and generation. 领先的研究明确了 催化氧化的三种反应途径，包括 机制、 中间机制和 iSCR 反应机制。因此，结合 FT-IR 机理分析， 的存在对 氧化的影响可能有两种途径：（a）与 竞争活性氧，导致醛、羧酸和碳酸盐在催化剂表面沉积，从而需要更高的完全转化温度；（b）促进 在苯环上脱氢生成苯甲醇，以促进氧化。 对单一催化氧化和协同催化氧化效果的比较还显示了对活性氧的竞争，这可以避免 被过度氧化为 和 ，因为单独催化时， 和 的生成温度分别对应于 和 ，而协同催化氧化时， 和 分别对应于 和 。因此，可以说 首先脱氢生成 和 ，然后与氧气反应生成 或 ，而且产物之间还可以相互反应。以 为例，在 上， 和 可以反应生成 ，然后再转化为 和 ，此外，表面的酸性位点还可以对 产生强烈的吸附作用，从而减少 和 的生成。相比之下，在 CuMn 和 上， 的脱氢和 的开环会受到抑制，只有提高温度才能促进完全转化，但反过来又会导致 与气态 直接反应，造成选择性降低。这就是总转化率和选择性相互抑制的原因。另外， 和 的副产物可以相互反应生成酰胺，然后生成 和羧酸盐，这也是避免生成 和 的途径。
Combining the FT-IR results, the reaction mechanism of co-catalytic oxidation of on can obtained and shown in Fig. 10 . 结合傅立叶变换红外光谱结果，可以得出 在 上协同催化氧化的反应机理，如图 10 所示。
3.4. Kinetic modeling 3.4.动力学模型
Sorption of and on at the temperature of , , and reflected the kinetics of adsorption. Fig. 11 showed the fitted curves for the adsorption of . Both the pseudo-first as well as second-order kinetic curves were nearly overlap, and the correlation coefficient was between 0.96 and 0.98 , but the fitted was very different from the actual value, for example, the fitted values of the pseudo-first and second-order models at were 207.18 and 345.28 , respectively, while the measured value was 131.59 . The Elovich model showed the largest fit bias, with only reaching 0.82 . By contrast, the best results were obtained using Banham equation with of 0.995 and the calculated of 144.84 was very close to the measured value. Therefore, the Banham equation can be used in description of the kinetic process of adsorption by . Similarly, the results of kinetic fitting of were shown in Fig. 11 (d-e), where the Banham model showed the highest fitting quality exceed to 0.995 and the smallest calculation error in . In practical application, pseudo-first and secondorder kinetic models were more common. However, in pursuing a higher fitting quality of pseudo-first-order kinetic, should be measured accurately, which took a long time for the equilibrium, thus, pseudofirst-order kinetic model was suitable for the kinetic description of the initial stage of adsorption. The second-order kinetic model contains all the processes of adsorption, such as external diffusion, surface 和 在 上的吸附温度分别为 、 和 ，这反映了吸附动力学。图 11 显示了 的吸附拟合曲线。伪一阶和二阶动力学曲线几乎重合，相关系数 在 0.96 和 0.98 之间，但拟合的 与实际值相差很大，例如，在 ，伪一阶和二阶模型的拟合 值分别为 207.18 和 345.28，而实测值为 131.59。埃洛维奇模型的拟合偏差最大， 只达到 0.82。相比之下，使用 Banham 方程得到的结果最好， 为 0.995，计算得到的 为 144.84，与测量值非常接近。因此，Banham 方程可用于描述 对 的吸附动力学过程。同样， 的动力学拟合结果如图 11（d-e）所示，Banham 模型的拟合质量最高，超过 0.995，计算误差最小， 。在实际应用中，伪一阶和二阶动力学模型更为常见。然而，为了追求更高的伪一阶动力学拟合质量， ，必须精确测量，这需要较长的平衡时间，因此伪一阶动力学模型适用于吸附初始阶段的动力学描述。二阶动力学模型包含了吸附的所有过程，如外部扩散、表面吸附、吸附剂的吸附、吸附剂的吸附、吸附剂的吸附、吸附剂的吸附和吸附剂的吸附。
adsorption and internal diffusion, but the calculated bias was too large. More detailed results based on the different models were given in Tab. S. 3 Supporting Material. 但计算得出的 偏差过大。基于不同模型的更详细结果见表 S. 3 佐证材料。S. 3 辅助材料。
3.5. Discussion 3.5.讨论情况
Here, a small and integrated process of adsorption/oxidation was proposed to achieve the synergistic treatment of VOCs and . Catalysts and adsorbents with high saturation adsorption capacity, high catalytic activity and selectivity were developed and preferred. The interaction and reaction mechanism between VOCs and in the synergistic catalytic and i-VNT process were well investigated, which provided good ideas for the synergistic treatment of multiple pollutants. 在此，我们提出了一种小型的吸附/氧化一体化工艺，以实现 VOCs 和 的协同处理。开发并优选了高饱和吸附容量、高催化活性和高选择性的催化剂和吸附剂。对协同催化和 i-VNT 过程中 VOCs 和 之间的相互作用和反应机理进行了深入研究，为多种污染物的协同处理提供了很好的思路。
The proposed small equipment's prototype is referenced the VOC removal rotor, the combined regeneration method of enclosed and aeration regeneration ensures the continuous operation and emissions meet environmental requirements. And in the actual application, the ratio of enclosed regeneration and aeration regeneration distinct can be adjusted or designed according to the pollutant concentration. The combined regeneration method is expected to be applied to all types of thermal regeneration-based adsorption/desorption applications. 拟建小型设备的原型参考了挥发性有机物去除转轮，采用封闭再生和曝气再生相结合的再生方式，确保设备连续运行，排放符合环保要求。在实际应用中，可根据污染物浓度调整或设计封闭再生和曝气再生的比例。组合再生法有望应用于所有类型的基于热再生的吸附/解吸应用。
From the perspective of application, the types of pollutants in the actual environment are more complex and not only limited to , but there may also be moisture, ash and sulfur, so improving the treatment of complex gases and improving the stability of materials are still the focus of the later research. 从应用的角度来看，实际环境中的污染物种类较为复杂，不仅限于 ，还可能存在水分、灰分、硫分等，因此提高复杂气体的处理能力、提高材料的稳定性仍是后期研究的重点。
4. Conclusion 4.结论
This study is reported the interaction and reaction mechanism between VOCs and in the synergistic treatment process, and the i-VNT process was proposed relying on a rotary reactor. Transition metal doped were finally optimized to validated the feasibility of the iVNT process. The catalysts exhibited excellent adsorption performance for is of and for is of , but decreased by and , respectively during the synergistic adsorption process. Moreover, the materials were able to completely achieve the single catalytic degradation of and at . However, this changed during the synergistic catalytic oxidation process, because the reaction windows of the two reactants were not consistent and competed with each other for the active oxygen. As a result, inhibitory and restorative effects are observed in the oxidation of . A novel regeneration method combining enclosed and aeration regeneration ensured that the adsorption time of the material was maintained at 50 min after three regenerations, which ensures the reusability of the material. In situ FTIR further revealed the synergistic reaction mechanism, and the formation of , carboxylates, aldehydes, etc. was observed. This study has certain reference significance in the synergistic treatment of multiple pollutants. 本研究报告了 VOCs 与 在协同处理过程中的相互作用和反应机理，并提出了依托旋转反应器的 i-VNT 工艺。最后对掺杂过渡金属的 进行了优化，验证了 iVNT 工艺的可行性。催化剂对 is of 和 is of 具有优异的吸附性能，但在协同吸附过程中， 和 的吸附性能分别有所下降。此外，这些材料还能在 上完全实现 和 的单一催化降解。然而，在协同催化氧化过程中，这种情况发生了变化，因为两种反应物的反应窗口并不一致，相互竞争活性氧。因此，在 的氧化过程中出现了抑制和恢复效应。封闭再生和曝气再生相结合的新型再生方法确保了材料在三次再生后的吸附时间保持在 50 分钟，从而保证了材料的可重复使用性。原位傅立叶变换红外光谱进一步揭示了协同反应机理，并观察到 、羧酸盐、醛类等物质的生成。该研究对多种污染物的协同处理具有一定的参考意义。
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. 作者声明，他们没有任何可能会影响本文所报告工作的已知经济利益或个人关系。
Data availability 数据可用性
The data that has been used is confidential. 所使用的数据是保密的。
Acknowledgements 致谢
The authors thank the Shandong Key Research and Development Plan (NO. 2020CXGC011402), Taishan Scholar Project (NO. tsqn202306021), and Cyrus Chung Ying Tang Foundation (SDU20220503) for the financial support. 作者感谢山东省重点研发计划（NO.2020CXGC011402）、泰山学者项目（NO.tsqn202306021）和赛勒斯-钟应堂基金会（SDU20220503）的资助。
Appendix A. Supplementary data 附录 A.补充数据
Supplementary data to this article can be found online at https://doi. org/10.1016/j.seppur.2024.126555. 本文的补充数据可在线查阅：https://doi. org/10.1016/j.seppur.2024.126555。
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Corresponding author at: School of Energy and Power Engineering, Shandong University, Jinan 250061, China. 通讯作者：山东大学能源与动力工程学院山东大学能源与动力工程学院，中国济南 250061。
