Chinese Journal of Catalysis最新文献_第7页

Reactant-modulated catalytic alcoholysis of polylactic acid from real-life biodegradable plastic waste 生物可降解塑料废弃物中聚乳酸的反应物调节催化醇解

IF 17.7 1区化学 Q1 CHEMISTRY, APPLIED

Chinese Journal of Catalysis

Pub Date : 2025-10-27 DOI: 10.1016/S1872-2067(25)64811-X

Chang He , Zhenbo Guo , Zhijun Wang , Yi Ji , Linrui Li , Xin Qiu , Zhuo Liu , Zhaowen Dong , Guangjin Hou , Meng Wang , Fan Zhang

Alcoholysis is one of the most effective methods for recycling polyester plastics. While many researchers claim that both alcohol and polymer reactants are activated simultaneously in the alcoholysis reaction, more reliable experimental evidence is needed to fully understand the process, and the catalytic mechanism remains elusive. To address this issue, we proposed a reactant-modulated catalytic depolymerization strategy involving a pre-mixing of alcohol or polylactic acid (PLA) with an organic base catalyst. Through systematic experimental and theoretical investigations, we have confirmed that different intermediates are formed during pre-mixing the catalyst with PLA or methanol, which can either slow down or accelerate the subsequent alcoholysis reaction. By employing the methanol-modulated depolymerization technique, we successfully achieved PLA alcoholysis at temperatures as low as –40 °C. We further investigated the solubility and reactivity of different polyesters, including PET, PC, PBS, PBAT, PCL, and PLA, revealing an efficient recycling method for PLA. By optimizing reaction conditions in a continuous flow reactor, we recovered 127.3 g of methyl lactate from 100 g of plastic cups in just 4 h at room temperature. These findings greatly improve our grasp of polyester solvolysis processes and create new opportunities within the plastics sector recycling.

醇解法是回收聚酯塑料最有效的方法之一。虽然许多研究人员认为醇解反应中醇和聚合物反应物同时被激活，但需要更可靠的实验证据来充分理解这一过程，催化机制仍然难以捉摸。为了解决这个问题，我们提出了一种反应物调节的催化解聚策略，包括酒精或聚乳酸（PLA）与有机碱催化剂的预混合。通过系统的实验和理论研究，我们证实了催化剂在与PLA或甲醇预混的过程中会形成不同的中间体，从而减缓或加速后续的醇解反应。通过采用甲醇调节解聚技术，我们成功地在低至-40°C的温度下实现了PLA醇解。我们进一步研究了不同聚酯的溶解性和反应性，包括PET， PC， PBS， PBAT， PCL和PLA，揭示了PLA的有效回收方法。通过优化连续流反应器的反应条件，我们在室温下仅用4小时就从100 g塑料杯中回收了127.3 g乳酸甲酯。这些发现大大提高了我们对聚酯溶剂分解工艺的掌握，并在塑料回收领域创造了新的机会。

{"title":"Reactant-modulated catalytic alcoholysis of polylactic acid from real-life biodegradable plastic waste","authors":"Chang He , Zhenbo Guo , Zhijun Wang , Yi Ji , Linrui Li , Xin Qiu , Zhuo Liu , Zhaowen Dong , Guangjin Hou , Meng Wang , Fan Zhang","doi":"10.1016/S1872-2067(25)64811-X","DOIUrl":"10.1016/S1872-2067(25)64811-X","url":null,"abstract":"<div><div>Alcoholysis is one of the most effective methods for recycling polyester plastics. While many researchers claim that both alcohol and polymer reactants are activated simultaneously in the alcoholysis reaction, more reliable experimental evidence is needed to fully understand the process, and the catalytic mechanism remains elusive. To address this issue, we proposed a reactant-modulated catalytic depolymerization strategy involving a pre-mixing of alcohol or polylactic acid (PLA) with an organic base catalyst. Through systematic experimental and theoretical investigations, we have confirmed that different intermediates are formed during pre-mixing the catalyst with PLA or methanol, which can either slow down or accelerate the subsequent alcoholysis reaction. By employing the methanol-modulated depolymerization technique, we successfully achieved PLA alcoholysis at temperatures as low as –40 °C. We further investigated the solubility and reactivity of different polyesters, including PET, PC, PBS, PBAT, PCL, and PLA, revealing an efficient recycling method for PLA. By optimizing reaction conditions in a continuous flow reactor, we recovered 127.3 g of methyl lactate from 100 g of plastic cups in just 4 h at room temperature. These findings greatly improve our grasp of polyester solvolysis processes and create new opportunities within the plastics sector recycling.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"78 ","pages":"Pages 192-201"},"PeriodicalIF":17.7,"publicationDate":"2025-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145371281","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Interfacial Zn–N bond bridges direct S-scheme charge transfer 界面Zn-N键桥接直接S-scheme电荷转移

IF 17.7 1区化学 Q1 CHEMISTRY, APPLIED

Chinese Journal of Catalysis

Pub Date : 2025-10-27 DOI: 10.1016/S1872-2067(25)64809-1

Feiyan Fu , Yunfeng Li

引用次数: 0

Refining lignin into aromatic nitrogen-heterocyclic compounds: Sustainable avenue toward value-added chemicals 木质素精制成芳香族氮杂环化合物：增值化学品的可持续发展途径

IF 17.7 1区化学 Q1 CHEMISTRY, APPLIED

Chinese Journal of Catalysis

Pub Date : 2025-10-27 DOI: 10.1016/S1872-2067(25)64798-X

Wentao Su , Shenglong Tian , Huamei Yang , Changzhi Li , Tao Zhang

Lignin is the only largest renewable aromatic resource in nature. Currently, most lignin is underutilized for low-value applications due to the complex structure and recalcitrant chemical properties. Over the past decades, extensive research has been devoted to valorizing lignin into aromatic N-heterocycles in the presence of nitrogen sources. It overcomes the element limitation, expands the products portfolio and would play a momentous role in value-added biorefinery concept. In this review, the latest research progress in the synthesis of N-heterocyclic compounds from lignin, lignin model compounds, and lignin-derived monomers (phenols, aromatic alcohols, aldehydes, ketones, and ethers) is presented. According to the structural characteristics of the products, these achievements are classified by the construction of five-, six-, and seven-membered N-heterocyclic compounds through one-step, multi-step, or one-pot multi-step reactions. Furthermore, the tailor-designed routes and catalytic systems, along with the reaction mechanisms/pathways involved are entirely discussed to elucidate the challenges regarding the structural complexity of lignin, the incompatible catalysis for C–O cleavage and C–N formation, as well as the nitrogen-heterocyclic ring construction. The prospects, future research efforts and process developments for the refining of lignin into aromatic N-heterocyclic compounds are outlined in terms of economy, environmental friendliness, and safety so as to draw some guidelines for lignin valorization.

木质素是自然界中唯一最大的可再生芳香资源。目前，大多数木质素由于结构复杂和化学性质顽固，在低价值应用中未得到充分利用。在过去的几十年里，广泛的研究致力于在氮源存在的情况下将木质素转化为芳香n杂环。它克服了元素限制，扩大了产品组合，将在增值生物炼制概念中发挥重要作用。本文综述了木质素、木质素模型化合物和木质素衍生单体（酚类、芳香醇类、醛类、酮类和醚类）合成n-杂环化合物的最新研究进展。根据产物的结构特点，将这些成果分为通过一步、多步或一锅多步反应构建五元、六元和七元n杂环化合物。此外，本文还全面讨论了定制路线和催化体系，以及所涉及的反应机制/途径，以阐明木质素在结构复杂性，C-O裂解和C-N形成的不相容催化以及氮杂环构建方面的挑战。从经济、环保、安全等方面对木质素精制成芳香n杂环化合物的前景、研究方向和工艺发展进行了展望，以期为木质素的增值提供指导。

{"title":"Refining lignin into aromatic nitrogen-heterocyclic compounds: Sustainable avenue toward value-added chemicals","authors":"Wentao Su , Shenglong Tian , Huamei Yang , Changzhi Li , Tao Zhang","doi":"10.1016/S1872-2067(25)64798-X","DOIUrl":"10.1016/S1872-2067(25)64798-X","url":null,"abstract":"<div><div>Lignin is the only largest renewable aromatic resource in nature. Currently, most lignin is underutilized for low-value applications due to the complex structure and recalcitrant chemical properties. Over the past decades, extensive research has been devoted to valorizing lignin into aromatic N-heterocycles in the presence of nitrogen sources. It overcomes the element limitation, expands the products portfolio and would play a momentous role in value-added biorefinery concept. In this review, the latest research progress in the synthesis of N-heterocyclic compounds from lignin, lignin model compounds, and lignin-derived monomers (phenols, aromatic alcohols, aldehydes, ketones, and ethers) is presented. According to the structural characteristics of the products, these achievements are classified by the construction of five-, six-, and seven-membered N-heterocyclic compounds through one-step, multi-step, or one-pot multi-step reactions. Furthermore, the tailor-designed routes and catalytic systems, along with the reaction mechanisms/pathways involved are entirely discussed to elucidate the challenges regarding the structural complexity of lignin, the incompatible catalysis for C–O cleavage and C–N formation, as well as the nitrogen-heterocyclic ring construction. The prospects, future research efforts and process developments for the refining of lignin into aromatic N-heterocyclic compounds are outlined in terms of economy, environmental friendliness, and safety so as to draw some guidelines for lignin valorization.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"78 ","pages":"Pages 25-46"},"PeriodicalIF":17.7,"publicationDate":"2025-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145371272","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Decoupling the HOR enhancement on PtRu: Dynamically matching interfacial water to reaction coordinates PtRu上HOR增强的解耦：界面水与反应坐标的动态匹配

IF 17.7 1区化学 Q1 CHEMISTRY, APPLIED

Chinese Journal of Catalysis

Pub Date : 2025-10-27 DOI: 10.1016/S1872-2067(25)64785-1

Jin Liu , Zhuoyang Xie , Qiong Xiang , Xia Chen , Mengting Li , Jiawei Liu , Li Li , Zidong Wei

Platinum-ruthenium alloys (PtRu) represent state-of-the-art alkaline hydrogen oxidation reaction (HOR) catalysts, yet the atomic-scale origin of their superiority over pure Pt remains incompletely understood. Here, we employ density functional theory calculations, ab initio molecular dynamics simulations, and microkinetic modeling on Pt(111) and PtRu(111) surfaces to systematically investigate the key factors, including active sites distribution, species adsorption, and solvent reorganization, that affect the HOR activity and decouple their contributions. The results reveal that while the moderate hydrogen binding energy and improved hydroxyl (OH) species adsorption both contribute to the enhanced activity, the dominant factor is the substantial reduction in solvent reorganization energy on the PtRu(111). This is facilitated by the spatial separation of active sites: Pt atoms preferentially stabilize adsorbed hydrogen, while Ru atoms strongly bind OH and interfacial water molecules. This configuration increases the probability of hydrogen interacting with OH/water and enhances the fraction of “H-up” water molecules, forming a well-organized hydrogen bond network within the electric double layer. The dynamically compatible interfacial water structure and HOR coordination promote H desorption and proton transfer in the Volmer step, thereby accelerating the HOR kinetics.

铂钌合金（PtRu）代表了最先进的碱性氢氧化反应（HOR）催化剂，但其优于纯铂的原子尺度起源仍不完全清楚。本文采用密度泛函理论计算、从头算分子动力学模拟和Pt（111）和PtRu（111）表面的微动力学模型，系统地研究了影响HOR活性的关键因素，包括活性位点分布、物种吸附和溶剂重组，并解耦合了它们的贡献。结果表明，虽然适度的氢结合能和羟基吸附的改善都有助于提高活性，但主要因素是PtRu上溶剂重组能的大幅降低（111）。这得益于活性位点的空间分离：Pt原子优先稳定吸附的氢，而Ru原子强烈结合OH和界面水分子。这种结构增加了氢与OH/水相互作用的可能性，并增加了“H-up”水分子的比例，在电双层内形成了一个组织良好的氢键网络。动态相容的界面水结构和HOR配位促进了Volmer步骤中的H解吸和质子转移，从而加速了HOR动力学。

{"title":"Decoupling the HOR enhancement on PtRu: Dynamically matching interfacial water to reaction coordinates","authors":"Jin Liu , Zhuoyang Xie , Qiong Xiang , Xia Chen , Mengting Li , Jiawei Liu , Li Li , Zidong Wei","doi":"10.1016/S1872-2067(25)64785-1","DOIUrl":"10.1016/S1872-2067(25)64785-1","url":null,"abstract":"<div><div>Platinum-ruthenium alloys (PtRu) represent state-of-the-art alkaline hydrogen oxidation reaction (HOR) catalysts, yet the atomic-scale origin of their superiority over pure Pt remains incompletely understood. Here, we employ density functional theory calculations, <em>ab initio</em> molecular dynamics simulations, and microkinetic modeling on Pt(111) and PtRu(111) surfaces to systematically investigate the key factors, including active sites distribution, species adsorption, and solvent reorganization, that affect the HOR activity and decouple their contributions. The results reveal that while the moderate hydrogen binding energy and improved hydroxyl (OH) species adsorption both contribute to the enhanced activity, the dominant factor is the substantial reduction in solvent reorganization energy on the PtRu(111). This is facilitated by the spatial separation of active sites: Pt atoms preferentially stabilize adsorbed hydrogen, while Ru atoms strongly bind OH and interfacial water molecules. This configuration increases the probability of hydrogen interacting with OH/water and enhances the fraction of “H-up” water molecules, forming a well-organized hydrogen bond network within the electric double layer. The dynamically compatible interfacial water structure and HOR coordination promote H desorption and proton transfer in the Volmer step, thereby accelerating the HOR kinetics.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"78 ","pages":"Pages 303-312"},"PeriodicalIF":17.7,"publicationDate":"2025-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145371159","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Breaking the selectivity barrier in glycerol electrooxidation to glyceraldehyde via redox mediation 通过氧化还原介质打破甘油电氧化制甘油醛的选择性屏障

IF 17.7 1区化学 Q1 CHEMISTRY, APPLIED

Chinese Journal of Catalysis

Pub Date : 2025-10-27 DOI: 10.1016/S1872-2067(25)64816-9

Zhenghao Mao , Wenjing Xu , Na Han , Yanguang Li

Aldehydes are valuable intermediates with widespread industrial applications, and their traditional synthesis relies on chemical oxidation that is often hazardous and environmentally unfriendly. Electrochemical oxidation offers a more sustainable and milder alternative; however, it faces challenges such as aldehyde overoxidation and susceptibility to base-catalyzed Cannizzaro disproportionation. Electrochemical glycerol oxidation to glyceraldehyde is a representative example, which typically requires precious metal-based electrocatalysts but still suffers from low selectivity and activity. Here, we report a metal-free oxidation strategy mediated by 2,2,6,6-tetramethylpiperidine-1-oxyl. By systematically investigating the redox thermodynamics and kinetics of TEMPO across a broad pH range, we construct a Pourbaix diagram and elucidate the relative kinetics of each reaction step. These insights allow us to explain the anomalously high apparent Faradaic efficiency (~200%) observed under acidic conditions, and identify neutral media as the optimal environment for selective glyceraldehyde production. Under optimized conditions, our system achieves a glyceraldehyde Faradaic efficiency exceeding 93% and a partial current density of 23.3 mA cm^–2 at 0.57 V — more than doubling the performance of the best reported precious metal-based systems. Furthermore, the versatility of this strategy extends to the selective oxidation of other primary alcohols to their corresponding aldehydes with near-unity selectivity.

醛是一种具有广泛工业应用价值的中间体，其传统合成依赖于化学氧化，这往往是危险和不环保的。电化学氧化提供了更可持续、更温和的替代方案；然而，它面临着醛过氧化和碱催化的坎尼扎罗歧化的敏感性等挑战。电化学氧化甘油制甘油醛是一个典型的例子，通常需要贵金属基电催化剂，但仍然存在低选择性和低活性的问题。在这里，我们报道了一种由2,2,6,6-四甲基哌啶-1-氧介导的无金属氧化策略。通过系统地研究TEMPO在广泛pH范围内的氧化还原热力学和动力学，我们构建了Pourbaix图，并阐明了每个反应步骤的相对动力学。这些见解使我们能够解释在酸性条件下观察到的异常高的表观法拉第效率（~200%），并确定中性介质是选择性甘油醛生产的最佳环境。在优化的条件下，我们的系统实现了甘油醛法拉第效率超过93%，在0.57 V下的分电流密度为23.3 mA cm-2，比目前报道的最佳贵金属基系统性能提高了一倍多。此外，这种策略的多功能性扩展到其他伯醇以接近统一的选择性氧化成相应的醛。

{"title":"Breaking the selectivity barrier in glycerol electrooxidation to glyceraldehyde via redox mediation","authors":"Zhenghao Mao , Wenjing Xu , Na Han , Yanguang Li","doi":"10.1016/S1872-2067(25)64816-9","DOIUrl":"10.1016/S1872-2067(25)64816-9","url":null,"abstract":"<div><div>Aldehydes are valuable intermediates with widespread industrial applications, and their traditional synthesis relies on chemical oxidation that is often hazardous and environmentally unfriendly. Electrochemical oxidation offers a more sustainable and milder alternative; however, it faces challenges such as aldehyde overoxidation and susceptibility to base-catalyzed Cannizzaro disproportionation. Electrochemical glycerol oxidation to glyceraldehyde is a representative example, which typically requires precious metal-based electrocatalysts but still suffers from low selectivity and activity. Here, we report a metal-free oxidation strategy mediated by 2,2,6,6-tetramethylpiperidine-1-oxyl. By systematically investigating the redox thermodynamics and kinetics of TEMPO across a broad pH range, we construct a Pourbaix diagram and elucidate the relative kinetics of each reaction step. These insights allow us to explain the anomalously high apparent Faradaic efficiency (~200%) observed under acidic conditions, and identify neutral media as the optimal environment for selective glyceraldehyde production. Under optimized conditions, our system achieves a glyceraldehyde Faradaic efficiency exceeding 93% and a partial current density of 23.3 mA cm<sup>–2</sup> at 0.57 V — more than doubling the performance of the best reported precious metal-based systems. Furthermore, the versatility of this strategy extends to the selective oxidation of other primary alcohols to their corresponding aldehydes with near-unity selectivity.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"78 ","pages":"Pages 336-342"},"PeriodicalIF":17.7,"publicationDate":"2025-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145371265","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

An atom-efficient electrosynthesis strategy for organic halides 有机卤化物的原子高效电合成策略

IF 17.7 1区化学 Q1 CHEMISTRY, APPLIED

Chinese Journal of Catalysis

Pub Date : 2025-10-27 DOI: 10.1016/S1872-2067(25)64796-6

Yiwei Liu , Xiaoxia Chang , Bingjun Xu

Existing organic halide synthesis routes typically employ elemental halogens (X₂, X = Cl or Br), leading to low atom economy and significant environmental pollution. In this work, we developed an atom efficient electrosynthesis and separation strategy for halogenation reagents — N-chlorosuccinimide (NCS) and N-bromosuccinimide (NBS) — at high current densities. Faradic efficiency (FE) of 91.0% and 81.3% was achieved for NCS and NBS generation on RuO_x/TiO₂/Ti in a batch cell, respectively. Electrosynthesis of NCS likely involves both heterogeneous catalytic and homogeneous tandem pathways, while NBS is likely formed in a Langmuir-Hinshelwood mechanism with a proton-coupled electron transfer as the rate-determining step. A coupled continuous electrocatalytic synthesis and in situ separation setup was developed for the efficient production of NCS and NBS, which yielded 0.77 g of NCS in 12000 s and 0.81 g of NBS in 15000 s, both with relative purity exceeding 95%. The halogenation of acetone using NCS and NBS enabled gram-scale production of the key intermediate in organic synthesis, 1-halogenacetone, with over 95% recovery of succinimide.

现有的有机卤化物合成路线通常使用元素卤素（X2, X = Cl或Br），导致低原子经济性和严重的环境污染。在这项工作中，我们开发了一种在高电流密度下原子高效电合成和分离卤化试剂- n -氯琥珀酰亚胺（NCS）和n -溴琥珀酰亚胺（NBS）的策略。在批量电池中，在RuOx/TiO2/Ti上生成NCS和NBS的效率分别为91.0%和81.3%。NCS的电合成可能包括非均相催化和均相串联两种途径，而NBS可能以Langmuir-Hinshelwood机制形成，以质子耦合电子转移为速率决定步骤。建立了连续电催化合成和原位分离耦合装置，高效制备NCS和NBS，分别在12000 s和15000 s内制得0.77 g和0.81 g NBS，相对纯度均超过95%。利用NCS和NBS对丙酮进行卤化反应，实现了有机合成关键中间体1-卤代丙酮的克级生产，琥珀酰亚胺的回收率超过95%。

{"title":"An atom-efficient electrosynthesis strategy for organic halides","authors":"Yiwei Liu , Xiaoxia Chang , Bingjun Xu","doi":"10.1016/S1872-2067(25)64796-6","DOIUrl":"10.1016/S1872-2067(25)64796-6","url":null,"abstract":"<div><div>Existing organic halide synthesis routes typically employ elemental halogens (<em>X</em><sub>2</sub>, <em>X</em> = Cl or Br), leading to low atom economy and significant environmental pollution. In this work, we developed an atom efficient electrosynthesis and separation strategy for halogenation reagents — <em>N</em>-chlorosuccinimide (NCS) and <em>N</em>-bromosuccinimide (NBS) — at high current densities. Faradic efficiency (FE) of 91.0% and 81.3% was achieved for NCS and NBS generation on RuO<sub><em>x</em></sub>/TiO<sub>2</sub>/Ti in a batch cell, respectively. Electrosynthesis of NCS likely involves both heterogeneous catalytic and homogeneous tandem pathways, while NBS is likely formed in a Langmuir-Hinshelwood mechanism with a proton-coupled electron transfer as the rate-determining step. A coupled continuous electrocatalytic synthesis and in situ separation setup was developed for the efficient production of NCS and NBS, which yielded 0.77 g of NCS in 12000 s and 0.81 g of NBS in 15000 s, both with relative purity exceeding 95%. The halogenation of acetone using NCS and NBS enabled gram-scale production of the key intermediate in organic synthesis, 1-halogenacetone, with over 95% recovery of succinimide.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"78 ","pages":"Pages 170-181"},"PeriodicalIF":17.7,"publicationDate":"2025-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145371279","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

The synergistic effect of non-compensated Cu/N co-doping and graphene enhances the dual-channel generation of H2O2 over TiO2 photocatalysts 非补偿Cu/N共掺杂与石墨烯的协同作用增强了TiO2光催化剂上H2O2的双通道生成

IF 17.7 1区化学 Q1 CHEMISTRY, APPLIED

Chinese Journal of Catalysis

Pub Date : 2025-10-27 DOI: 10.1016/S1872-2067(25)64799-1

Qianqian Shen , Chenlong Dong , Shilong Feng , Xueli Zhang , Qiurong Li , Jinbo Xue

Modulating the electronic structure of a photocatalyst and constructing spatially separated redox sites are key strategies for achieving the photocatalytic dual-channel generation of H₂O₂. In this study, a graphene-modified non-compensated Cu/N-co-doped titanium dioxide (Cu-N-TiO₂/rGO) photocatalyst was designed for the efficient synthesis of H₂O₂ via a dual-channel pathway. Precise modulation of the TiO₂ conduction band position was achieved through the synergistic coupling of Cu 3d orbitals hybridized with Ti 3d orbitals and hybridization of N 2p orbitals with O 2p orbitals. This approach significantly improved the utilization of sunlight while satisfying the redox potential requirements. Cu doping not only promoted the formation of oxygen vacancies but also reduced the formation of Ti³⁺ ions, the photogenerated charge recombination centers. The non-compensated doping of N effectively increased the solubility of Cu²⁺ ions in the titanium dioxide lattice, enhanced the adsorption of hydroxyl radical intermediates, and created conditions for the subsequent hydroxyl radical combinations promoting the generation of H₂O₂. In addition, the introduction of highly conductive graphene improved the interfacial carrier separation efficiency while realizing the spatial separation of redox sites, creating conditions for dual-channel reactions. The experimental results showed that the H₂O₂ yield of Cu-N-TiO₂/rGO under simulated sunlight reached 1266.7 µmol/L, which was 25.2 times higher than that of pristine TiO₂. This study elucidated the synergistic mechanism of the energy band structure modulation and interfacial optimization, which provided a new idea for the design of dual-channel H₂O₂ production photocatalysts.

调节光催化剂的电子结构和构建空间分离的氧化还原位点是实现光催化双通道生成H2O2的关键策略。在本研究中，设计了一种石墨烯修饰的非补偿Cu/ n共掺杂二氧化钛（Cu- n- tio2 /rGO）光催化剂，通过双通道途径高效合成H2O2。通过Cu三维轨道与Ti三维轨道杂化和N 2p轨道与O 2p轨道杂化的协同耦合，实现了TiO2导带位置的精确调制。这种方法在满足氧化还原电位要求的同时显著提高了对阳光的利用。Cu掺杂不仅促进了氧空位的形成，还减少了Ti3+离子的形成，即光生电荷复合中心。N的非补偿掺杂有效地提高了Cu2+离子在二氧化钛晶格中的溶解度，增强了羟基自由基中间体的吸附，为后续羟基自由基结合创造条件，促进H2O2的生成。此外，高导电性石墨烯的引入提高了界面载流子分离效率，同时实现了氧化还原位点的空间分离，为双通道反应创造了条件。实验结果表明，Cu-N-TiO2/rGO在模拟阳光下的H2O2产率达到1266.7µmol/L，是原始TiO2的25.2倍。本研究阐明了能带结构调制与界面优化的协同作用机理，为双通道产H2O2光催化剂的设计提供了新的思路。

{"title":"The synergistic effect of non-compensated Cu/N co-doping and graphene enhances the dual-channel generation of H2O2 over TiO2 photocatalysts","authors":"Qianqian Shen , Chenlong Dong , Shilong Feng , Xueli Zhang , Qiurong Li , Jinbo Xue","doi":"10.1016/S1872-2067(25)64799-1","DOIUrl":"10.1016/S1872-2067(25)64799-1","url":null,"abstract":"<div><div>Modulating the electronic structure of a photocatalyst and constructing spatially separated redox sites are key strategies for achieving the photocatalytic dual-channel generation of H<sub>2</sub>O<sub>2</sub>. In this study, a graphene-modified non-compensated Cu/N-co-doped titanium dioxide (Cu-N-TiO<sub>2</sub>/rGO) photocatalyst was designed for the efficient synthesis of H<sub>2</sub>O<sub>2</sub> via a dual-channel pathway. Precise modulation of the TiO<sub>2</sub> conduction band position was achieved through the synergistic coupling of Cu 3<em>d</em> orbitals hybridized with Ti 3<em>d</em> orbitals and hybridization of N 2<em>p</em> orbitals with O 2<em>p</em> orbitals. This approach significantly improved the utilization of sunlight while satisfying the redox potential requirements. Cu doping not only promoted the formation of oxygen vacancies but also reduced the formation of Ti<sup>3+</sup> ions, the photogenerated charge recombination centers. The non-compensated doping of N effectively increased the solubility of Cu<sup>2+</sup> ions in the titanium dioxide lattice, enhanced the adsorption of hydroxyl radical intermediates, and created conditions for the subsequent hydroxyl radical combinations promoting the generation of H<sub>2</sub>O<sub>2</sub>. In addition, the introduction of highly conductive graphene improved the interfacial carrier separation efficiency while realizing the spatial separation of redox sites, creating conditions for dual-channel reactions. The experimental results showed that the H<sub>2</sub>O<sub>2</sub> yield of Cu-N-TiO<sub>2</sub>/rGO under simulated sunlight reached 1266.7 µmol/L, which was 25.2 times higher than that of pristine TiO<sub>2</sub>. This study elucidated the synergistic mechanism of the energy band structure modulation and interfacial optimization, which provided a new idea for the design of dual-channel H<sub>2</sub>O<sub>2</sub> production photocatalysts.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"78 ","pages":"Pages 252-264"},"PeriodicalIF":17.7,"publicationDate":"2025-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145371352","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

MOF encapsulation derived slow-release oxygen species to enhance the activity and selectivity of methane selective oxidation: A transient DRIFTs Study MOF包封衍生的缓释氧增强甲烷选择性氧化的活性和选择性：一项瞬态漂移研究

IF 17.7 1区化学 Q1 CHEMISTRY, APPLIED

Chinese Journal of Catalysis

Pub Date : 2025-10-27 DOI: 10.1016/S1872-2067(25)64803-0

Ke-Xin Li , Hao Yuan , Ralph T. Yang , Zhun Hu

The methane selective oxidation was a “holy grail” reaction. However, peroxidation and low selectivity limited the application. Herein, we combined three Au contents with TiO₂ in both encapsulation (xAu@TiO₂) and surface-loaded (xAu/TiO₂) ways by MOF derivation strategy, reported a catalyst 0.5Au@TiO₂ exhibited a CH₃OH yield of 32.5 μmol·g^–1·h^–1 and a CH₃OH selectivity of 80.6% under catalytic conditions of only CH₄, O₂, and H₂O. Mechanically speaking, the catalytic activity was controlled by both electron-hole separation efficiency and core-shell structure. The interfacial contact between Au nanoparticles and TiO₂ in xAu@TiO₂ and xAu/TiO₂ induced the formation of oxygen vacancies, with 0.5 Au content showing the highest oxygen vacancy concentration. At the same Au content, xAu@TiO₂ generated more oxygen vacancies than xAu/TiO₂. The oxygen vacancy acted as an effective electron cold trap, which enhanced the photogenerated carrier separation efficiency and thereby improved the catalytic activity. In-situ DRIFTs revealed that the isolated OH (non-hydrogen bond adsorption) were key species for the methane selective oxidation, playing a role in the activation of CH₄ to *CH₃. However, an overabundance of isolated OH led to severe overoxidation. Fortunately, the core-shell structure over xAu@TiO₂ provided a slow-release environment for isolated OH through the intermediate state of *OH (hydrogen bond adsorption) to balance the formation rate and consumption rate of isolated OH, doubling the methanol yield and increasing the > 29% selectivity. These results showed a new strategy for the control of the overoxidation rate via a strategy of MOF encapsulation followed by pyrolytic derivation for methane selective oxidation.

甲烷选择性氧化是一个“圣杯”反应。然而，过氧化和低选择性限制了其应用。本文通过MOF衍生策略将三种Au与TiO2以包封（xAu@TiO2）和表面负载（xAu/TiO2）两种方式结合，报道了一种催化剂0.5Au@TiO2在仅CH4、O2和H2O的催化条件下，CH3OH产率为32.5 μmol·g-1·h-1， CH3OH选择性为80.6%。从力学上讲，催化活性受电子空穴分离效率和核壳结构的双重控制。在xAu@TiO2和xAu/TiO2中，Au纳米颗粒与TiO2的界面接触诱导氧空位的形成，当Au含量为0.5时，氧空位浓度最高。在相同Au含量下，xAu@TiO2比xAu/TiO2生成更多的氧空位。氧空位作为有效的电子冷阱，提高了光生载流子分离效率，从而提高了催化活性。原位漂移表明，游离OH（非氢键吸附）是甲烷选择性氧化的关键物质，在CH4活化为*CH3中起作用。然而，过量的分离OH会导致严重的过度氧化。幸运的是，xAu@TiO2上的核壳结构通过*OH的中间状态（氢键吸附）为分离OH提供了一个缓释环境，平衡了分离OH的形成速率和消耗速率，使甲醇收率翻了一倍，并提高了29%的选择性。这些结果为甲烷选择性氧化的MOF包封后热解衍生控制过氧化速率提供了新的策略。

{"title":"MOF encapsulation derived slow-release oxygen species to enhance the activity and selectivity of methane selective oxidation: A transient DRIFTs Study","authors":"Ke-Xin Li , Hao Yuan , Ralph T. Yang , Zhun Hu","doi":"10.1016/S1872-2067(25)64803-0","DOIUrl":"10.1016/S1872-2067(25)64803-0","url":null,"abstract":"<div><div>The methane selective oxidation was a “holy grail” reaction. However, peroxidation and low selectivity limited the application. Herein, we combined three Au contents with TiO<sub>2</sub> in both encapsulation (<em>x</em>Au@TiO<sub>2</sub>) and surface-loaded (<em>x</em>Au/TiO<sub>2</sub>) ways by MOF derivation strategy, reported a catalyst 0.5Au@TiO<sub>2</sub> exhibited a CH<sub>3</sub>OH yield of 32.5 μmol·g<sup>–1</sup>·h<sup>–1</sup> and a CH<sub>3</sub>OH selectivity of 80.6% under catalytic conditions of only CH<sub>4</sub>, O<sub>2</sub>, and H<sub>2</sub>O. Mechanically speaking, the catalytic activity was controlled by both electron-hole separation efficiency and core-shell structure. The interfacial contact between Au nanoparticles and TiO<sub>2</sub> in <em>x</em>Au@TiO<sub>2</sub> and <em>x</em>Au/TiO<sub>2</sub> induced the formation of oxygen vacancies, with 0.5 Au content showing the highest oxygen vacancy concentration. At the same Au content, <em>x</em>Au@TiO<sub>2</sub> generated more oxygen vacancies than <em>x</em>Au/TiO<sub>2</sub>. The oxygen vacancy acted as an effective electron cold trap, which enhanced the photogenerated carrier separation efficiency and thereby improved the catalytic activity. <em>In-situ</em> DRIFTs revealed that the isolated OH (non-hydrogen bond adsorption) were key species for the methane selective oxidation, playing a role in the activation of CH<sub>4</sub> to *CH<sub>3</sub>. However, an overabundance of isolated OH led to severe overoxidation. Fortunately, the core-shell structure over <em>x</em>Au@TiO<sub>2</sub> provided a slow-release environment for isolated OH through the intermediate state of *OH (hydrogen bond adsorption) to balance the formation rate and consumption rate of isolated OH, doubling the methanol yield and increasing the > 29% selectivity. These results showed a new strategy for the control of the overoxidation rate <em>via</em> a strategy of MOF encapsulation followed by pyrolytic derivation for methane selective oxidation.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"78 ","pages":"Pages 202-214"},"PeriodicalIF":17.7,"publicationDate":"2025-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145371344","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Dual-hole extraction strategy promotes photoelectrochemical water splitting of bismuth vanadate photoanode 双孔萃取策略促进了钒酸铋光阳极的电化学水分解

IF 17.7 1区化学 Q1 CHEMISTRY, APPLIED

Chinese Journal of Catalysis

Pub Date : 2025-09-15 DOI: 10.1016/S1872-2067(25)64778-4

Hua Yang , Dingyanyan Zhou , Kaige Tian , Lingjiang Kong , Pengfei An , Jing Zhang , Yujin Ji , Youyong Li , Junqing Yan

Elemental doping of BiVO₄ crystal lattices effectively enhances carrier separation, thereby facilitating efficient photoelectrochemical water splitting. However, the positive effect of elementally induced lattice distortions on hole extraction has been neglected. Herein, the crystal lattice of BiVO₄ is distorted by doping with an inexpensive Cs metal; then, CoFe₂O₄ is used as an efficient hole-extraction layer to further modify the surface of the doped photoanode. Benefiting from the above design, the newly prepared CoFe₂O₄-Cs-BiVO₄ photoanode achieved a photocurrent density of 5.66 mA cm^–2 at 1.23 V vs. a reversible hydrogen electrode, indicating a 3.9-fold improvement in photocurrent density. Detailed physicochemical characterization and density functional theory calculations showed that the lattice distortion induced by Cs doping promoted the directional migration of BiVO₄ bulk-phase holes to the CoFe₂O₄ layer. Additionally, the coupled CoFe₂O₄ can be used as a hole extraction layer to further enhance the interfacial migration of carriers. The synergistic effect of the two effectively promotes the directional migration of photogenerated carriers from the BiVO₄ bulk phase to the active sites of the oxygen evolution reaction, thereby effectively inhibiting carrier recombination. This study revealed the positive effect of the dual-hole extraction strategy on solar energy conversion, thereby opening new avenues for the rational design of photoanodes.

BiVO4晶格的元素掺杂有效地增强了载流子分离，从而促进了高效的光电化学水分解。然而，元素引起的晶格畸变对空穴提取的积极作用被忽视了。其中，BiVO4的晶格通过掺杂廉价的Cs金属而被扭曲；然后，利用CoFe2O4作为高效的空穴萃取层，进一步修饰掺杂光阳极的表面。得益于上述设计，与可逆氢电极相比，新制备的CoFe2O4-Cs-BiVO4光阳极在1.23 V下的光电流密度达到5.66 mA cm-2，光电流密度提高了3.9倍。详细的物理化学表征和密度泛函理论计算表明，Cs掺杂引起的晶格畸变促进了BiVO4本体相空穴向CoFe2O4层的定向迁移。此外，耦合的CoFe2O4可以作为空穴萃取层，进一步增强载流子的界面迁移。两者的协同作用有效地促进了光生载流子从BiVO4体相向析氧反应活性位点的定向迁移，从而有效地抑制了载流子的重组。本研究揭示了双孔提取策略对太阳能转换的积极作用，从而为合理设计光阳极开辟了新的途径。

{"title":"Dual-hole extraction strategy promotes photoelectrochemical water splitting of bismuth vanadate photoanode","authors":"Hua Yang , Dingyanyan Zhou , Kaige Tian , Lingjiang Kong , Pengfei An , Jing Zhang , Yujin Ji , Youyong Li , Junqing Yan","doi":"10.1016/S1872-2067(25)64778-4","DOIUrl":"10.1016/S1872-2067(25)64778-4","url":null,"abstract":"<div><div>Elemental doping of BiVO<sub>4</sub> crystal lattices effectively enhances carrier separation, thereby facilitating efficient photoelectrochemical water splitting. However, the positive effect of elementally induced lattice distortions on hole extraction has been neglected. Herein, the crystal lattice of BiVO<sub>4</sub> is distorted by doping with an inexpensive Cs metal; then, CoFe<sub>2</sub>O<sub>4</sub> is used as an efficient hole-extraction layer to further modify the surface of the doped photoanode. Benefiting from the above design, the newly prepared CoFe<sub>2</sub>O<sub>4</sub>-Cs-BiVO<sub>4</sub> photoanode achieved a photocurrent density of 5.66 mA cm<sup>–2</sup> at 1.23 V <em>vs.</em> a reversible hydrogen electrode, indicating a 3.9-fold improvement in photocurrent density. Detailed physicochemical characterization and density functional theory calculations showed that the lattice distortion induced by Cs doping promoted the directional migration of BiVO<sub>4</sub> bulk-phase holes to the CoFe<sub>2</sub>O<sub>4</sub> layer. Additionally, the coupled CoFe<sub>2</sub>O<sub>4</sub> can be used as a hole extraction layer to further enhance the interfacial migration of carriers. The synergistic effect of the two effectively promotes the directional migration of photogenerated carriers from the BiVO<sub>4</sub> bulk phase to the active sites of the oxygen evolution reaction, thereby effectively inhibiting carrier recombination. This study revealed the positive effect of the dual-hole extraction strategy on solar energy conversion, thereby opening new avenues for the rational design of photoanodes.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"77 ","pages":"Pages 236-249"},"PeriodicalIF":17.7,"publicationDate":"2025-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145061246","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Synergistic interface engineering in Cu-Zn-Ce catalysts for efficient CO2 hydrogenation to methanol Cu-Zn-Ce催化剂催化CO2加氢制甲醇的协同界面工程

IF 17.7 1区化学 Q1 CHEMISTRY, APPLIED

Chinese Journal of Catalysis

Pub Date : 2025-09-15 DOI: 10.1016/S1872-2067(25)64773-5

Yang Chen , Diwen Zhou , Yongli Chang , Hongqiao Lin , Yunzhao Xu , Yong Zhang , Ding Yuan , Lizhi Wu , Yu Tang , Chengyi Dai , Xingang Li , Qinhong Wei , Li Tan

CO₂ hydrogenation to CH₃OH is of great significance for achieving carbon neutrality. Here, we show a urea-assisted grinding strategy for synthesizing Cu-Zn-Ce ternary catalysts (CZC-G) with optimized interfacial synergy, achieving superior performance in CO₂ hydrogenation to methanol. The CZC-G catalyst demonstrated exceptional methanol selectivity (96.8%) and a space-time yield of 73.6 g_MeOH·kg_cat^–1·h^–1 under optimized conditions. Long-term stability tests confirmed no obvious deactivation over 100 h of continuous operation. Structural and mechanistic analyses revealed that the urea-assisted grinding method promotes the formation of Cu/Zn-O_v-Ce ternary interfaces and inhibits the reduction of ZnO, enabling synergistic interactions for efficient CO₂ activation and selective stabilization of formate intermediates (HCOO*), which are critical for methanol synthesis. In-situ diffuse reflectance infrared Fourier transform spectra and X-ray absorption spectroscopy studies elucidated the reaction pathway dominated by the formate mechanism, while suppressing the reverse water-gas shift reaction. This work underscores the critical role of synthetic methodologies in engineering interfacial structures, offering a strategy for designing high-performance catalysts for sustainable CO₂ resource utilization.

CO2加氢生成CH3OH对实现碳中和具有重要意义。在这里，我们展示了一种尿素辅助研磨策略来合成Cu-Zn-Ce三元催化剂（CZC-G），具有优化的界面协同作用，在CO2加氢制甲醇中取得了优异的性能。在优化条件下，CZC-G催化剂的甲醇选择性为96.8%，空时产率为73.6 gMeOH·kgcat-1·h-1。长期稳定性试验证实连续运行100小时无明显失活。结构和机理分析表明，尿素辅助研磨方法促进了Cu/Zn-Ov-Ce三元界面的形成，抑制了ZnO的还原，实现了有效的CO2活化和甲酸酯中间体（HCOO*）的选择性稳定，这对甲醇合成至关重要。现场漫反射红外傅里叶变换光谱和x射线吸收光谱研究阐明了以甲酸酯机制为主的反应途径，同时抑制了逆水气移位反应。这项工作强调了合成方法在工程界面结构中的关键作用，为设计可持续利用二氧化碳资源的高性能催化剂提供了策略。

{"title":"Synergistic interface engineering in Cu-Zn-Ce catalysts for efficient CO2 hydrogenation to methanol","authors":"Yang Chen , Diwen Zhou , Yongli Chang , Hongqiao Lin , Yunzhao Xu , Yong Zhang , Ding Yuan , Lizhi Wu , Yu Tang , Chengyi Dai , Xingang Li , Qinhong Wei , Li Tan","doi":"10.1016/S1872-2067(25)64773-5","DOIUrl":"10.1016/S1872-2067(25)64773-5","url":null,"abstract":"<div><div>CO<sub>2</sub> hydrogenation to CH<sub>3</sub>OH is of great significance for achieving carbon neutrality. Here, we show a urea-assisted grinding strategy for synthesizing Cu-Zn-Ce ternary catalysts (CZC-G) with optimized interfacial synergy, achieving superior performance in CO<sub>2</sub> hydrogenation to methanol. The CZC-G catalyst demonstrated exceptional methanol selectivity (96.8%) and a space-time yield of 73.6 g<sub>MeOH</sub>·kg<sub>cat</sub><sup>–1</sup>·h<sup>–1</sup> under optimized conditions. Long-term stability tests confirmed no obvious deactivation over 100 h of continuous operation. Structural and mechanistic analyses revealed that the urea-assisted grinding method promotes the formation of Cu/Zn-O<sub>v</sub>-Ce ternary interfaces and inhibits the reduction of ZnO, enabling synergistic interactions for efficient CO<sub>2</sub> activation and selective stabilization of formate intermediates (HCOO*), which are critical for methanol synthesis. <em>In-situ</em> diffuse reflectance infrared Fourier transform spectra and X-ray absorption spectroscopy studies elucidated the reaction pathway dominated by the formate mechanism, while suppressing the reverse water-gas shift reaction. This work underscores the critical role of synthetic methodologies in engineering interfacial structures, offering a strategy for designing high-performance catalysts for sustainable CO<sub>2</sub> resource utilization.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"77 ","pages":"Pages 171-183"},"PeriodicalIF":17.7,"publicationDate":"2025-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145061311","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0