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Highlights

胡啟章教授 Chi-Chang Hu
 
Trapped interfacial redox introduces reversibility in the oxygen reduction reaction in a non-aqueous Ca2+ electrolyte
Yi-Ting Lua,b, Alex R. Nealea, Chi-Chang Hub, Laurence J. Hardwicka
a Department of Chemistry, University of Liverpool
b Department of Chemical Engineering, National Tsing Hua University,
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This work proposes a new design concept for non-aqueous rechargeable metal-air batteries (more specifically, calcium-air batteries). In designing non-aqueous electrolyte formulations for metal-air cells, how to effectively utilize the so-called trapped interfacial redox in order to achieve highly reversible oxygen electrochemistry at the air electrode could be critical. 
In this work, the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) have been investigated in the Ca2+-containing dimethyl sulfoxide electrolyte. While the ORR/OER redox appears irreversible, the introduction of tetrabutyl-ammonium perchlorate (TBAClO4) co-salt in excess concentrations results in the quasi-reversibility of the ORR/OER redox process. Through the systematic investigations, the degree of reversibility depends on the competition between Ca2+ and TBA+ to form ion pair with the newly generated superoxide (O2-). This finding has made important progress on the development of rechargeable calcium-air batteries.
In situ Raman spectroscopy and rotating ring-disc electrode (RRDE) experiments detailed about the nature of species formed at the electrode surface and revealed a new charge storage mechanism: the trapped interfacial redox. In this mechanism, the first step of the ORR involves the generation of O2-, followed primarily by the irreversible partial passivation of the surface via the CaxOproduct formation (the dominant initial reaction). Once this product matrix has been constructed, the highly reversible TBA+--O2- is formed and stored within the CaxOy product interlayer at the electrode surface, and consequently, undergoes a facile oxidation reaction to regenerate O2.
此研究對於有機系金屬-空氣電池(-空氣電池)的發展,提供了另一種電池設計上的方式在未來思考許多有機系金屬-空氣電池的電解液系統時,如何有效獲得所謂的受限介面氧化還原對,可能是有機系金屬-空氣電池的正極可逆性優劣的關鍵。
我們在含有鈣離子的二甲基亞碸中進行一系列的電化學測試,用以研究鈣-空氣電池其氧氣還原/析出反應的行為。雖然在鈣電解液中,氧氣還原/析出反應已被證明是不可逆的;不過當我們引入過量的四丁基銨鹽後,卻發現了氧氣還原/析出反應開始有其可逆性。我們發現鈣離子與四丁基銨離子對超氧離子(O2-)的競爭反應是此現象背後的主因,並為鈣-空氣電池的充放電可逆性跨出重要的一步。
藉由使用臨場拉曼光譜與旋轉環盤電極,我們研究了電極介面上主要參與反應的物種之性質,並由此發現了一種新的電荷儲存機制:受限介面氧化還原對。另外,我們也提出了此種電解液中的氧氣還原反應機制。亦即氧氣還原形成超氧離子時,超氧離子與鈣離子會先在電極表面上形成一層產物層(CaxOy),隨後四丁基銨根與超氧離子的結合主要發生於此產物層內部,此種受限於表面的氧氣還原反應導致其逆反應氧氣產生反應所需的能量減少許多,開啟了氧氣還原/析出反應的電化學可逆性。
 


周鶴修教授 Ho-Hsiu Chou


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Journal of Materials Chemistry A2021, 9, 6109-6116

雙模式可自修復之高分子應用於仿皮膚之感測元件
Disulfide bond and Diels–Alder reaction bond hybrid polymers with high stretchability, transparency, recyclability, and intrinsic dual healability for skin-like tactile sensing
Chun-Ming Yeh, Chun-Hsiu Lin, Tzung-You Han, Yu-Ting Xiao, Yi-An Chen, Ho-Hsiu Chou*
Department of Chemical Engineering, National Tsing Hua University
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Abstract: For next-generation electronics, it is crucial to be able to accurately mimic the nature of human skin and develop skin-inspired materials and devices for electronic skin (e-skin) applications. However, it is a great challenge to design such a materials because they require the complex integration of stretchability, skin adhesiveness, transparency, healability, and tactile sensing. Herein, we present the first dual covalently reversible dynamic bond-based polymer that can be inte- grated with various functional materials and used as a skin-like sensor. A series of polymers was designed using polypropylene glycol (PPG)- based polyurethane (PU) as the polymer backbone, and these poly- mers could integrate two types of covalent reversible dynamic bonds, Diels–Alder and disulfide bonds, in one polymer for the first time. Based on our design, a polymer was created with the advantages of high stretchability, fast healing abilities (60 C, 5 min), skin adhesion, recyclability, high transparency, and tactile sensing abilities. We provide an alternative strategy for the construction of skin-inspired multifunctional materials for e-skin applications.
 

宋信文教授 Hsing-Wen Sung
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Nature Communications 2020, 11, 534.

Photosynthesis-Inspired H2 Generation Using a Chlorophyll-Loaded Liposomal Nanoplatform to Detect and Scavenge Excess ROS
Wei-Lin Wan, Bo Tian, Yu-Jung Lin, Chiranjeevi Korupalli, Ming-Yen Lu, Qinghua Cui, Dehui Wan, Yen Chang , Hsing-Wen Sung*
Department of Chemical Engineering, National Tsing Hua University
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A disturbance of reactive oxygen species (ROS) homeostasis may cause the pathogenesis of many diseases. Inspired by natural photosynthesis, this work proposes a photo-driven H2-evolving liposomal nanoplatform (Lip NP) that comprises an upconversion nanoparticle (UCNP) that is conjugated with gold nanoparticles (AuNPs) via an ROS-responsive linker, which is encapsulated inside the liposomal system in which the lipid bilayer embeds chlorophyll a (Chla). The UCNP functions as a transducer, converting NIR light into upconversion luminescence for simultaneous imaging and therapy in situ. Functioning as light-harvesting antennas, AuNPs are used to detect the local concentration of ROS for FRET biosensing, while the Chla activates the photosynthesis of H2 gas to scavenge local excess ROS. The results thus obtained indicate the potential of using the Lip NPs in the analysis of biological tissues, restoring their ROS homeostasis, possibly preventing the initiation and progression of diseases.
許多疾病的生成都和氧化壓力有關。在此研究中,我們結合葉綠素及上轉換奈米粒子成功開發出一微脂體奈米平台。在光激發下能夠產生氫氣來達到抗氧化與抗發炎的功效,同時利用螢光共振能量轉移效應做為偵測局部氧化壓力的指標。此奈米平台將治療及偵測的功能結合在一起,預期將能廣泛性應用在發炎性疾病當中。


 

胡育誠教授Yu-Chen Hu 
Biomaterials. 252: 120094. (IF 10.317).
CRISPR interference-mediated Noggin knockdown promotes BMP2-induced osteogenesis and calvarial bone healing
Hsu, M.-N., Yu, F.-J., Chang, Y.-H., Huang, K-L., Pham, N. N., Troung, A.V., Lin, M.-W., Nguyen, N.T.K., Hwang, S.-M., Hu, Y.-C.*
Department of Chemical Engineering, National Tsing Hua University
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Bone regeneration often requires stimulation by the growth factor BMP2, but BMP2 also stimulates cells to produce antagonist Noggin, thus reducing the bone repair efficiency. CRISPRi is a new tool for suppressing gene expression. Professor Yu-Chen Hu’s team developed and applied CRISPRi to inhibit Noggin's expression upon simultaneous BMP2 co-expression, thus improving the efficiency of adipose-derived stem cell differentiation towards osteogenic lineage.  Implanting the engineered stem cell into a large skull defect can effectively stimulate the regeneration of the skull. The results were published in September 2020 in the internationally renowned journal Biomaterials (2020, 252: 120094).
硬骨修復目前常應用BMP2生長因子刺激骨再生,但是BMP2也會刺激細胞產生拮抗劑Noggin,因此減弱骨修復效果。CRISPRi是嶄新抑制基因表現的工具。胡育誠教授團隊開發應用CRISPRi在表現BMP2的同時,抑制Noggin的表現,因此能提升脂肪幹細胞往骨分化的效率。將此幹細胞植入大範圍頭蓋骨缺陷,則可以有效刺激頭蓋骨的再生。成果已於2020年9月發表於國際知名期刊Biomaterials 2020, 252: 120094.
 


何榮銘教授Rong-Ming Ho
Science advances20206, eabc3644.
Networks with controlled chirality via self-assembly of chiral triblock terpolymers

Wang, H.F.; Chiu, P.T.; Yang, C.Y.; Xie, Z.H.; Hung, Y.C.; Lee, J.Y.; Tsai, J.C.; Prasad, I.; Jinnai, H.; Thomas, E.L. and Ho, R.M.
Department of Chemical Engineering, National Tsing Hua University
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Nanonetwork-structured materials can be found in nature and synthetic materials. A double gyroid (DG) with a pair of chiral networks but opposite chirality can be formed from the self-assembly of diblock copolymers. For triblock terpolymers, an alternating gyroid (GA) with two chiral networks from distinct end blocks can be formed; however, the network chirality could be positive or negative arbitrarily, giving an achiral phase. Here, by taking advantage of chirality transfer at different length scales, GA with controlled chirality can be achieved through the self-assembly of a chiral triblock terpolymer. With the homochiral evolution from monomer to multichain domain morphology through self-assembly, the triblock terpolymer composed of a chiral end block with a single-handed helical polymer chain gives the chiral network from the chiral end block having a particular handed network. Our real-space analyses reveal the preferred chiral sense of the network in the GA, leading to a chiral phase.
 奈米網狀結構廣泛的存在於自然界以及合成材料中,其中最為人所知的莫過於雙螺旋二十四面體(double gyroid),一個由兩股掌性網狀結構互相穿插交織而成的結構。一般而言,製備此結構時會使用雙嵌段共聚物,但由於兩股網狀結構的組成相同,無法將其分離;若要控制其掌性,則需使用三嵌段共聚物來形成交替雙螺旋二十四面體(GA),但其掌性分布會隨機生成,無法控制。此研究使用帶有掌性嵌段的三嵌段共聚物,利用同掌性演化效應自組裝形成可控掌性之GA。由實空間影像可清晰觀察到各嵌段形成特定的掌性,而透過分析三圍影像重建的二面角結果也證實了此可控掌性的網狀結構。此結構可用以製備具有單螺旋奈米通道的奈米多孔聚合物,並將其用於模板化合成,例如模板化原子層沉積、電化學沉積、溶膠-凝膠反應和化學電鍍,得到有序的奈米混成材料。這種材料可用於掌性分束器、負折射和准直效應之類的掌性超穎材料。

 

呂世源教授 Shih-Yuan Lu
Appl. Catal. B. – Environ., 279, 119375, (2020)

組份平衡之三金屬金屬有機骨架材料做為超高效穩定析氧反應電觸媒
Composition-Balanced Trimetallic MOFs as Ultra-Efficient Electrocatalysts for Oxygen Evolution Reaction at High Current Densities

Duraisamy Senthil Raja, Chun-Lung Huang, Yu-An Chen, YongMan Choi, Shih-Yuan Lu,*
Department of Chemical Engineering, National Tsing Hua University
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Renewable energy driven electrolytic water splitting is regarded as the most promising way to supply clean hydrogen fuel to answer the present and future energy and environmental issues. It is highly critical to develop cost-effective, highly efficient, robust electrodes to achieve low overpotentials and high stability at high current densities for large-scale commercial electrolytic water splitting applications. In this regard, exploration and design of synergistic effects between constituent active species of multi-component catalysts are an effective way to drastically boost the electrocatalytic performances of the catalysts. Furthermore, metal-organic framework (MOF), possessing versatile catalytic activities, remarkable structural diversity, high surface areas, and tunable pore structure, was recently demonstrated an outstanding catalyst for the OER. Combining the above two observations leads to the motivation of development of multi-metal based MOFs as OER catalysts. There however are lacking guidelines for composition design of multi-component catalysts. Herein, a maximized-entropy concept was proposed to maximize the synergistic effects for maximum enhancements in electrocatalytic efficiencies of multi-component catalysts. The concept is based on maximizing the configurational entropy of the multi-component system, from which equimolar system is derived to be the one giving the maximum configurational entropy. Accordingly, composition-balanced trimetallic MOF materials were developed as direct OER electrocatalysts, which deliver and sustain high current densities at ultra-low overpotentials. Equimolar iron, cobalt, and nickel based trimetallic MOFs grown in-situ on nickel foam (NF), was demonstrated outstanding OER performances with ultra-low overpotentials of 196 and 284 mV at current densities of 10 and 1,000 mA cm−2, respectively, as well as an ultra-low Tafel slope of 29.5 mV dec−1 in alkaline aqueous media (1 M KOH). The stability of the electrocatalyst was also outstanding at large current densities, experiencing only 5% loss in current densities, when chronoamperometrically tested at an ultra-high and industrially relevant current density of 1,000 mA cm−2 for over 50 hours. The present composition-balanced Fe, Co, Ni based trimetallic MOF outperforms almost all top rated OER electrocatalysts in efficiency and stability, particularly at high current densities.
以可再生能源發電(太陽能、風力、水力等)搭配電解水產氫,是一能永續發展的絕佳綠色產氫技術,同時亦可以此解決可再生能源發電之不穩定性及間歇性問題。電解水產氫技術之發展,價廉、高效、穩定的電觸媒為其關鍵,期能降低電解水的兩個基本電化學反應:析氫反應與析氧反應之過電位,使此製程更具競爭優勢。其中析氧反應更為關鍵,其為瓶頸所在。以金屬有機骨架材料(Metal-Organic Framework, MOF)為基礎的觸媒,具多樣催化活性、高比表面積、結構多樣性、孔洞可調性等優點,吸引眾多研究人員投入研發。單成份觸媒之發展已達飽和需借助多成份觸媒之成份偕同效應來增益觸媒效能,但多成份觸媒之組成設計是一挑戰。本篇論文提出一熵極大化原理以設計多成分電觸媒,獲得最大程度偕同效應以獲致最佳電催化效能,並據以合成等莫爾金屬MOF,展現優異產氧催化效能。其達成10及1000 mA/cm2電流密度僅需196及284 mV之超低過電位,且在超高初始電流密度1000 mA/cm2下連續操作50小時,電流密度僅下降5%,為一突破性析氧電觸媒。本篇論文發表於環境工程領域之旗艦期刊Appl. Catal. B. – Environ.。

 

段興宇教授Hsing-Yu Tuan
Advanced Science, 2019, 6, 1801354

紅磷鉀離子電池電極
Red Phosphorus Potassium‐Ion Battery Anodes

Wei-Chung Chang, Jen-Hsuan Wu, Kuan-Ting Chen, and Hsing-Yu Tuan*
Department of Chemical Engineering, National Tsing Hua University
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Phosphorus (P) possess the highest theoretical specific capacity (865 mA h g-1) among all the elements for potassium-ion battery (PIB) anodes. Although Red P (RP) has intrinsic advantages over its allotropes, including low cost and non-toxicity, and simpler preparation, it is yet unknown to effectively activate it into a high performance PIB anode. Here, we report high-performance RP potassium-ion battery anodes. Two important factors are found to facilitate RP react with K-ions reversibly: (i) Nanoscale RP particles are dispersed evenly in a conductive carbon matrix composed of multi-wall carbon nanotubes (MWCNTs) and Ketjen black (KB) that provide an efficient electrical pathway and a tough scaffold. (ii) The XPS spectrum of RP/C composites was examined for both dry ball milling and wet ball milling processes, which perhaps show that no P-C bonds formation is beneficial to allow K ions to react with RP effectively. As a result, the RP/C electrodes deliver a reversible specific capacity of ~750 mA h g-1 and exhibit a high rate capability (~300 mA h g-1 at 1000 mA g-1). RP/C full cells using KMnHCF as cathode show a long cycling life (680 cycles) at a current density of 1000 mA g-1, in addition, a pouch type battery is built to demonstrate practical applications.
在鉀離子電池(PIB)陽極的所有元素中,磷(P)具有最高的理論比容量(865 mA h g-1)。儘管紅磷(RP)在同素異形體方面具有內在的優勢,包括低成本,無毒,製備簡單等,但尚未有效地將其激活為高性能PIB陽極。此處報導了高性能RP PIB陽極。已發現促進RP與K離子可逆反應的兩個重要因素:i)奈米級RP顆粒均勻地分散在由多壁碳奈米管和科琴黑組成的導電碳基質中,提供了有效的電通路和堅韌的支架。 ii)X射線光電子能譜和電化學性能的結果可能表明,沒有形成P-C鍵有利於使K-離子與RP有效反應。結果,RP / C電極提供了約750 mA h g-1的可逆比容量,並顯示出高倍率容量(在1000 mA g-1時約為300 mA h g-1)。使用六氰合鐵酸錳酸鉀作為陰極的RP / C全電池在1000 mA g-1的電流密度下顯示出較長的循環壽命(680個循環),此外,還製作了袋裝電池來演示實際應用。\

 

周鶴修教授 Ho-Hsiu Chou

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Applied Catalysis B: Environmental 2021, 283, 119659

含N-摻雜碳量子點嵌入之高分子奈米顆粒於可見光產氫之應用
Visible-light-driven hydrogen evolution using nitrogen-doped carbon quantum dot-implanted polymer dots as metal-free photocatalysts

Mohamed Hammad Elsayed, Jayachandran Jayakumar, Mohamed Abdellah, Tharwat Hassan Mansoure, Kaibo Zheng, Ahmed M.Elewa, Chih-Li Chang, Li-YuTing, Wei-Cheng Lin, Hsiao-hua Yu, Wen-Hsin Wang, Chih-Chia Chung, Ho-Hsiu Chou*
Department of Chemical Engineering, National Tsing Hua University
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Abstract: Given the photocatalytic properties of semiconducting polymers and carbon quantum dots (CQDs), we report a new  structure for a metal-free photocatalytic system with a promising efficiency for hydrogen production through the combination of an organic semiconducting polymer (PFTBTA) and N-doped carbon quantum dots (NCQDs) covered by PS-PEGCOOH to produce heterostructured photocatalysts in the form of polymer dots (Pdots). This design could provide strong interactions between the two materials owing to the space confinement effect in nanometer-sized Pdots. Small particle size NCQDs are easy to insert inside the Pdot, which leads to an increase in the stability of the Pdot structure and enhances the hydrogen evolution rate by approximately 5-fold over that of pure PFTBTA Pdots. The photophysics and the mechanism behind the catalytic activity of our design are investigated by transient absorption measurement, demonstrating the role of NCQDs to enhance the charge separation and the photocatalytic efficiency of the PFTBTA Pdot.