圖1：原理示意圖      

電化學(xué)原位紅外光譜分析是紅外分析技術(shù)的一個重要分支，能夠定性分析電催化(如CO2電還原等)反應(yīng)、各種類型電池(如鋰離子、鋰硫電池等)充放電過程中電極表面的產(chǎn)物或中間產(chǎn)物隨時間(電位)不斷變化的趨勢，是研究電化學(xué)反應(yīng)機(jī)理以及電化學(xué)反應(yīng)動力學(xué)的重要手段之一。

一 基本原理：

內(nèi)反射模式:

(1)在單晶硅(Si)上化學(xué)鍍或真空鍍一層納米金膜，納米金屬膜具有表面增強(qiáng)效應(yīng)。

(2)納米金膜可作為導(dǎo)電基底，在導(dǎo)電基底上滴涂或電沉積上電催化劑，作為工作電極。

(3)表面增強(qiáng)紅外，可得到電催化劑吸附態(tài)產(chǎn)物以及中間產(chǎn)物信息。

 圖2：內(nèi)反射模式基本原理

外反射模式:

(1)在基底電極(如GCE)表面電沉積或滴涂電催化劑作為工作電極。

(2)工作電極距離晶體的距離可以調(diào)節(jié)。

(3)晶體可選Ge，ZnSe，CaF₂，Si等。

圖3：外反射模式基本原理

二 附件組成：

(1)紅外光譜儀主機(jī)適配底板,適配主流紅外光譜儀。

(2)平面鏡加曲面鏡。

(3)入射角度調(diào)節(jié)系統(tǒng)。

(4)衰減全反射晶體。

(5)玻璃電化學(xué)池(單池或H型池)以及PEEK外反射池。

(6)電極(玻碳電極、對電極、參比電極)。

(7)距離調(diào)節(jié)系統(tǒng)。

三 主要特點(diǎn)：

(1)可變?nèi)肷浣枪鈱W(xué)臺，30-80度連續(xù)可調(diào)，以保證不同電催化劑處于最大光通量狀態(tài)。

(2)衰減全反射晶體上具有一層增透膜，光通量增大10％以上

(3)電化學(xué)池密封性能好，可通入反應(yīng)氣體。

(4)晶體拆卸簡單，方便打磨清洗。

(5)晶體種類可選，如Si，CaF₂，ZnSe等。

(6)電化學(xué)單池或H型池，切換方便。

(7)提供現(xiàn)場技術(shù)服務(wù)。

(7)可根據(jù)客戶需求定制反應(yīng)池并提供可行性方案。

四  ATR Crystal characteristics for FTIR sampling

 
應(yīng)用案例

CO₂電還原 J. Am. Chem. Soc.2022, 144, 259?269

氧氣析出反應(yīng) J. Am. Chem. Soc. 2022, 144, 21, 9271–9279

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4. Yang Peng*, et al. Breaking Linear Scaling Relationship by Compositional and Structural Crafting of Ternary Cu-Au/Ag Nanoframes for Electrocatalytic Ethylene Production. Angew. Chem. Int. Ed. 2021, 60, 2508-2518 

5. Zhuo Yu, Yonggang Wang*, et al. Boosting Polysulfide Redox Kinetics by Graphene-Supported Ni Nanoparticles with Carbon Coating. Adv. Energy Mater. 2020, 10, 2000907

6. Xinwei Ding, Zhi Yang*, et al. Biomimetic Molecule Catalysts to Promote the Conversion of Polysulfides for Advanced Lithium–Sulfur Batteries Adv. Funct. Mater. 2020, 30, 2003354 

7. Hong Guo*, Xueliang Sun*, et al. Dual Active Site of the Azo and Carbonyl-Modified Covalent Organic Framework for High-Performance Li Storage. ACS Energy Lett. 2020, 5, 1022-1031

8. Bin Zhang* et al. Superficial Hydroxyl and Amino Groups Synergistically Active Polymeric Carbon Nitride for CO₂ Electroreduction. ACS Catal. 2019, 9, 10983-10989 

9. Suya Zhou, Zhi Yang*, et al. Dual-Regulation Strategy to Improve Anchoring and Conversion of Polysulfides in Lithium–Sulfur Batteries ACS Nano. 2020, 14, 7538–7551

10. Yongyao Xia*, et al. Low-Temperature Charge/Discharge of Rechargeable Battery Realized by Intercalation Pseudocapacitive Behavior. Adv. Sci. 2020, 7, 2000196

11. Lei Wang*, Yonggang Wang, et al. Pencil-drawing on nitrogen and sulfur co-doped carbon paper: An effective and stable host to pre-store Li for high-performance lithium–air batteries. Energy Storage Materials. 2020, 26, 593-603

12. Bin Zhang, et al. Unveiling in situ evolved In/In2O3? x heterostructure as the active phase of In2O3 toward efficient electroreduction of CO₂ to formate. Science Bulletin. 2020, 65, 1547-1554

13. Huani Li, Shubiao Xia*, Hong Guo*, et al. Red Phosphorus Confined in Hierarchical Hollow Surface-Modified Co9S8 for Enhanced Sodium Storage. Sustainable Energy Fuels. 2020, 4, 2208-2219 

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15. Guanglei Cui*, et al. Investigation on the Cathodic Interfacial Stability of Nitrile Electrolyte and its performance with High Voltage LiCoO₂ Chem. Commun. 2020, 56, 4998-5001 

16. Zhongbin Zhuang*, et al. A highly-active, stable and low-cost platinum-free anode catalyst based on RuNi for hydroxide exchange membrane fuel cells. Nat. Commun. 2020, 11, 5651 

17. Tiancun Liu, Yong Wang*, et al. Organic supramolecular protective layer with rearranged and defensive Li deposition for stable and dendrite-free lithium metal anode. Energy Storage Materials. 2020, 32, 261–271

18. X. Yin, Y. Wang*, et al. Designing cobalt-based coordination polymers for high-performance sodium and lithium storage: from controllable synthesis to mechanism detection. Materials Today Energy. 2020, 17, 100478

19. Song Chen, Jintao Zhang*, et al. Regulation of Lamellar Structure of Vanadium Oxide via Polyaniline Intercalation for High-Performance Aqueous Zinc-Ion Battery. Adv. Funct. Mater. 2020, 30, 2003890 

20. Yanrong Xue, Zhongbin Zhuang*, et al. Sulfate-Functionalized RuFeOx as Highly Efficient Oxygen Evolution Reaction Electrocatalyst in Acid. Adv. Funct. Mater. 2021, 31, 2101405

21. Hong Guo*, et al. Cooperative catalytic interface accelerates redox kinetics of sulfur species for high-performance Li-S batteries. Energy Storage Materials. 2021, 40, 139-149

22. Bin Zhang*, et al. Promoting nitric oxide electroreduction to ammonia over electron-rich Cu modulated by Ru doping. SCIENCE CHINA Chemistry. 2021, 64, 1493–1497

23. Yang Peng*, et al. Geometric Modulation of Local CO Flux in Ag@Cu2O Nanoreactors for Steering the CO₂RR pathway toward High-Efficacy Methane Production. Adv. Mater. 2021, 33, 2101741

24. Yonggang Wang*, et al. Molecular Tailoring of n/p-type Phenothiazine Organic Scaffold for Zinc Batteries. Angew. Chem. Int. Ed. 2021, 60, 20826-20832 

25. Hongliang Jiang*, Chunzhong Li*, et al. Dynamically Formed Surfactant Assembly at the Electrified Electrode–Electrolyte Interface Boosting CO₂ Electroreduction. J. Am. Chem. Soc. 2022, 144, 6613–6622

26. Yang Peng*, et al. Au-activated N motifs in non-coherent cupric porphyrin metal organic frameworks for promoting and stabilizing ethylene production. Nat. Commun. 2022, 13, 63 

27. Jie Zeng*, et al. Copper-catalysed exclusive CO₂ to pure formic acid conversion via single-atom alloying. Nature Nanotechnology. 2021, 16, 1386-1393 

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30. Rui Lin, Jianhui Wang, et al. Asymmetric donor-acceptor moleculeregulated core-shell-solvation electrolyte for high-voltage aqueous batteries. Joule 2022, 6, 399–417 

31. Xiaogang Zhang*, et al. Successive Cationic and Anionic (De)-Intercalation/Incorporation into an Ion-Doped Radical Conducting Polymer. Batteries & Supercaps 2019, 2, 979-984

32. Zhongju Wang, Yongzhu Fu*, et al. Biredox‐Ionic Anthraquinone‐Coupled Ethylviologen Composite Enables Reversible Multielectron Redox Chemistry for Li‐Organic Batteries. Adv. Sci. 2022, 9, 2103632 

33. Jintao Zhang*, et al. Defect evolution of hierarchical SnO₂ aggregatesfor boosting CO₂ electrocatalytic reduction. J. Mater. Chem. A 2021, 9, 14741-14751

34. Fei Ai, Yijun Lu*, et al. Heteropoly acid negolytes for high-power-density aqueous redox flow batteries at low temperatures. Nature Energy 2022, 7, 417–426 

35. Zhejun Li, Yijun Lu*. Polysulfide-based redox flow batteries with long life and low levelized cost enabled by charge-reinforced ion-selective membranes. Nature Energy 2021, 6, 517–528

36. Shanshan Lu, Wei Zhou. et al. Phenanthrenequinone-like moiety functionalized carbon for electrocatalytic acidic oxygen evolution. Chem. 2022, 8, 1415-1426.  

37. Tieliang Li, Yifu Yu, Bin Zhang*, et al. Sulfate-Enabled Nitrate Synthesis from Nitrogen Electrooxidation on Rhodium Electrocatalyst. Angew. Chem. Int. Ed. 2022, e202204541 

38. Yanbo Li, Bin Zhang, Yifu Yu*, et al. Electrocatalytic Reduction of Low-Concentration Nitric Oxide into Ammonia over Ru Nanosheets. ACS Energy Letters 2022, 7, 1187-1194 

39. Yanmei Huang, Yifu Yu, Bin Zhang*, et al. Direct Electrosynthesis of Urea from Carbon Dioxide and Nitric Oxide. ACS Energy Letters 2022, 7, 284-291

40. Wenfu Xie, Hao Li, Min Wei*, et al. NiSn Atomic Pair on Integrated Electrode for Synergistic Electrocatalytic CO₂ Reduction. Angew. Chem. Int. Ed. 2021, 60, 7382–7388

41. Rui Sui, Jiajing Pei, Zhongbin Zhuang*, et al. Engineering Ag?Nx Single-Atom Sites on Porous Concave N-Doped Carbon for Boosting CO₂ Electroreduction. ACS Appl. Mater. Interfaces 2021, 13, 17736-17744 

42. Tiliang Li, Yuting Wang, Yifu Yu*, Bin Zhang*, et al. Ru-Doped Pd Nanoparticles for Nitrogen Electrooxidation to Nitrate. ACS Catal. 2021, 11, 14032-14037

43. Bin Zhang*, et al. Promoting selective electroreduction of nitrates to ammonia over electron-deficient Co modulated by rectifying Schottky contacts. Science China Chemistry 2020, 63, 1469-1476

44. Jiangwei Shi, Bin Zhang*, et al. Promoting nitric oxide electroreduction to ammonia over electron-rich Cu modulated by Ru doping. Science China Chemistry 2021, 64, 1493-1497 

45. Jintao Zhang* et al. Atomic Bridging Structure of Nickel-Nitrogen-Carbon for Highly Efficient Electrocatalytic Reduction of CO2. Angew. Chem.Int. Ed. 2022, 61, e202113918

46. Lang Xu* et al. Gadolinium Changes the Local Electron Densities of Nickel 3d Orbitals for Efficient Electrocatalytic CO2 Reduction. Angew. Chem.Int. Ed. 2022, 61, e202201166

47. Bin Zhang* et al. Phenanthrenequinone-like moiety functionalized carbon for electrocatalytic acidic oxygen evolution. Chem. 2022, 8, 1415-1426

48. Sheng Dai*, Minghui Zhua*, Yifan Han* et al. Probing the role of surface hydroxyls for Bi, Sn and In catalysts during CO2 Reduction. Applied Catalysis B: Environmental 2021, 298,

49. Nan Wang, Yonggang Wang*, et al. Zinc-organic Battery with a Wide Operation-temperature Window from -70 to 150 oC. Angew. Chem. Int. Ed. 2020,59,14577-14583

50. Nannan Meng, Yifu Yu, Bin Zhang*, et al. Efficient Electrosynthesis of Syngas with Tunable CO/H2 Ratios over ZnxCd1-xS-Amine Inorganic-Organic Hybrids. Angew. Chem. Int. Ed. 2019, 58, 18908–18912