Accelerating the Activation of NO x − on Ru Nanoparticles for Ammonia Production by Tuning Their Electron Deficiency
2022; Chinese Chemical Society; Volume: 4; Issue: 11 Linguagem: Inglês
10.31635/ccschem.022.202101756
ISSN2096-5745
AutoresGuangyao Zhai, Qiyuan Li, Shi‐Nan Zhang, Dong Xu, Siyuan Xia, Peng Gao, Xiu Lin, Yun‐Xiao Lin, Jinhuan Cheng, Weiyao Hu, Lu‐Han Sun, Xin‐Hao Li, Jie‐Sheng Chen,
Tópico(s)Catalytic Processes in Materials Science
ResumoOpen AccessCCS ChemistryCOMMUNICATION7 Nov 2022Accelerating the Activation of NOx− on Ru Nanoparticles for Ammonia Production by Tuning Their Electron Deficiency Guang-Yao Zhai, Qi-Yuan Li, Shi-Nan Zhang, Dong Xu, Si-Yuan Xia, Peng Gao, Xiu Lin, Yun-Xiao Lin, Jin-Huan Cheng, Wei-Yao Hu, Lu-Han Sun, Xin-Hao Li and Jie-Sheng Chen Guang-Yao Zhai School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules, Shanghai Jiao Tong University, Shanghai 200240 , Qi-Yuan Li School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules, Shanghai Jiao Tong University, Shanghai 200240 , Shi-Nan Zhang School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules, Shanghai Jiao Tong University, Shanghai 200240 , Dong Xu School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules, Shanghai Jiao Tong University, Shanghai 200240 , Si-Yuan Xia School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules, Shanghai Jiao Tong University, Shanghai 200240 , Peng Gao School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules, Shanghai Jiao Tong University, Shanghai 200240 , Xiu Lin School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules, Shanghai Jiao Tong University, Shanghai 200240 , Yun-Xiao Lin School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules, Shanghai Jiao Tong University, Shanghai 200240 , Jin-Huan Cheng School of Environmental Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240 , Wei-Yao Hu School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules, Shanghai Jiao Tong University, Shanghai 200240 , Lu-Han Sun School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules, Shanghai Jiao Tong University, Shanghai 200240 , Xin-Hao Li *Corresponding authors: E-mail Address: [email protected] E-mail Address: [email protected] School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules, Shanghai Jiao Tong University, Shanghai 200240 and Jie-Sheng Chen *Corresponding authors: E-mail Address: [email protected] E-mail Address: [email protected] School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules, Shanghai Jiao Tong University, Shanghai 200240 https://doi.org/10.31635/ccschem.022.202101756 SectionsSupplemental MaterialAboutAbstractPDF ToolsAdd to favoritesDownload CitationsTrack Citations ShareFacebookTwitterLinked InEmail Stable and portable ammonia (NH3) is a promising, low-cost, and environment-friendly medium for energy storage. How to achieve the rapid production of NH3 from reducing NOx− in aqueous systems and industrial wastewater via electrochemical methods remains the main challenge for practical application on a large scale. The corresponding electrocatalysts as the key materials in electrochemical devices suffer from low activity, especially in neutral systems. In this work, we successfully elevated the activity of the bench-mark Ru electrocatalysts to more than 30 times via construction of rectifying contact of Ru metals and noble carbons. We theoretically predicted and then rationally designed a new type of P–O rich carbon with large work functions as "noble" supports to attract a pronounced number of electrons from Ru metals at the rectifying interface. The resulting electron deficiency of Ru metals largely promotes the pre-adsorption and activation of NOx− anions, providing high Faradaic efficiencies (>96%) and record-high turnover frequency values for universal NO2− and NO3− reduction in neutral solution. Download figure Download PowerPoint Introduction Ammonia is regarded as a promising next-generation energy storage material because of its outstanding features of high energy density (3 kWh kg−1), high hydrogen content (17.6%), and zero-carbon emission.1–5 Concerning the need for excess electricity power at specific locations or times, electrocatalytic reduction of various nitrogen sources (NOx−, N2, and NO) into relatively stable and portable NH3 is a promising, low-cost, and environment-friendly route for energy storage.6–11 Especially, aquatic ecosystems polluted by NOx− pose adverse effects on ecological balances, threatening human health.12–16 Thus, developing powerful electrocatalysts for universally converting NOx− contamination to high-value NH3 as an energy carrier is of great importance for maintaining a globally balanced nitrogen cycle and exploring a sustainable energy supply based on ammonia-mediated energy systems.17–22 Pioneering work has shown the advantages of Ru-based nanomaterials as efficient catalysts for reducing NO3− to NH3 in base or acid solutions,23 even though the final selectivity and yield are far from satisfactory, especially in neutral systems. There is a consensus in the literature that the electron-deficient metal nanoparticles in metal/doped-carbon dyads induced by the interfacial Mott Schottky effect exhibit strong adsorption of small molecules (Figure 1a).24,25 Considering the comparable work functions of noble metal Ru and graphitic carbon materials, it is still very challenging but desirable to explore "more noble" carbon materials with very high work functions to attract more electrons from as-embedded Ru metals and thus boost the universal capture and electroreduction of NOx− for the highly selective production of ammonia. Figure 1 | Design principle and structures of Ru on P–O doped carbon (POC) samples. (a) Proposed adsorption behavior of electron-deficient metal surface in a Schottky heterojunction for selective enrichment of anions (exemplified with NOx−) adjacent to Helmholtz layer. (b) The calculated band structure of carbon, carbon material doped with N atoms (NC), carbon material doped with P atoms (PC), and POC via DFT calculation methods. (c) Synthetic method for preparing P–O rich POC support and depositing Ru nanoparticles. (d) STEM images and corresponding element mapping images and (e) HRTEM image of typical Ru/POC-2.0 catalyst and. (f) P 2p X-ray photoemission spectra of POC-x samples (P contents: x atom %). color code: C, gray; N, blue; O, yellow; P, red; Ru, cyan. Download figure Download PowerPoint Herein, we first predicted the ultrahigh work function of carbon material doped with P–O groups (POC) and then experimentally synthesized enhanced electron-deficient Ru nanoparticles by using the rectifying contact with the designed P–O doped carbon support (Ru/POC). Both theoretical simulation and experimental results demonstrate the key importance of enhanced electron deficiency of supported Ru nanoparticles on POC to facilitate the fixation of NOx− anions for ammonia production with remarkably high Faradaic efficiencies (>96%) in neutral systems. The optimized Ru/POC electrocatalyst also delivers the highest turnover frequency (TOF) of 2531 h−1 for NO3− reduction, which is 30 times higher than that of the state-of-the-art metal nanoparticles-based catalysts in the literature in neutral systems. Results and Discussion With respect to the on-demand design of more "noble" carbon support material, our theoretical calculation results (Figure 1b and Supporting Information Figure S1) predict that introducing P–O groups, rather than P and N heteroatoms, into the carbon matrix can significantly lower the valance band and Fermi level of carbon supports.26 As a result, a biomass phytic acid was optimized as the non-toxic P source for fabricating P–O rich carbon monoliths (POC) from polycondensation with glucose and dicyandiamide via a modified nanoconfinement method as depicted in Figure 1c.27–29 More experimental details and characterizations are available in the Supporting Information. Transmission electron microscopy observations and scanning electron microscopy images (Figure 1d and Supporting Information Figures S2 and S3) reveal a wrinkled and layered structure of P- and O-rich P–carbon support and well-dispersed tiny Ru nanoparticles, suggesting a strong interaction that keeps the as-formed Ru nanoparticles from aggregating during the H2 reduction process at 750 °C. The high-resolution transmission electron microscopy (HRTEM) (Figure 1e) observations demonstrate the formation of Ru nanocrystals with a mean size of 2.8 nm and typical lattice (101) of 0.21 nm for Ru metal ( Supporting Information Figure S4), which has been doubly confirmed by X-ray diffraction ( Supporting Information Figure S5) and X-ray photoemission spectroscopy (XPS) ( Supporting Information Figure S6) analysis results.30,31 The P atomic contents in POC-x samples, mainly in the form of C–P–O, and C–P bonds, could be linearly tuned from 0 to 2.0 atom %, as estimated from their P 2p XPS patterns (Figure 1f and Supporting Information Figure S7 and Table S1),32–35 via optimizing the amount of phytic acid in the precursors and condensation temperatures (for experimental details, please see Supporting Information). The gradually enlarged D-band peaks of POC-x samples in the Raman spectra ( Supporting Information Figure S8) further indicate the successful introduction of heteroatom defects in the carbon lattice.36 A moderate condensation temperature (1000 °C) maintains relatively higher P–O content (1.5 atom %) in the POC-2.0 sample ( Supporting Information Figure S7). Inspired by the successful design of P–O rich carbon materials, we initially evaluated the possibility of manipulating the electron density of as-embedded Ru metal nanocrystals with comparable surface areas ( Supporting Information Figure S9) to boost their activity for universal electrochemical reduction of NO3− and NO2− to NH3 in neutral electrolytes. The concentration of produced ammonium was quantified according to the standard calibration curve by 1H NMR analysis and a colorimetric method ( Supporting Information Figure S10). Blank reactions at an open-circuit potential or in Ar-saturated 1M Na2SO4 electrolyte did not produce a detectable amount of NH3, excluding the possible influence of surroundings ( Supporting Information Figure S11).37 Linear sweep voltammetry (LSV) curves demonstrated that the electrocatalyst displays significantly larger current density after the addition of NOx− to the electrolyte, suggesting possible electrocatalytic activity of Ru/POC for reducing NOx− ions (Figure 2a). As compared with bare POC, the significantly enhanced NH3 production and Faradaic efficiency for NO3− reduction on Ru/POC (Figure 2b and Supporting Information Figure S12) certainly indicates the synergistic effects between P–O rich carbon and Ru nanocrystal in Ru/POC catalyst. Under optimized conditions (Figure 2c), the Ru/POC electrode delivers an excellent NH3 production of 1.32 mmol h−1 mg−1 with a Faradaic efficiency of 96% at −0.8 V (vs. Reversible Hydrogen Electrode [RHE]) from the electrocatalytic reduction of NO3− solution ( Supporting Information Figure S13). Similarly, the Ru/POC-based electrode reached a Faradaic efficiency of 99% with an NH3 yield rate of 2.06 mmol h−1 mg−1 (Figure 2d and Supporting Information Figure S14) for NO2− reduction at −0.8 V (vs. RHE), exhibiting the universal promotion effect of Ru/POC heterojunctions on the catalytic performance of NOx− reduction in neutral electrolytes. Figure 2 | Electrocatalytic reduction of NOx− on Ru on P–O doped carbon (POC) catalysts. (a) LSV curves of Ru/POC-based electrode (exemplified with Ru/POC-2.0 sample) in 1 M Na2SO4, 1 M NO2−, and 1 M NO3− electrolytes. (b) NH3 yield rates and Faradaic efficiencies of Ru/C, Ru/POC, and POC electrodes for NO3− reduction −0.8 V versus RHE. (c and d) Performance of Ru/POC catalyst for (c) NO3− reduction and (d) NO2− reduction at varied potentials. (e) 1H NMR spectra of the products of 15NH4+ and 14NH4+ from the reduction of 15NO2− and 14NO3−, respectively. (f) The recycling uses of Ru/POC-based electrode at −0.8 V versus RHE. Download figure Download PowerPoint Additionally, 15N isotopic labeling experiments (Figure 2e) further confirmed the formation of ammonia originated from the electrocatalytic reduction of NO3− and NO2− over the Ru/POC electrocatalyst. Most importantly, the Ru/POC-based electrode remained durable over 10 cycles of reuse, with consistent NO3− reduction activity (Faradic efficiency: 93.8–96%; yield: 1.308–1.336 mmol h−1 mg−1) (Figure 2f) and negligible changes in structure ( Supporting Information Figures S15 and S16). All these results suggest the key role of the interfacial synergy of Ru/POC in universally boosting NOx− reduction for practical uses. To further investigate the origins of interfacial synergy in the Ru/POC dyad, we theoretically demonstrate the enhanced electron-deficiency of a Ru nanoparticle model after the formation of a rectifying contact with the P–O rich carbon support model according to the electron density difference (EDD) stereograms of the Ru/POC model (Figure 3a and Supporting Information Figure S17). The enhanced electron-deficiency of Ru nanoparticles was then experimentally confirmed by the gradually increased work functions (Φ) of 6.8–7.3 eV as more P–O groups were introduced into the carbon support (Figure 3b and Supporting Information Figure S18). The upshift of the Ru 2p XPS peaks to higher energy (Figure 3c) from Ru/C to Ru/POC-2.0 further indisputably proves the more pronounced electron deficiencies of the as-embedded Ru nanoparticles induced by the rectifying contact with more "noble" carbon supports. Figure 3 | Roles of electron-deficient Ru nanoparticles in NO3− capture. (a) Calculated electron density difference (EDD) stereograms of Ru on P–O doped carbon (POC) model by the DFT method (electron-deficient area (δ−), blue; electron-rich area (δ+), red). (b) Measured work functions of Ru/C and Ru/POC-x samples. (c) Ru 3p X-ray photoemission spectra of Ru/C and Ru/POC-x samples. (d–e) Simulated distribution of the NO3− concentration near the surface of (d) Ru/C model with nearly neutral Ru metal and (e) Ru/POC model with electron-deficient Ru metal in 1 M NO3− solution by finite-element numerical method. (f) The measured adsorption capacities of NO3− on Ru/C and Ru/POC-x samples in 0.2 mM NO3− solution. (g) NH3 Faradaic efficiencies of Ru/C and Ru/POC-x electrodes at −0.8 V versus RHE. Download figure Download PowerPoint The enhanced electron-deficiency of Ru nanoparticles promotes the adsorption of NOx− anion on the electrocatalyst surface. According to the finite-element numerical simulation results (Figure 3d and 3e and Supporting Information Figure S19), the concentration of the NO3− anion on the electron-deficient Ru nanoparticle surface in a 1 M NaNO3 solution increased from 1.25 M, on the neutral Ru nanoparticle surface, to 1.64 M, theoretically demonstrating the key role of the electron-deficiency of Ru metal in promoting the adsorption of NOx− anions. Indeed, the estimated adsorption capacities of NO3− on Ru/C and Ru/POC-x samples (Figure 3f and Supporting Information Figure S20) exhibit a linear relationship with the concentration of P–O groups in carbon supports. The accumulation effect of NO3− anions on the surface of electron-deficient Ru sample ensures the selective and complete reduction of NO3− to ammonia via an eight-electron transfer reaction, resulting in the highest Faradaic efficiency of 96% on Ru/POC-2.0 catalyst with the most pronounced electron deficiency among all control samples in this work (Figure 3g and Supporting Information Figure S21). Besides the high selectivity, the activity of Ru nanoparticles for ammonia production is also significantly promoted by the enhanced electron deficiency. The Gibbs free energies calculated for all steps of electrocatalytic reduction of nitrate (Figure 4a) over the electron-deficient Ru model (Ru-e−) are much lower than those over the neutral Ru model (Ru) ( Supporting Information Figure S22). As the rate-limiting step for the reduction reactions for both the NO3− and NO2− ions,17 the formation barrier of the key intermediate *ONH from NO intermediate ( Supporting Information Figure S23) is largely depressed from 1.13 eV on the Ru model to 0.22 eV on the Ru-e− model, again speaking for more favorable reaction kinetics on the electron-deficient Ru nanoparticles. More importantly, the desorption energy of the NH3 molecule from the Ru surface also decreases with the enhanced electron deficiency, thereby benefiting after reloading of reactants in a higher production rate ( Supporting Information Figure S24). Figure 4 | Roles of electron-deficient Ru nanoparticles in NO3− reduction. (a) Calculated absorption configurations and corresponding Gibbs free energy diagrams for each step of NO3− reduction process on electron-deficient Ru (Ru-e−, insets) and neutral Ru (Ru) ( Supporting Information Figure S22) models. (b) and (c) The turnover frequency (TOF) and Faradaic efficiency values of Ru/POC-2.0 and state-of-the-art electrocatalysts in the literature for (b) NO2− and (c) NO3− reduction in neutral electrolytes. Download figure Download PowerPoint It should be noted that the as-formed enhanced electron-deficient Ru/POC electrocatalyst could universally convert NOx− contamination with high Faradaic efficiency and achieve record-high TOF values for NH3 production. For electrocatalytic NO2− reduction, the TOF value is 5.6 times higher than the best in the literature (Figure 4b and Supporting Information Table S2). More remarkably, the TOF value for NO3− reduction could even reach 30 times higher than that of the state-of-the-art metal nanoparticles-based catalysts in neutral systems (Figure 4c and Supporting Information Table S2), demonstrating the superiority of our Ru/POC material as a powerful and universal catalyst for NOx− electroreduction to NH3. Conclusion We have successfully designed a more noble P–O-rich carbon material to enhance the electron deficiency of as-embedded Ru nanoparticles by constructing rectifying contact between them for universally and efficiently reducing NOx− to NH3. 15N isotope labeling experiments confirmed that the produced ammonia originated from the NOx− reduction. Experimental results combined with density functional theory (DFT) calculations demonstrate the key role of pronounced electron deficiency of Ru metals in enhancing the capture and activation of NOx− anions to finally boost the ammonia production, far outperforming the reported electrocatalysts. More importantly, cycle experiments revealed the material remains durable and stable after long-term use. Considering the vast volume of our water system with a relatively low concentration of NOx− anions and a pH value around 7, we will further extend the applications of the powerful electron-deficient Ru electrocatalysts for selective capturing and rapid reduction of NOx− anions to ammonia for energy storage in large scale electrolyzers. Supporting Information Supporting Information is available and includes detailed materials preparation and characterization, experimental methods, computational details, and additional Figures S1–S24 and Tables S1 and S2. Conflict of Interest There is no conflict of interest to report. Acknowledgments This work was supported by the National Natural Science Foundation of China (grant nos. 21931005, 21720102002, and 22071146), Shanghai Science and Technology Committee (grant nos. 19JC1412600 and 20520711600), and the SJTU-MPI partner group. References 1. Ashida Y.; Arashiba K.; Nakajima K.; Nishibayashi Y.Molybdenum-Catalysed Ammonia Production with Samarium Diiodide and Alcohols or Water.Nature2019, 568, 536–540. Google Scholar 2. Cui C.; Luo Z.; Yao J.Enhanced Catalysis of Pt3 Clusters Supported on Graphene for N–H Bond Dissociation.CCS Chem.2019, 1, 215–225. Abstract, Google Scholar 3. Chen G.-F.; Yuan Y.; Jiang H.; Ren S.-Y.; Ding L.-X.; Ma L.; Wu T.; Lu J.; Wang H.Electrochemical Reduction of Nitrate to Ammonia via Direct Eight-Electron Transfer Using a Copper–Molecular Solid Catalyst.Nat. Energy2020, 5, 605–613. Google Scholar 4. Tang C.; Qiao S. Z.How to Explore Ambient Electrocatalytic Nitrogen Reduction Reliably and Insightfully.Chem. Soc. Rev.2019, 48, 3166–3180. Google Scholar 5. Chang F.; Gao W.; Guo J.; Chen P.Emerging Materials and Methods toward Ammonia-Based Energy Storage and Conversion.Adv. Mater.2021, 33, e2005721. Google Scholar 6. Wang Y.; Xu A.; Wang Z.; Huang L.; Li J.; Li F.; Wicks J.; Luo M.; Nam D. H.; Tan C. S.; Ding Y.; Wu J.; Lum Y.; Dinh C. T.; Sinton D.; Zheng G.; Sargent E. H.Enhanced Nitrate-to-Ammonia Activity on Copper-Nickel Alloys via Tuning of Intermediate Adsorption.J. Am. Chem. Soc.2020, 142, 5702–5708. Google Scholar 7. Soto-Hernández J.; Santiago-Ramirez C. R.; Ramirez-Meneses E.; Luna-Trujillo M.; Wang J.-A.; Lartundo-Rojas L.; Manzo-Robledo A.Electrochemical Reduction of NOx Species at the Interface of Nanostructured Pd and PdCu Catalysts in Alkaline Conditions.Appl. Catal. B Environ.2019, 259, 118048. Google Scholar 8. Hu Q.; Qin Y.; Wang X.; Zheng H.; Gao K.; Yang H.; Zhang P.; Shao M.; He C.Grain Boundaries Engineering of Hollow Copper Nanoparticles Enables Highly Efficient Ammonia Electrosynthesis from Nitrate.CCS Chem.2021, 3, 2092–2103. Google Scholar 9. Xue Z. H.; Zhang S. N.; Lin Y. X.; Su H.; Zhai G. Y.; Han J. T.; Yu Q. Y.; Li X. H.; Antonietti M.; Chen J. S.Electrochemical Reduction of N2 into Nh3 by Donor-Acceptor Couples of Ni and Au Nanoparticles with a 67.8% Faradaic Efficiency.J. Am. Chem. Soc.2019, 141, 14976–14980. Google Scholar 10. Chen J.; Wang H.; Wang Z.; Mao S.; Yu J.; Wang Y.; Wang Y.Redispersion of Mo-Based Catalysts and the Rational Design of Super Small-Sized Metallic Mo Species.ACS Catal.2019, 9, 5302–5307. Google Scholar 11. Shang Z.; Song B.; Li H.; Zhang H.; Feng F.; Kaelin J.; Zhang W.; Xie B.; Cheng Y.; Lu K.; Chen Q.Atomically Dispersed Manganese Lewis Acid Sites Catalyze Electrohydrogenation of Nitrogen to Ammonia.CCS Chem.2021, 3, 2104–2115. Google Scholar 12. Chen J. G.; Crooks R. M.; Seefeldt L. C.; Bren K. L.; Bullock R. M.; Darensbourg M. Y.; Holland P. L.; Hoffman B.; Janik M. J.; Jones A. K.; Kanatzidis M. G.; King P.; Lancaster K. M.; Lymar S. V.; Pfromm P.; Schneider W. F.; Schrock R. R.Beyond Fossil Fuel-Driven Nitrogen Transformations.Science2018, 360, eaar6611. Google Scholar 13. Canfield D. E.; Glazer A. N.; Falkowski P. G.The Evolution and Future of Earth's Nitrogen Cycle.Science2010, 330, 192–196. Google Scholar 14. Wang H.; Chen Y.; Fan R.; Chen J.; Wang Z.; Mao S.; Wang Y.Selective Electrochemical Reduction of Nitrogen to Ammonia by Adjusting the Three-Phase Interface.Research (Wash D C)2019, 2019, 1401209. Google Scholar 15. van Langevelde P. H.; Katsounaros I.; Koper M. T. M.Electrocatalytic Nitrate Reduction for Sustainable Ammonia Production.Joule2021, 5, 290–294. Google Scholar 16. Wu Z. Y.; Karamad M.; Yong X.; Huang Q.; Cullen D. A.; Zhu P.; Xia C.; Xiao Q.; Shakouri M.; Chen F. Y.; Kim J. Y. T.; Xia Y.; Heck K.; Hu Y.; Wong M. S.; Li Q.; Gates I.; Siahrostami S.; Wang H.Electrochemical Ammonia Synthesis via Nitrate Reduction on Fe Single Atom Catalyst.Nat. Commun.2021, 12, 2870. Google Scholar 17. Guo Y.; Stroka J. R.; Kandemir B.; Dickerson C. E.; Bren K. L.Cobalt Metallopeptide Electrocatalyst for the Selective Reduction of Nitrite to Ammonium.J. Am. Chem. Soc.2018, 140, 16888–16892. Google Scholar 18. Gao P.; Xue Z. H.; Zhang S. N.; Xu D.; Zhai G. Y.; Li Q. Y.; Chen J. S.; Li X. H.Schottky Barrier-Induced Surface Electric Field Boosts Universal Reduction of NOx- in Water to Ammonia.Angew. Chem. Int. Ed.2021, 60, 20711–20716. Google Scholar 19. Wang Y.; Zhou W.; Jia R.; Yu Y.; Zhang B.Unveiling the Activity Origin of a Copper-Based Electrocatalyst for Selective Nitrate Reduction to Ammonia.Angew. Chem. Int. Ed.2020, 59, 5350–5354. Google Scholar 20. Sun W. J.; Ji H. Q.; Li L. X.; Zhang H. Y.; Wang Z. K.; He J. H.; Lu J. M.Built-in Electric Field Triggered Interfacial Accumulation Effect for Efficient Nitrate Removal at Ultra-Low Concentration and Electroreduction to Ammonia.Angew. Chem. Int. Ed.2021, 660, 22933–22939. Google Scholar 21. Rosca V.; Duca M.; de Groot M. T.; Koper M. T.Nitrogen Cycle Electrocatalysis.Chem. Rev.2009, 109, 2209–2244. Google Scholar 22. Gao J.; Sun Q.; Huang C.Graphdiyne-Based Nanostructure Materials and Their Application in Energy Storage and Conversion.Chem. J. Chin. Univ.2021, 42, 1501–1513. Google Scholar 23. Li J.; Zhan G.; Yang J.; Quan F.; Mao C.; Liu Y.; Wang B.; Lei F.; Li L.; Chan A. W. M.; Xu L.; Shi Y.; Du Y.; Hao W.; Wong P. K.; Wang J.; Dou S. X.; Zhang L.; Yu J. C.Efficient Ammonia Electrosynthesis from Nitrate on Strained Ruthenium Nanoclusters.J. Am. Chem. Soc.2020, 142, 7036–7046. Google Scholar 24. Liu Y. X.; Wang H. H.; Zhao T. J.; Zhang B.; Su H.; Xue Z. H.; Li X. H.; Chen J. S.Schottky Barrier Induced Coupled Interface of Electron-Rich N-Doped Carbon and Electron-Deficient Cu: In-Built Lewis Acid-Base Pairs for Highly Efficient CO2 Fixation.J. Am. Chem. Soc.2019, 141, 38–41. Google Scholar 25. Lin Y. X.; Zhang S. N.; Xue Z. H.; Zhang J. J.; Su H.; Zhao T. J.; Zhai G. Y.; Li X. H.; Antonietti M.; Chen J. S.Boosting Selective Nitrogen Reduction to Ammonia on Electron-Deficient Copper Nanoparticles.Nat. Commun.2019, 10, 4380. Google Scholar 26. Patel M. A.; Luo F.; Khoshi M. R.; Rabie E.; Zhang Q.; Flach C. R.; Mendelsohn R.; Garfunkel E.; Szostak M.; He H.P-Doped Porous Carbon as Metal Free Catalysts for Selective Aerobic Oxidation with Mechanism.ACS Nano2016, 10, 2305–2315. Google Scholar 27. Lv L. B.; Cui T. L.; Zhang B.; Wang H. H.; Li X. H.; Chen J. S.Wrinkled Graphene Monoliths as Superabsorbing Building Blocks for Superhydrophobic and Superhydrophilic Surfaces.Angew. Chem. Int. Ed.2015, 54, 15165–15169. Google Scholar 28. Zhai G. Y.; Xu D.; Zhang S. N.; Xue Z. H.; Su H.; Yu Q. Y.; Wang H. H.; Lin X.; Lin Y. X.; Sun L. H.; Li X. H.; Chen J. S.Isoelectric Si Heteroatoms as Electron Traps for N2 Fixation and Activation.Adv. Funct. Mater.2020, 30, 2005779. Google Scholar 29. Lin X.; Zhang S. N.; Xu D.; Zhang J. J.; Lin Y. X.; Zhai G. Y.; Su H.; Xue Z. H.; Liu X.; Antonietti M.; Chen J. S.; Li X. H.Electrochemical Activation of C-H by Electron-Deficient W2C Nanocrystals for Simultaneous Alkoxylation and Hydrogen Evolution.Nat. Commun.2021, 12, 3882. Google Scholar 30. Wu X.; Wang Z.; Zhang D.; Qin Y.; Wang M.; Han Y.; Zhan T.; Yang B.; Li S.; Lai J.; Wang L.Solvent-Free Microwave Synthesis of Ultra-Small Ru-Mo2[email protected] with Strong Metal-Support Interaction for Industrial Hydrogen Evolution.Nat. Commun.2021, 12, 4018. Google Scholar 31. Zhou Y.; Xie Z.; Jiang J.; Wang J.; Song X.; He Q.; Ding W.; Wei Z.Lattice-Confined Ru Clusters with High Co Tolerance and Activity for the Hydrogen Oxidation Reaction.Nat. Catal.2020, 3, 454–462. Google Scholar 32. Latorre-Sanchez M.; Primo A.; Garcia H.P-Doped Graphene Obtained by Pyrolysis of Modified Alginate as a Photocatalyst for Hydrogen Generation from Water-Methanol Mixtures.Angew. Chem. Int. Ed.2013, 52, 11813–11816. Google Scholar 33. Zhang J.; Qu L.; Shi G.; Liu J.; Chen J.; Dai L.N,P-Codoped Carbon Networks as Efficient Metal-Free Bifunctional Catalysts for Oxygen Reduction and Hydrogen Evolution Reactions.Angew. Chem. Int. Ed.2016, 55, 2230–2234. Google Scholar 34. Zhang J.; Zhao Z.; Xia Z.; Dai L.A Metal-Free Bifunctional Electrocatalyst for Oxygen Reduction and Oxygen Evolution Reactions.Nat. Nanotechnol.2015, 10, 444–452. Google Scholar 35. Yang N.; Zheng X.; Li L.; Li J.; Wei Z.Influence of Phosphorus Configuration on Electronic Structure and Oxygen Reduction Reactions of Phosphorus-Doped Graphene.J. Phys. Chem. C2017, 121, 19321–19328. Google Scholar 36. Yang J.; Guo D.; Zhao S.; Lin Y.; Yang R.; Xu D.; Shi N.; Zhang X.; Lu L.; Lan Y. Q.; Bao J.; Han M.Cobalt Phosphides Nanocrystals Encapsulated by P-Doped Carbon and Married with P-Doped Graphene for Overall Water Splitting.Small2019, 15, e1804546. Google Scholar 37. Andersen S. Z.; Colic V.; Yang S.; Schwalbe J. A.; Nielander A. C.; McEnaney J. M.; Enemark-Rasmussen K.; Baker J. G.; Singh A. R.; Rohr B. A.; Statt M. J.; Blair S. J.; Mezzavilla S.; Kibsgaard J.; Vesborg P. C. K.; Cargnello M.; Bent S. F.; Jaramillo T. F.; Stephens I. E. L.; Norskov J. K.; Chorkendorff I.A Rigorous Electrochemical Ammonia Synthesis Protocol with Quantitative Isotope Measurements.Nature2019, 570, 504–508. Google Scholar Previous articleNext article FiguresReferencesRelatedDetails Issue AssignmentVolume 4Issue 11Page: 3455-3462Supporting Information Copyright & Permissions© 2022 Chinese Chemical SocietyKeywordselectron deficiency of Ru nanoparticlesP–O rich carbonelectrochemical NOx− reductionenergy storageammonia productionAcknowledgmentsThis work was supported by the National Natural Science Foundation of China (grant nos. 21931005, 21720102002, and 22071146), Shanghai Science and Technology Committee (grant nos. 19JC1412600 and 20520711600), and the SJTU-MPI partner group. Downloaded 666 times PDF downloadLoading ...
Referência(s)