N-doped nanoporous carbon from biomass as a highly efficient

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N-doped nanoporous carbon from biomass as a highly efficient electrocatalysts for CO2 reduction reaction pengfei Yao, Yanling Qiu, Taotao Zhang, panpan Su, Xianfeng Li, and Huamin Zhang ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.8b06160 • Publication Date (Web): 04 Feb 2019 Downloaded from http://pubs.acs.org on February 5, 2019

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ACS Sustainable Chemistry & Engineering

N-doped nanoporous carbon from biomass as a highly efficient electrocatalysts for CO2 reduction reaction Pengfei Yao†, ‡, Yanling Qiu ‡, Taotao Zhang†, ‡, Panpan Su ‡, Xianfeng Li* ‡,§ , Huamin Zhang* ‡,§ †

University of Chinese Academy of Sciences, Beijing 100049, China.

‡

Division of Energy Storage, Dalian Institute of Chemical Physics, Chinese

Academy of Sciences, Zhongshan Road 457, Dalian 116023, China. §Collaborative

innovation Center of Chemistry for Energy Materials (iChEM), Dalian 116023. Corresponding authors: Prof. Dr. Xianfeng Li

Email: [email protected]

Prof. Huamin Zhang

Email: [email protected]

Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Zhongshan Road 457, Dalian 116023, China.

ABSTRACT: Electrocatalytic reduction of carbon dioxide to high value-added chemicals is essential for sustainable development of human civilization. Seeking for catalysts with high activity, selectivity, stability and low cost is vital for CO2 conversion. Heteroatom doped carbon materials are proved to be very promising catalyst for CO2 reduction due to their low cost, high surface area, high conductivity, excellent stability as well as high electrochemical activity. Herein, we report a N-doped nanoporous carbon sheet derived from cheap and

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renewable biomass Typha with high surface area, pore volume and pyridinic N content, which achieved a much higher selectivity (90%) for CO at a much lower overpotential (-0.31 V) than most N-doped carbon materials. The calcination temperature has a great effect on porous structure and the kinds of N species in the catalyst, in which the pyridinic N species play important roles in catalytic performance.

Keywords: carbon dioxide reduction , nanoporous carbon sheet , catalysts , low overpotential , higher selectivity, pyridinic N Introduction With an increasing of energy demand, enormous fossil fuels have been consumed and the direct consequence is the massive emission of carbon dioxide. As a result, serious global climate problems become prominent. Thus, reducing carbon dioxide emissions and converting it into high value-added fuels or chemical feedstocks are of very importance. Among many kinds of carbon dioxide conversion methods, electrochemical reduction of CO2 (ERC) is one of the most attractive approaches because of its superior merits.1-5 For example, it can be performed at ambient conditions, and the supporting electrolytes can be completely recycled so that the reduction only consumes water. Additionally, the renewable electricity can be used to drive CO2 electrochemical reduction.6 However, CO2 is thermodynamically stable inert molecule. There are many critical challenges in the CO2 reduction process including high


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overpotential, slow electron transfer dynamics, low product selectivity and poor stability.7 Thus, designing robust catalysts are necessary to overcome those problems. In the past few decades, many metals and bimetals have been used to catalyse ERC. Among all metals explored, copper is widely investigated to produce highly efficient hydrocarbons and oxygenates.8 However, there are some challenges for Cu based catalyst, such as high overpotential (1V), poor selectivity, and low stability.6 Nanostructured precious metal Ag and Au can selectively transform CO2 into CO at lower overpotential. For example, the Faradaic efficiency of nanoporous Ag reached to approximately 92% at −0.6 V vs. reversible hydrogen electrode (RHE).

9

Sun et al.

reported ultrathin Au nanowires with abundant edge sites, which catalysed CO2 reduction at more positive onset potential of about -0.2 V vs. RHE and Faradaic efficiency reached to 94% at the potential of -0.35 V vs. RHE.10 However, the high cost of precious metals limited their large-scale application. Therefore, seeking for economical and sustainable electrocatalysts is necessary and urgent. Metal-free carbon materials have received more and more attention due to their unique properties, such as low cost, high surface area, high conductivity, excellent stability as well as high electrochemical activity. N-doped carbons can effectively improve ERC catalytic activity compared with pure nanocarbon materials, because the N atom insets in carbon lattice can alter charge and spin density of some carbon atoms and act as active sites for CO2 reduction.11 Metal-free N-Doped carbons can be developed as efficient catalysts for the reduction of CO2 to CO, 12 HCOO- 13 and CXHYOZ. 14 N-doped three-dimensional graphene foam was synthesized by Wu et al. via chemical vapor



deposition and realized 85% faradaic efficiency for CO at relatively low overpotential. 11

Theoretical computation has demonstrated that pyridinic N is the most active site for

ERC. Meyer et al. reported that PEI functionalized N-doped CNT could catalyze CO2 reduction to formate with a faradaic efficiency of 87% at -1.8 V (vs. SCE).12 PEI can not only stabilize the reaction intermediate CO2•−, but also concentrate CO2. Thus, Ndoped CNT and PEI synergistically transform CO2 to HCOO-. Some nanoporous carbons materials derived from biomass have been researched in oxygen reduction reaction (ORR) electrocatalysts because of their abundance and renewability, and they are rich of hierarchical structures and large surface area, which play important roles in electrochemical applications.15-17 Furthermore, doping the carbon with heteroatoms and surface modification methods can enhance the catalytic properties.18 To some extent, ERC is very similar to ORR, involving three phase boundary reaction and proton-electron transfer. Thus, ERC reaction also requires electrocatalyst with high surface area and specific pore structure. The Typha is a wetland plant, widely distributed all over the world, with very low cost. Typha has large cylindrical flower spikes, which contain a lot of Typha fibers.19 The superficial structure of the fibre is highly hollow and contain cellulose and cerolipoid, which are ideal to be used as precursor to produce porous carbon. Thus, we fabricated N-doped carbon materials with abundant micropores derived from a convenient, accessible and renewable Typha by hydrothermal process and calcining in NH3. The abundant micropores can increase active surface and doping N into carbon structure generates the active sites for electrocatalytic CO2 reduction, which achieved a much higher


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selectivity (90%) for CO at a much lower overpotential (-0.31 V) than most N-doped carbon materials. Porous carbon materials can dramatically increase the kinetics of reduction processes. Some porous carbons have been studied before as electrocatalysts, the effect of porosity and small pore (0.9), which indicates the


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existence of macropore derived from packing nanosheets. Macropores are beneficial to transporting CO2 to micropores, which is contribute to improving CO2 adsorption capacity. The porous structure facilitates the diffusion of carbon dioxide to the active sites for improving ERC activity. Further structural information of NCs can be obtained from Raman spectra (Figure S3). The typical peaks located at 1340 cm-1 and 1600 cm1

belong to disordered carbon atoms (D band) and sp2-hybridized graphitic carbon,

respectively.

24

The ID/IG are about 0.925, 0.920, 0.906 and 0.915 for NC-700, NC-

800, NC-900 and NC-950, respectively, indicating the NC-900 has the best graphitization degree in accordance with HRTEM.

Figure 3. (a) Linear sweep curves of NC-900 in N2- and CO2-saturated 0.5 M KHCO3. (b) Faradaic efficiencies for CO production at various applied potentials on NCs samples. (c) Tafel plots of NCs. (d) Stability of NC-900 at -0.5 V vs. RHE. The electrochemical activities of the NCs were examined by linear sweep voltammogram in N2-saturated and CO2-saturated 0.5 M NaHCO3 solutions. As shown



in Fig.3a, the current densities were due to the evolution of hydrogen in N2-saturated 0.5 M NaHCO3 solutions, and the onset potential for HER is about -0.5 V (vs. RHE), which was the competing reaction of ERC. In comparison to CO2-free solution, higher cathode current densities in the entire potential range were yielded in CO2-saturated bicarbonate solutions. The onset potential of NC-900 is about -0.3 V (vs. RHE), which is consistent with CO occurrence detected online by a gas chromatograph. The NC-900 possesses the more positive onset potential and the higher current densities than other samples indicating high activity toward ERC (Fig. S4), which is owing to the higher pyridinic N and bigger porosity of NC-900. Porous structure is conducive to transporting CO2 and improving concentration of carbon dioxide at the reaction surface. Pyridinic N can exist in small pores and enhance interactions between intermediates and carbon surface in these pores, which can greatly lower onset potential. The gas products on NC-900 are mainly CO and H2. For all samples, the Faradic efficiency (FE) of HCOO- is lower than 1%. With the increase of potential, the change of FECO is similar to a volcanic-like curve for the NCs (Fig. 3b). The NC-900 exhibits a maximum FECO of 82% at about −0.5 V vs RHE, which is much higher than that of NC-700 and NC-800, and only 2% lower than that of NC-950. However, the potential of NC-900 is 100 mV more positive than that of NC-950 at the maximum FECO, indicating that the NC-900 has the better comprehensive catalytic performance for ERC combining with its higher current density shown in Fig.S4a. Although NC-900 contains lower content of pyridinic N than NC-800 (Table S1), NC-900 maintains the highest surface area and pore volume, which is beneficial to exposing pyridinic N on the surface


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of catalyst during the CO2 electroreduction process. What’s more, large pores mean higher CO2 transport rate, further increasing the utilization of active sites. The change of FEH2 is opposite to FECO for the NCs as shown in Fig. S5. Additionally, the effect of the electrolyte concentration on the catalytic property and product selectivity of NC-900 was investigated (Fig. S6). When the concentration of NaHCO3 was decreased, the CO was still the main product. At low concentrate CO2-saturated NaHCO3 solution, the selectivity of CO could be further enhanced, in accordance with the previous report, the lower bicarbonate concentrations can significantly suppress HER and enhance selectivity at higher overpotential. 25 The highest FECO achieves 88% at -0.7 V vs RHE in 0.1 M NaHCO3 solution. The more negative potential for the maximum FECO in the diluted NaHCO3 solution may be attributed to the increasing solution resistance as the potentials are not IR compensated. The Tafel plots of NCs were measured in order to explore electrodynamics for the CO formation (Fig. 3c). The Tafel plot for NC-900 is 127 mV dec-1, which is lower than that of NC-700, NC-800 and NC-950 with Tafel slop of 163, 130 and 140 mV dec-1, respectively. These results suggest that NC-900 shows the fastest kinetics for CO formation. These values of slops are close to the 118 mV dec-1, indicating the ratedetermining step for ERC is that CO2 obtains one-electron to form CO2•– key intermediate. The electrochemical impedance spectroscopy (EIS) results further verify this statement (Fig.S7). The NC-900 has the lowest interfacial charge-transfer resistance than other samples, leading to rapid electron transfer in CO2 reduction process. These results indicate that NC-900 can strongly bind CO2•–intermediates than



other samples, which is conducive to forming CO at a relatively low overpotential. Based on previous results and analysis, the high catalytic activity of NC-900 may owe to four factors: (1) its plentiful active sites are thoroughly exposed by high surface area; (2) Rich macropores are beneficial to transporting CO2; (3) Abundant micropores are helpful for capturing CO2 and further reaction; (4) Low interfacial charge-transfer resistance provides fast electrokinetics and rapid electron transfer rate from catalyst to CO2. The stability of catalyst also plays an important role in developing CO2 reduction system. Thus, the long-term performance of NC-900 was measured at constant potential of -0.5 V (vs. RHE) for 10 h and the results are shown in Fig. 3d. Over the test period, the FECO slightly undulates around 75% and the current density maintains at around 0.40 mA cm-2, without obvious change, which indicates the relatively high stability of NC-900. The 10h test was far from reaching the end of the catalyst life. In order to further improve the catalytic performance, the NC-900 was activated with KOH before doping N, denoted as NC-900-HH. The FECO of NC-900-HH reached 90% at the same potential with NC-900 as shown in Fig. S8a, which was ascribed to the structure difference between the two samples. In Fig.S8b, the surface area and pore volume of NC-900-HH are about two times higher than those of NC-900, and there are more abundant micropores and mesoporous of NC-900-HH than that of NC-900 (Fig. S8c), which are conducive to exposing more active sites and promoting mass transport and capturing CO2. This result further supports the fact that higher surface area and pore volume are important for better exposure and utilization of pyridinic N. Thus, NC-


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900-HH exhibits a maximum FECO than other samples. We compared the overpotential at the maximum FECO for NC-900-HH with other N-doped carbon materials as shown in Table 1. The NC-900-HH displays relatively lower overpotential at the maximum FECO and higher Faradic efficiency of CO than most N-doped carbon materials. Although the maximum FECO for NC-900-HH is lower than CN/MWCNT, the overpotential is much lower than CN/MWCNT, indicating higher energy efficiency. Table1. Comparison of overpotential of FEcomax and FECOmax of NC-900-HH with other N-doped carbon catalysts. Catalysts N-doped Graphene NC-900-HH N-CNT CN-H-CNT g-C3N4/MWCNTS CN/ MWCNT N/S- porous carbon MPC-1000 N-CNT

FEmax (CO%) 85 90 80 88 60 98 11.3 62 90

Overpotential of FEcomax (V RHE) -0.47 -0.39 -0.69 -0.39 -0.64 -0.68 -0.88 -0.59 -0.79

Reference 12 This work 26 27 28 29 18 30 31

Based on the above experimental results, the mechanism of electrochemical reduction of CO2 is further explored. The Tafel plot of samples is close to 118 mV dec-1, which means forming CO2•– intermediate is a rate-determining step for ERC. Then, the CO2•– gets another electron and two protons, forming *CO (or CO*) species and H2O followed by *CO desorption. The C-900 exhibits much lower surface area and FECO （6%）at −0.6 V than that of NC-900(Fig. S9). This result reveals nitrogen defect sites inside the carbon matrix can significantly improve the catalytic performance. Previous research suggested that the catalytic active sites are attributed to pyridinic nitrogen defect sites inside the carbon matrix, which can bind CO2. Furthermore, DFT



calculations indicate the pyridinic nitrogen has the lowest free-energy barrier for COOH*.

32

Wu et al. found that the change trend of maximum FE for CO is positive

correlation with pyridinic-N content,

12

because pyridinic nitrogen atoms possessing

excess negative charges, which can efficiently bind with CO2, leading to its reduction on the active sites and positive charged carbon atoms adjacent to pyridinic nitrogen atoms can stabilize CO2•– intermediates. From that we can see, pyridinic nitrogen plays an important role in improving ERC activity and selectivity for formation of CO in NaHCO3 aqueous solution, whereas the pyrrolic N leads to low activity for ERC.32,33 In order to understand the relationship between catalytic performance and N specie of NCs, we investigated the trend of N content of different N species in NCs (Figure S2e). In this work, although the NC-900 contains lower content of pyridinic N than that of NC-800, the NC-800 contains much more pyrrolic nitrogen than that of NC-900. Additionally, NC-900 maintains the higher surface area and pore volume than NC-800, which is beneficial to exposing active sites on the surface of catalyst during the CO2 electroreduction process. Thus, NC-900 exhibits lower overpotential and higher FECO than NC-800. Conclusions In summary, we have synthesized N doped nanoporous carbon nanosheets derived from cheap and renewable biomass Typha. The calcination temperature has a great effect on catalytic performance of NCs. This may owe to the diverse kinds of N species and porous structure caused by different treating temperature. Among these NCs, the NC-900 exhibits an excellent catalytic property with FECO as high as 82%,


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which may result from high surface area, porosity and pyridinic N content. The high surface area is conducive to exposing more active sites, resulting in the low onset potential(-0.3V). Rich large pores are beneficial to transporting CO2 and micropores(＜1nm) are helpful for capturing CO2, which is beneficial to improve concentration of carbon dioxide at the reaction interface. Furthermore, the high pyridinic-N can lower free-energy barrier for COOH*, which greatly improve catalytic activities and selectivity. The NC-900 also show high stability during 10h continuous ERC reaction. Additionally, faradic efficiency of CO on NC-900 reaches about 90% activated by KOH at low overpotential(-0.39V). These results reveal that the excellent performance for ERC should balance among porosity, surface area, types and contents of N species. This low-cost and high selectivity carbon nanosheets derived from biomass are ideal material replacing noble metal for next emerging generation of electrochemical carbon dioxide catalysts. Experimental Section Synthesis of N-doped nanoporous carbon material (NC) Firstly, 3.0 g Typha were put into 100 ml Teflon-lined stainless-steel autoclave and 30 ml distilled water was added. Then, the autoclave was put into an oven at 180°C for 12 h. The obtained black carbonaceous were washed with distilled water for three times and freeze-dried for 12 h. Subsequently, the carbonaceous were calcined at 900°C in a flowing NH3 atmosphere (NC-900) for 1.5 h at a rate of 3°C min-1, and then naturally cooled to room temperature at Ar atmosphere. As control samples, other samples were fabricated by the same steps as NC-900 with only changing carbonization temperature. The carbon samples were denoted as NC-X, where X is the reaction temperature (in °C).



For comparison, the NC was also activated with KOH. Firstly, 4.0 g black carbonaceous, 7.5 g KOH and 30 ml distilled water were mixed for 12 h. Subsequently, the mixture was freeze-dried for 12 h and calcined at 700 °C for 1 h in a flowing Ar atmosphere. Then, the sample was treated by 10% HCl. Finally, the products were obtained by calcined at 900°C in a flowing NH3 for 1.5 h (NC-900-HH). The NCs (treated in different temperature) are grinded at least an hour so as to make it homogeneity before electrode preparation. Electrode preparation The catalysts were coated onto a glass carbon electrode (2×1.5×2.0 cm2) by the following steps. 3.0 mg catalysts were ultrasonically dispersed in 328 μL mixed solvent including 300 μL ethanol, 28 μL 5% Nafion solution. Then 90 μL catalyst inks were coated on glassy carbon electrode. The loading weight was 0.27 mg cm-2. Materials Characterization The scanning electron microscopy (SEM) images were obtained on a JEOL JSM6360 operating at an acceleration voltage of 20 kV. Transmission electron microscopy (TEM) pattern were recorded on a JEOL JEM-2000EX (120 kV) microscope. X-ray photoelectron spectroscopy (XPS) measurements were carried out using an ESCALAB 250Xi spectrometer equipped with a nonmonochromatized Al Ka X-ray source. The pore structures of sample were measured by a gas adsorption analyzer (ASAP-2010) and the pore size distributions for all carbons were calculated from isotherms using NLDFT. Micro-Raman spectra were obtained from an InVia Raman


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microspectrometer (Renishaw, UK) with 532 nm radiation at a laser power of 0.4 mW in the range of 500-2000 cm-1. Electrochemical Measurements Electrochemical measurements were conducted with 2273 potentiostat (EG&G Instrument) in a two-compartment electrochemical cell separated by Nafion 115 membrane with three electrode systems. Pt wire was a counter electrode and the Hg2Cl2/Hg/saturated KCl electrode (SCE) was the reference electrode. All the potentials are converted to the reversible hydrogen electrode scale by ERHE=ESCE + 0.242 +0.059pH. The reference and working electrode were put in the cathode chamber, while the counter electrode was placed in the anode chamber. The prepared electrode was used as working electrode. Constant potential electrolysis was used to measure the performance of the samples. CO2-saturated 0.5 M NaHCO3 aqueous solution was used as electrolyte and the cathodic electrolyte continually bubbled with CO2 gas flow rate at 20 ml min-1 and stirred at 500 rpm during testing to maintain its saturation. The gas product was analyzed every 15 min by gas chromatograph (GC, Shimadzu GC-2014). The CO and hydrogen gas were quantified by a flame ionization detector (FID) and thermal conductivity detector (TCD), respectively. The aqueous product was quantified by ion chromatography (ICS-1100, Dionex Corporation). The EIS measurement was conducted by the electrochemical interface (Solartron S1 1287) and the Impedance/Gain-Phase Analyzer (Solartron S1 1260). The testing frequency is from 100 kHz to 0.01 Hz. The measurement was carried out in 0.5 M NaHCO3 aqueous solution after the solution is saturated with CO2.



AUTHOR INFORMATION Corresponding Authors *Email: [email protected], [email protected]. Notes The authors declare no competing financial interest. Supporting Information Additional material characterizations including SEM, TEM images, XPS spectra, Raman spectra, EIS, BET and Faradaic efficiencies of NCs and C-900, summary of N contents for NCs. ■

ACKNOWLEDGMENT

The authors thank the financial grants from the National Natural Science Foundation of China (No.21577141 and No. 21576255). ■

REFERENCES

1. Kuhl, K. P.; Hatsukade, T.; Cave, E. R.; Abram, D. N.; Kibsgaard, J.; Jaramillo, T. F., Electrocatalytic conversion of carbon dioxide to methane and methanol on transition metal surfaces. Journal of the American Chemical Society 2014, 136 (40), 14107-13, DOI 10.1021/ja505791r. 2. Lu, Q.; Rosen, J.; Jiao, F., Nanostructured Metallic Electrocatalysts for Carbon Dioxide Reduction. ChemCatChem 2015, 7 (1), 38-47, DOI 10.1002/cctc.201402669. 3. Goeppert, A.; Czaun, M.; Jones, J. P.; Surya Prakash, G. K.; Olah, G. A., Recycling of carbon dioxide to methanol and derived products - closing the loop. Chemical Society reviews 2014, 43 (23), 7995-8048, DOI 10.1039/C4CS00122B.


Page 18 of 22

Page 19 of 22 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


4. Jiang, K.; Kharel, P.; Peng, Y.; Gangishetty, M. K.; Lin, H.-Y. G.; Stavitski, E.; Attenkofer, K.; Wang, H., Silver Nanoparticles with Surface-Bonded Oxygen for Highly Selective CO2 Reduction. ACS Sustainable Chemistry & Engineering 2017, 5 (10), 8529-8534, DOI 10.1021/acssuschemeng.7b02380. 5. Siahrostami, S.; Jiang, K.; Karamad, M.; Chan, K.; Wang, H.; Nørskov, J., Theoretical Investigations into Defected Graphene for Electrochemical Reduction of CO2. ACS Sustainable Chemistry & Engineering 2017, 5 (11), 11080-11085, DOI 10.1021/acssuschemeng.7b03031. 6. Wang, Z.-L.; Li, C.; Yamauchi, Y., Nanostructured nonprecious metal catalysts for electrochemical reduction of carbon dioxide. Nano Today 2016, 11 (3), 373-391, DOI 10.1016/j.nantod.2016.05.007. 7. Ma, T.; Fan, Q.; Tao, H.; Han, Z.; Jia, M.; Gao, Y.; Ma, W.; Sun, Z., Heterogeneous electrochemical CO2 reduction using nonmetallic carbon-based catalysts: current status and future challenges. Nanotechnology 2017, 28 (47), 472001, DOI 10.1088/1361-6528/aa8f6f. 8. Kuhl, K. P.; Cave, E. R.; Abram, D. N.; Jaramillo, T. F., New insights into the electrochemical reduction of carbon dioxide on metallic copper surfaces. Energy & Environmental Science 2012, 5 (5), 7050, DOI 10.1039/c2ee21234j. 9. Lu, Q.; Rosen, J.; Zhou, Y.; Hutchings, G. S.; Kimmel, Y. C.; Chen, J. G.; Jiao, F., A selective and efficient electrocatalyst

for

carbon

dioxide

reduction.

Nature

communications

2014,

5,

DOI

10.1038/ncomms4242. 10. Zhu, W.; Zhang, Y. J.; Zhang, H.; Lv, H.; Li, Q.; Michalsky, R.; Peterson, A. A.; Sun, S., Active and selective conversion of CO2 to CO on ultrathin Au nanowires. Journal of the American Chemical Society 2014, 136 (46), 16132-5, DOI 10.1021/ja5095099. 11. Zhu, D. D.; Liu, J. L.; Qiao, S. Z., Recent Advances in Inorganic Heterogeneous Electrocatalysts for Reduction

of

Carbon

Dioxide.

Advanced

materials

2016,

28

(18),

3423-52,

DOI

10.1002/adma.201504766. 12. Wu, J.; Liu, M.; Sharma, P. P.; Yadav, R. M.; Ma, L.; Yang, Y.; Zou, X.; Zhou, X. D.; Vajtai, R.; Yakobson, B. I.; Lou, J.; Ajayan, P. M., Incorporation of Nitrogen Defects for Efficient Reduction of CO2 via TwoElectron Pathway on Three-Dimensional Graphene Foam. Nano letters 2016, 16 (1), 466-70, DOI 10.1021/acs.nanolett.5b04123. 13. Zhang, S.; Kang, P.; Ubnoske, S.; Brennaman, M. K.; Song, N.; House, R. L.; Glass, J. T.; Meyer, T. J., Polyethylenimine-enhanced electrocatalytic reduction of CO(2) to formate at nitrogen-doped carbon nanomaterials. Journal of the American Chemical Society 2014, 136 (22), 7845-8, DOI 10.1021/ja5031529. 14. Song, Y.; Chen, W.; Zhao, C.; Li, S.; Wei, W.; Sun, Y., Metal-Free Nitrogen-Doped Mesoporous Carbon for Electroreduction of CO2 to Ethanol. Angewandte Chemie 2017, 56 (36), 10840-10844, DOI 10.1002/ange.201706777. 15. Gao, S.; Chen, Y.; Fan, H.; Wei, X.; Hu, C.; Wang, L.; Qu, L., A green one-arrow-two-hawks strategy for nitrogen-doped carbon dots as fluorescent ink and oxygen reduction electrocatalysts. Journal of Materials Chemistry A 2014, 2 (18), 6320, DOI 10.1039/c3ta15443b. 16. Deng, L.; Fang, H.; Zhang, P.; Abdelkader, A.; Ren, X.; Li, Y.; Xie, N., Nitrogen and Sulfur Dual-Doped Carbon Microtubes with Enhanced Performances for Oxygen Reduction Reaction. Journal of The Electrochemical Society 2016, 163 (5), H343-H349, DOI 10.1149/2.1131605jes. 17. Shi, H.; Shen, Y.; He, F.; Li, Y.; Liu, A.; Liu, S.; Zhang, Y., Recent advances of doped carbon as nonprecious catalysts for oxygen reduction reaction. J. Mater. Chem. A 2014, 2 (38), 15704-15716, DOI 10.1039/c4ta02790f.



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18. Li, W.; Seredych, M.; Rodriguez-Castellon, E.; Bandosz, T. J., Metal-free Nanoporous Carbon as a Catalyst for Electrochemical Reduction of CO2 to CO and CH4. ChemSusChem 2016, 9 (6), 606-16, DOI 10.1002/cssc.201501575. 19. Chen, P.; Wang, L.-K.; Wang, G.; Gao, M.-R.; Ge, J.; Yuan, W.-J.; Shen, Y.-H.; Xie, A.-J.; Yu, S.-H., Nitrogen-doped nanoporous carbon nanosheets derived from plant biomass: an efficient catalyst for oxygen reduction reaction. Energy Environ. Sci. 2014, 7 (12), 4095-4103, DOI 10.1039/c4ee02531h. 20. Wickramaratne, N. P.; Jaroniec, M., Activated carbon spheres for CO2 adsorption. ACS applied materials & interfaces 2013, 5 (5), 1849-55, DOI 10.1021/am400112m. 21. Li, W.; Fechler, N.; Bandosz, T. J., Chemically heterogeneous nitrogen sites of various reactivity in porous carbons provide high stability of CO2 electroreduction catalysts. Applied Catalysis B: Environmental 2018, 234, 1-9, DOI 10.1016/j.apcatb.2018.04.021. 22. Wan, W.; Wang, Q.; Zhang, L.; Liang, H.-W.; Chen, P.; Yu, S.-H., N-, P- and Fe-tridoped nanoporous carbon derived from plant biomass: an excellent oxygen reduction electrocatalyst for zinc–air batteries. Journal of Materials Chemistry A 2016, 4 (22), 8602-8609, DOI 10.1039/c6ta02150f. 23. Li, W.; Bandosz, T. J., Role of Heteroatoms in S,N-Codoped Nanoporous Carbon Materials in CO2 (Photo)electrochemical

Reduction.

ChemSusChem

2018,

11

(17),

2987-2999,

DOI

10.1002/cssc.201801073. 24. Liang, J.; Jiao, Y.; Jaroniec, M.; Qiao, S. Z., Sulfur and nitrogen dual-doped mesoporous graphene electrocatalyst for oxygen reduction with synergistically enhanced performance. Angewandte Chemie 2012, 51 (46), 11496-500, DOI 10.1002/anie.201206720. 25. Wuttig, A.; Yaguchi, M.; Motobayashi, K.; Osawa, M.; Surendranath, Y., Inhibited proton transfer enhances Au-catalyzed CO2-to-fuels selectivity. Proceedings of the National Academy of Sciences of the United States of America 2016, 113 (32), E4585-93, DOI 10.1073/pnas.1602984113. 26. Wu, J.; Yadav, R. M.; Liu, M.; Sharma, P. P.; Tiwary, C. S.; Ma, L.; Zou, X.; Zhou, X.-D.; Yakobson, B. I.; Lou, J.; Ajayan, P. M., Achieving Highly Efficient, Selective, and Stable CO2 Reduction on Nitrogen-Doped Carbon Nanotubes. ACS nano 2015, 9 (5), 5364-5371, DOI 10.1021/acsnano.5b01079. 27. Cui, X.; Pan, Z.; Zhang, L.; Peng, H.; Zheng, G., Selective Etching of Nitrogen-Doped Carbon by Steam for Enhanced Electrochemical CO2 Reduction. Advanced Energy Materials 2017, 1701456, DOI 10.1002/aenm.201701456. 28. Lu, X.; Tan, T. H.; Ng, Y. H.; Amal, R., Highly Selective and Stable Reduction of CO2 to CO by a Graphitic Carbon Nitride/Carbon Nanotube Composite Electrocatalyst. Chemistry 2016, 22 (34), 119916, DOI 10.1002/chem.201601674. 29. Jhong, H. R. M.; Tornow, C. E.; Smid, B.; Gewirth, A. A.; Lyth, S. M.; Kenis, P. J. A., A Nitrogen-Doped Carbon Catalyst for Electrochemical CO2 Conversion to CO with High Selectivity and Current Density. Chemsuschem 2017, 10 (6), 1094-1099, DOI 10.1002/cssc.201600843. 30. Pan, F.; Liang, A.; Duan, Y.; Liu, Q.; Zhang, J.; Li, Y., Self-growth-templating synthesis of 3D N,P,Codoped mesoporous carbon frameworks for efficient bifunctional oxygen and carbon dioxide electroreduction. J. Mater. Chem. A 2017, 5 (25), 13104-13111, DOI 10.1039/c7ta03005c. 31. Xu, J.; Kan, Y.; Huang, R.; Zhang, B.; Wang, B.; Wu, K. H.; Lin, Y.; Sun, X.; Li, Q.; Centi, G.; Su, D., Revealing the Origin of Activity in Nitrogen-Doped Nanocarbons towards Electrocatalytic Reduction of Carbon Dioxide. ChemSusChem 2016, 9 (10), 1085-9, DOI 10.1002/cssc.201600202. 32. Sharma, P. P.; Wu, J.; Yadav, R. M.; Liu, M.; Wright, C. J.; Tiwary, C. S.; Yakobson, B. I.; Lou, J.; Ajayan, P. M.; Zhou, X. D., Nitrogen-Doped Carbon Nanotube Arrays for High-Efficiency Electrochemical


Page 21 of 22 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Reduction of CO2: On the Understanding of Defects, Defect Density, and Selectivity. Angewandte Chemie 2015, 54 (46), 13701-5, DOI 10.1002/anie.201506062. 33. Wang, R.; Sun, X.; Ould-Chikh, S.; Osadchii, D.; Bai, F.; Kapteijn, F.; Gascon, J., Metal-OrganicFramework-Mediated Nitrogen-Doped Carbon for CO2 Electrochemical Reduction. ACS applied materials & interfaces 2018, 10 (17), 14751-14758, DOI 10.1021/acsami.8b02226.

TOC Graphic



N-doped carbon sheets derived from renewable Typha achieved a high selectivity for CO (90%) at a much lower overpotential (-0.31 V).


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N-doped nanoporous carbon from biomass as a highly efficient

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