Abstract
In this study, a β-Mo2C/N, P-co-doped carbon (NPC) catalyst with a porous structure of β-Mo2C nanoparticles loading on NPC matrix was prepared by vacuum-rotary evaporation and followed by a facile pyrolysis process for hydrogen evolution reaction (HER). The porous structure is beneficial for exposing more active sites and the mass transfer during the HER. In addition, the carbon matrixes with the highly doped N and P heteroatoms also provide their positive contributions to its high catalytic activity for HER. Owing to the advantages mentioned above, the optimized catalyst shows a small overpotential of 181 mV for driving a cathodic current density of 10 mA cm−2, a low Tafel slope of 65.3 mV dec−1 and a high exchange current density of 1.5 × 10−2 mA cm−2 during HER processes in acid electrolyte. The excellent performance of the β-Mo2C/NPC makes it a great potential candidate as the HER electrocatalyst.
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References
Dresselhaus MS, Thomas IL (2001) Alternative energy technologies. Nature 414:332–337
Portney PR (2003) Energy resources and global development. Science 302:1528–1531
Walter MG, Warren EL, McKone JR, Boettcher SW, Mi Q, Santori EA, Lewis NS (2010) Solar water splitting cells. Chem Rev 110:6446–6473
Turner JA (2004) Sustainable hydrogen production. Science 305:972–974
Cook TR, Dogutan DK, Reece SY, Surendranath Y, Teets TS, Nocera DG (2010) Solar energy supply and storage for the legacy and nonlegacy worlds. Chem Rev 110:6474–6502
Marc Koper TM (2013) Hydrogen electrocatalysis: a basic solution. Nat Chem 5:255–256
Durst J, Siebel A, Simon C, Hasche F, Herranz J, Gasteiger HA (2014) New insights into the electrochemical hydrogen oxidation and evolution reaction mechanism. Energy Environ Sci 7:2255–2260
Zheng Y, Jiao Y, Zhu Y, Li LH, Han Y, Chen Y (2014) Hydrogen evolution by a metal-free electrocatalyst. Nat Commun 5:3783–3790
Hou J, Lei Y, Wang F, Ma X, Min S (2017) In-situ photochemical fabrication of transition metal-promoted amorphous molybdenum sulfide catalysts for enhanced photosensitized hydrogen evolution. Int J Hydrogen Energy 42:11118–11129
Peters AW, Li Z, Farha OK, Hupp JT (2016) Toward inexpensive photocatalytic hydrogen evolution: a nickel sulfide catalyst supported on a high-stability metal-organic framework. ACS Appl Mater Interfaces 8:20675
Tuomi S, Guil-Lopez R, Kallio T (2016) Molybdenum carbide nanoparticles as a catalyst for the hydrogen evolution reaction and the effect of ph. J Catal 334:102–109
Bukola S, Merzougui B, Akinpelu A, Zeama M (2016) Cobalt and nitrogen co-doped tungsten carbide catalyst for oxygen reduction and hydrogen evolution reactions. Electrochim Acta 190:1113–1123
Ma Y, He Z, Wu Z, Zhang B, Zhang Y, Ding S (2017) Galvanic-replacement mediated synthesis of copper–nickel nitrides as electrocatalyst for hydrogen evolution reaction. J Mater Chem A 5:24850–24858
Abghoui Y, Skúlason E (2017) Hydrogen evolution reaction catalyzed by transition-metal nitrides. J Phys Chem C 121:24036–24045
Zhou Z, Wei L, Wang Y, Karahan HE, Chen Z, Lei Y (2017) Hydrogen evolution reaction activity of nickel phosphide is highly sensitive to electrolyte ph. J Mater Chem A 5:20390–20397
Lin Y, Liu M, Pan Y, Zhang J (2017) Porous Co–Mo phosphide nanotubes: an efficient electrocatalyst for hydrogen evolution. J Mater Sci 52:1–12. https://doi.org/10.1007/s10853-017-1204-5
Straistari T, Fize J, Shova SS, Reglier M, Artero V, Orio M (2016) A thiosemicarbazone-nickel(ii) complex as efficient electrocatalyst for hydrogen evolution. Chemcatchem 9:2262–2268
Huang Y, Zhang B (2017) Active co-catalysts for photocatalytic hydrogen evolution derived from nickel or cobalt amine complexes. Angew Chem Int Ed 56:14804–14806
Regmi YN, Wam C, Duffee KD, Leonard BM (2015) Nanocrystalline Mo2C as a bifunctional water splitting electrocatalyst. ChemCatChem 7:3911–3915
Zhu J, Yao Y, Chen Z, Zhang A, Zhou M, Guo J, Wu WD, Chen XD, Li Y, Wu Z (2018) Controllable synthesis of ordered mesoporous Mo2C@graphitic carbon core-shell nanowire arrays for efficient electrocatalytic hydrogen evolution. ACS Appl Mater Interfaces 10:18761–18770
Guo J, Wang J, Xu C, Wu Z, Lei W, Zhu J, Xiao W, Wang D (2017) Molybdenum carbides embedded on carbon nanotubes for efficient hydrogen evolution reaction. J Electroanal Chem 801:7–13
Pu Z, Wang M, Kou Z, Amiinu IS, Mu S (2016) Mo2C quantum dot embedded chitosan-derived nitrogen-doped carbon for efficient hydrogen evolution in a broad pH range. Chem Commun 52:12753–12756
Mir RA, Pandety OP (2018) Influence of graphitic/amorphous coated carbon on HER activity of low temperature synthesized β-Mo2C@C nanocomposites. Chem Eng J 348:1037–1048
Long G, Wan K, Liu M, Liang Z, Piao J, Tsiakaras P (2017) Active sites and mechanism on nitrogen-doped carbon catalyst for hydrogen evolution reaction. J Catal 348:151–159
Lin Y, Zhang J, Pan Y, Liu Y (2017) Nickel phosphide nanoparticles decorated nitrogen and phosphorus co-doped porous carbon as efficient hybrid catalyst for hydrogen evolution. Appl Surf Sci 422:828–837
Kong X, Chen S, Zou Y, Lyu S, She X, Lu Y, Sun J, Zhang H, Yang D (2018) Cellulose nanocrystals (CNC) derived Mo2C@sulfur-doped carbon aerogels for hydrogen evolution. Int J Hydrogen Energy 43:13720–13726
Jiao Y, Zheng Y, Davey K, Qiao SZ (2016) Activity origin and catalyst design principles for electrocatalytic hydrogen evolution on heteroatom-doped graphene. Nat Energy 1:16130
Qu KG, Zheng Y, Jiao Y, Zhang XX, Dai S, Qiao SZ (2017) Polydopamine-inspired, dual heteroatom-doped carbon nanotubes for highly efficient overall water splitting. Adv Energy Mater 7:1602068
Qu KG, Zheng Y, Zhang XX, Davey K, Dai S, Qiao SZ (2017) Promotion of electrocatalytic hydrogen evolution reaction on nitrogen-doped carbon nanosheets with secondary heteroatoms. ACS Nano 11:7293–7900
Wan C, Regmi YN, Leonard BM (2014) Multiple phases of molybdenum carbide as electrocatalysts for the hydrogen evolution reaction. Angew Chem Int Ed 53:6407–6410
Mir RA, Sharma P, Pandey OP (2017) Thermal and structural studies of carbon coated Mo2C synthesized via in situ single step reduction carburization. Sci Rep 7:3518–3529
Teghil R, De Bonis A, Galasso A, Sansone M, Rau JV, Santagata A (2012) Nanostructured molybdenum carbide thin films obtained by femtosecond pulsed laser deposition. Phys Status Solidi C 9:2370–2373
Shen Y, Gong B (2015) Coupling Mo2C nanoparticles with graphite nanosheets as durable electrocatalysts for hydrogen evolution reaction. Angew Chem Int Ed 54:1–6
Huang Y, Gong Q, Song X, Feng K, Nie K, Zhao F, Wang Y, Zeng M, Zhong J, Li Y (2016) Mo2C nanoparticles dispersed on hierarchical carbon microflowers for efficient electrocatalytic hydrogen evolution. ACS Nano 10:11337–11343
Wu JB, Lin ML, Cong X, Liu HN, Tan PH (2018) Raman spectroscopy of graphene-based materials and its applications in related devices. Chem Soc Rev 47:1822–1873
Calizo I, Bejenari I, Rahman M, Liu G, Balandin AA (2009) Ultraviolet Raman microscopy of single and multiplayer graphene. J Appl Phys 106:043509
Jing S, Zhang L, Luo L, Lu J, Yin S, Shen PK, Panagiotis T (2018) N-doped porous molybdenum carbide nanobelts as efficient catalysts for hydrogen evolution reaction. Appl Catal B 224:553–5450
Dong J, Wu Q, Huang C, Yao W, Xu Q (2018) Cost effective Mo rich Mo2C electrocatalysts for the hydrogen evolution reaction. J Mater Chem A 6:10028–10035
Mao Y, Li W, Sun X, Ma Y, Xia J, Zhao Y, Lu X, Gan J, Liu Z, Chen J, Liu P, Tong Y (2011) Room-temperature ferromagnetism in hierarchically branched MoO3 nanostructures. CrystEngComm 14:1419–1424
Chen YY, Zhang Y, Jiang WJ, Zhang X, Dai Z, Wan LJ, Jin JS (2016) Pomegranate-like N,P-doped Mo2C@C nanospheres as highly active electrocatalysts for alkaline hydrogen evolution. ACS Nano 10:8851–8860
Huang Y, Ge J, Hu J, Zhang J, Hao J, Wei Y (2017) Nitrogen-doped porous molybdenum carbide and phosphide hybrids on a carbon matrix as highly effective electrocatalysts for the hydrogen evolution reaction. Adv Energy Mater 8:1701601
Zhang S, Xiao X, Lv T, Lv X, Liu B, Wei W, Liu J (2018) Cobalt encapsulated N-doped defect-rich carbon nanotube as pH universal hydrogen evolution electrocatalyst. Appl Surf Sci 446:10–17
Ji J, Wang J, Teng X, Dong H, He X, Chen Z (2018) N, P-doped molybdenum carbide nanofibers for efficient hydrogen production. ACS Appl Mater Interfaces 10:14632–14640
Wang J, Lu H, Hong Q, Cao Y, Li X, Bai J (2017) Porous N,S-codoped carbon architectures with bimetallic sulphide nanoparticles encapsulated in graphitic layers: highly active and robust electrocatalysts for the oxygen reduction reaction in Al-air batteries. Chem Eng J 330:1342–1350
Ann SH, Yu X, Manthiram A (2017) “Wiring” Fe-Nx-embedded porous carbon framework onto 1D nanotubes for efficient oxygen reduction reaction in alkaline and acidic media. Adv Mater 29:1606534
Ojha K, Saha S, Kolev H, Kumar B, Ganguli AK (2016) Composites of graphene-Mo2C rods: highly active and stable electrocatalyst for hydrogen evolution reaction. Electrochim Acta 193:268–274
García G, Roca-Ayats M, Guillén-Villafuerte O, Rodríguez JL, Arévalo MC, Pastor E (2017) Electrochemical performance of α-Mo2C as catalyst for the hydrogen evolution reaction. J Electroanal Chem 793:235–241
Zhou G, Yang Q, Guo X, Chen Y, Yang Q, Xu L, Sun D, Tang Y (2018) Coupling molybdenum carbide nanoparticles with N-doped carbon nanosheets as a high-efficiency electrocatalyst for hydrogen evolution reaction. Int J Hydrogen Energy 43:9326–9333
Zou X, Zhang Y (2015) Noble metal-free hydrogen evolution catalysts for water splitting. Chem Soc Rev 44:5148–5180
Li Z, Ma J, Zhou Y, Yin Z, Tang Y, Ma Y, Wang D (2018) Synthesis of sulfur-rich MoS2 nanoflowers for enhanced hydrogen evolution reaction performance. Electrochim Acta 283:306–312
Liu Y, Yu G, Li GD, Sun Y, Asefa T, Chen W, Asefa T, Chen W, Zou X (2015) Coupling Mo2C with nitrogen-rich nanocarbon leads to efficient hydrogen-evolution electrocatalytic sites. Angew Chem Int Ed 54:10752–10757
Wu Z, Wang J, Zhu J, Guo J, Xiao W, Xuan C, Lei W, Wang D (2017) Highly efficient and stable MoP-RGO nanoparticles as electrocatalysts for hydrogen evolution. Electrochim Acta 232:254–261
Zhang Y, Wang Y, Jia S, Xu H, Zang J, Lu J, Xu X (2016) A hybrid of NiMo-Mo2C/C as non-noble metal electrocatalyst for hydrogen evolution reaction in an acidic solution. Electrochim Acta 222:747–754
McCrory CCL, Jung S, Ferrer IM, Chatman SM, Peters JC, Jaramillo TF (2015) Benchmarking hydrogen evolving reaction and oxygen evolving reaction electrocatalysts for solar water splitting devices. J Am Chem Soc 137:4347–4357
Hu H, Tian M, Li F, Gao L, Xu N, Hu Y, Long X, Ma J, Jin J (2018) Phosphorus dual-doped moo2 nanosheets/multiwalled carbon nanotube hybrid as efficient electrocatalyst for hydrogen evolution. ChemElectroChem 5:2660–2665
Huo L, Liu B, Zhang G, Zhang J (2016) Universal strategy to fabricate a two-dimensional layered mesoporous Mo2C electrocatalyst hybridized on graphene sheets with high activity and durability for hydrogen generation. ACS Appl Mater Interfaces 8:18107–18118
Ma Y, Guan G, Hao X, Gao J, Abudula A (2017) Molybdenum carbide as alternative catalyst for hydrogen production—a review. Renew Sustain Energy Rev 75:1101–1129
Liu Y, Huang B, Xie Z (2018) Hydrothermal synthesis of core-shell MoO2/α-Mo2C heterojunction as high performance electrocatalyst for hydrogen evolution reaction. Appl Surf Sci 427:693–701
Lv CC, Huang ZP, Yang QP, Zhang C (2018) Nanocomposite of MoO2 and MoC loaded on porous carbon as an efficient electrocatalyst for hydrogen evolution reaction. Inorg Chem Front 5:446–453
Jian C, Cai Q, Hong W, Li J, Liu W (2018) Edge-riched MoSe2/MoO2 hybrid electrocatalyst for efficient hydrogen evolution reaction. Small 14:1703798
Li JS, Wang Y, Liu CH, Li SL, Wang YG, Dong LZ, Dai ZH, Li YF, Lan YQ (2016) Coupled molybdenum carbide and reduced graphene oxide electrocatalysts for efficient hydrogen evolution. Nat Commun 7:11204
Yan D, Dou S, Tao L, Liu Z, Liu Z, Huo J, Wang S (2016) Electropolymerized supermolecule derived N,P co-doped carbon nanofiber networks as a highly efficient metal-free electrocatalyst for the hydrogen evolution reaction. J Mater Chem A 4:13726–13730
Lin Y, Pan Y, Zhang J (2017) CoP nanorods decorated biomass derived N, P co-doped carbon flakes as an efficient hybrid catalyst for electrochemical hydrogen evolution. Electrochim Acta 232:561–569
Chi JQ, Gao WK, Lin JH, Dong B, Yan KL, Qin JF, Liu B, Chai YM, Liu CG (2018) N, P dual-doped hollow carbon spheres supported MoS2 hybrid electrocatalyst for enhanced hydrogen evolution reaction. Catal Today. https://doi.org/10.1016/j.cattod.2018.03.003
Chen J, Wei HM, Chen HJ, Yao WH, Lin HL, Han S (2018) N/P co-doped hierarchical porous carbon materials for superior performance supercapacitors. Electrochim Acta 271:49–57
Zhuang M, Ou X, Dou Y, Zhang L, Zhang Q, Wu R, Ding Y, Shao M, Luo Z (2016) Polymer-embedded fabrication of Co2P nanoparticles encapsulated in N,P-doped graphene for hydrogen generation. Nano Lett 16:4691–4698
Acknowledgements
This work is supported by the National Natural Science Foundation of China (Project Nos. 21706010 and 21276018), the Natural Science Foundation of Jiangsu Province of China (Project No. BK20161200) and the Fundamental Research Funds for the Central Universities (Project Nos. buctrc201526 and PYCC1706). Authors are specially thankful for the support from Advanced Catalysis and Green Manufacturing Collaborative Innovation Center, Changzhou University (Project Nos. ACGM2016-06-02 and ACGM2016-06-03).
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Tan, J., He, X., Yin, F. et al. β-Mo2C/N, P-co-doped carbon as highly efficient catalyst for hydrogen evolution reaction. J Mater Sci 54, 4589–4600 (2019). https://doi.org/10.1007/s10853-018-03190-0
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DOI: https://doi.org/10.1007/s10853-018-03190-0