Bridging Nanostructure Growth and Gas-Sensing Kinetics in Metal-Functionalized Graphene Using Machine-Learned Molecular Dynamics
Source abstract
Abstract
Graphene functionalized with catalytic transition metals offers high-performance chemiresistive gas sensing by coupling graphene’s exceptional electronic transport with the metal’s catalytic activity; yet the atomistic relationships connecting synthesis parameters, morphological outcomes, and sensor gas–surface reaction kinetics remain elusive. We developed an equivariant machine-learning interatomic potential with DFT accuracy to enable high-fidelity molecular dynamics (MD) simulations, from metal nanostructure growth on graphene to device-level sensing kinetics. Demonstrating our approach, we specifically investigate Pt-functionalized graphene for H 2 detection. MD simulations validated by TEM show that Pt deposition begins with dispersed nuclei coalescing into polycrystalline nanoclusters, while both MD and Raman spectroscopy reveal predominantly noncovalent metal–graphene interactions that induce moderate local strain and doping, while preserving graphene’s structural integrity. MD simulations confirm H 2 dissociative chemisorption and recombinative desorption primarily on Pt nanoclusters, with negligible spillover or chemical interaction with pristine graphene. However, H adsorption on Pt attenuates the Pt–graphene interfacial binding, providing an indirect electronic pathway for gas sensing. Adsorption/desorption kinetics reveal that an intermediate loading of metal nanostructures minimizes the detection limit; lower loadings facilitate faster response and recovery kinetics and enhance signal transduction, whereas higher loadings increase interfacial binding and graphene doping. The developed machine-learned MD framework accurately models metallic nanostructure growth on graphene, elucidates the gas-sensing mechanism, and correlates figures of merit─detection limit, sensitivity, and response/recovery times─extracted from gas–surface kinetics with metal nanostructure morphology, establishing a multiscale predictive pipeline from synthesis conditions to gas-sensor kinetics.
Source: openalex_inverted_index · Quality: baseline
Research context
OpenAlex topics: Gas Sensing Nanomaterials and Sensors · Graphene research and applications · 2D Materials and Applications
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
Affiliations
Department of Physics
University of Maryland Baltimore County
Center for Research and Exploration in Space Science and Technology
NASA Goddard Space Flight Center
Department of Astronomy
University of Maryland College Park
Planetary Environments Laboratory
Funding
Exploration Systems Development Mission Directorate · Office of Science · Division of Materials Research
References (100+)
Show source-provided references
1. 10.1007/978-981-15-4810-9_1010.1007/978-981-15-4810-9_10 ↗
2. 10.1021/acs.chemrev.4c0059210.1021/acs.chemrev.4c00592 ↗
3. 10.1063/1.498331010.1063/1.4983310 ↗
4. 10.1016/j.trac.2024.11779010.1016/j.trac.2024.117790 ↗
5. 10.1007/s11356-020-12231-810.1007/s11356-020-12231-8 ↗
6. 10.1016/j.ijhydene.2021.09.06410.1016/j.ijhydene.2021.09.064 ↗
7. 10.3847/1538-3881/aca90b10.3847/1538-3881/aca90b ↗
8. 10.1016/j.ijhydene.2010.04.17610.1016/j.ijhydene.2010.04.176 ↗
9. 10.3390/s13101421410.3390/s131014214 ↗
10. 10.1021/acsnano.0c0530710.1021/acsnano.0c05307 ↗
11. 10.1016/j.chempr.2019.04.01310.1016/j.chempr.2019.04.013 ↗
12. 10.1021/acs.chemrev.8b0034010.1021/acs.chemrev.8b00340 ↗
13. 10.1007/s40820-015-0073-110.1007/s40820-015-0073-1 ↗
14. 10.1016/j.aca.2015.02.00210.1016/j.aca.2015.02.002 ↗
15. 10.1039/D3NA00423F10.1039/D3NA00423F ↗
16. 10.1016/j.ssc.2008.02.02410.1016/j.ssc.2008.02.024 ↗
17. 10.1016/j.snb.2012.07.09210.1016/j.snb.2012.07.092 ↗
18. 10.1038/srep2003410.1038/srep20034 ↗
19. 10.1016/j.ces.2021.11701710.1016/j.ces.2021.117017 ↗
20. 10.1016/j.flatc.2016.11.00110.1016/j.flatc.2016.11.001 ↗
21. 10.1021/acs.chemrev.5b0062010.1021/acs.chemrev.5b00620 ↗
22. 10.1007/s12274-015-0768-010.1007/s12274-015-0768-0 ↗
23. 10.3390/ma1504132610.3390/ma15041326 ↗
24. 10.1021/acsanm.4c0341610.1021/acsanm.4c03416 ↗
25. 10.1080/10408436.2016.124465610.1080/10408436.2016.1244656 ↗
26. 10.1016/j.trac.2015.02.00810.1016/j.trac.2015.02.008 ↗
27. 10.1002/1521-4095(200109)13:183.0.CO;2-810.1002/1521-4095(200109)13:183.0.CO;2-8 ↗
28. 10.1038/ncomms578110.1038/ncomms5781 ↗
29. 10.1063/1.48047310.1063/1.480473 ↗
30. 10.1016/0039-6028(76)90232-610.1016/0039-6028(76)90232-6 ↗
31. 10.1021/acs.jpcc.9b0441910.1021/acs.jpcc.9b04419 ↗
32. 10.3390/cryst707021910.3390/cryst7070219 ↗
33. 10.1016/j.flatc.2024.10066110.1016/j.flatc.2024.100661 ↗
34. 10.1002/adma.20200482710.1002/adma.202004827 ↗
35. 10.1021/acsnano.9b0670110.1021/acsnano.9b06701 ↗
36. 10.1021/acsami.5b0018210.1021/acsami.5b00182 ↗
37. Owen, C. J.; Russotto, L.; O’Connor, C. R.; Marcella, N.; Johansson, A.; Musaelian, A.; Kozinsky, B. Atomistic evolution of active sites in multi-component heterogeneous catalysts. 2024. arXiv:2407.13607. arXiv.org e-Printarchive. https://doi.org/10.48550/arXiv.2407.13607.
38. 10.1149/1.358925010.1149/1.3589250 ↗
39. 10.1016/j.renene.2018.05.03310.1016/j.renene.2018.05.033 ↗
40. 10.1039/C7CP04241H10.1039/C7CP04241H ↗
41. 10.1016/j.ijhydene.2021.02.00410.1016/j.ijhydene.2021.02.004 ↗
42. 10.3390/en1418573810.3390/en14185738 ↗
43. 10.1088/2053-1591/ab2dc010.1088/2053-1591/ab2dc0 ↗
44. 10.1021/acsomega.4c0701710.1021/acsomega.4c07017 ↗
45. 10.1038/s41467-023-36329-y10.1038/s41467-023-36329-y ↗
46. 10.1038/s41467-022-29939-510.1038/s41467-022-29939-5 ↗
47. Geiger, M.; Smidt, T. e3nn: Euclidean Neural Networks 2022. arXiv:2207.09453. arXiv.org e-Printarchive. https://doi.org/10.48550/arXiv.2207.09453.
48. 10.1140/epjb/s10051-021-00156-110.1140/epjb/s10051-021-00156-1 ↗
49. 10.1038/s41563-020-0777-610.1038/s41563-020-0777-6 ↗
50. 10.1021/acs.jpcc.3c0616810.1021/acs.jpcc.3c06168 ↗
51. 10.1021/acs.cgd.3c0150410.1021/acs.cgd.3c01504 ↗
52. 10.1038/s41467-022-32294-010.1038/s41467-022-32294-0 ↗
53. 10.1021/acs.jpclett.3c0313510.1021/acs.jpclett.3c03135 ↗
54. 10.1016/j.commatsci.2020.10994610.1016/j.commatsci.2020.109946 ↗
55. 10.1016/j.softx.2024.10163210.1016/j.softx.2024.101632 ↗
56. 10.1063/1.132967210.1063/1.1329672 ↗
57. 10.1063/1.45966910.1063/1.459669 ↗
58. 10.1143/JJAP.46.423310.1143/JJAP.46.4233 ↗
59. 10.1016/0022-2852(61)90111-410.1016/0022-2852(61)90111-4 ↗
60. 10.1063/1.155570110.1063/1.1555701 ↗
61. Aliofkhazraei, M.; Ali, N. Comprehensive Materials Processing ; Elsevier: Oxford, 2014; pp 85–117.10.1016/B978-0-08-096532-1.00706-8 ↗
62. 10.1088/0965-0393/18/1/01501210.1088/0965-0393/18/1/015012 ↗
63. 10.1039/c2cp40527j10.1039/c2cp40527j ↗
64. 10.1016/j.progsurf.2015.07.00110.1016/j.progsurf.2015.07.001 ↗
65. 10.1088/1742-6596/100/7/07204210.1088/1742-6596/100/7/072042 ↗
66. Ester, M.; Kriegel, H.P.; Sander, J.; Xu, X. A Density-based Algorithm for Discovering Clusters in Large Spatial Databases with Noise ; KDD’96: Proceedings of the Second International Conference on Knowledge Discovery and Data Mining ACM, 1996; pp 226–231.
67. 10.1109/TIT.1983.105671410.1109/TIT.1983.1056714 ↗
68. Krone, M.; Stone, J. E.; Ertl, T.; Schulten, K.EuroVis (Short Papers). Fast Visualization of Gaussian Density Surfaces for Molecular Dynamics and Particle System Trajectories , The Eurographics Association, 2012 pp 067-071.
69. 10.1021/nl203359n10.1021/nl203359n ↗
70. 10.1038/srep1821910.1038/srep18219 ↗
71. 10.1007/s12274-020-2769-x10.1007/s12274-020-2769-x ↗
72. 10.1016/j.cocis.2015.10.01010.1016/j.cocis.2015.10.010 ↗
73. Kittel C. · 1996 · 122
74. 10.1088/0965-0393/24/5/05500710.1088/0965-0393/24/5/055007 ↗
75. 10.1088/0953-8984/20/47/47220410.1088/0953-8984/20/47/472204 ↗
76. 10.1016/j.carbon.2024.11880110.1016/j.carbon.2024.118801 ↗
77. 10.1039/C8EE00539G10.1039/C8EE00539G ↗
78. 10.1103/PhysRevLett.113.04610210.1103/PhysRevLett.113.046102 ↗
79. 10.1016/j.susc.2014.03.00610.1016/j.susc.2014.03.006 ↗
80. 10.1063/5.008598210.1063/5.0085982 ↗
81. 10.1021/acs.jpcc.4c0809710.1021/acs.jpcc.4c08097 ↗
82. 10.1016/j.mtsust.2023.10055410.1016/j.mtsust.2023.100554 ↗
83. 10.1021/jp902987s10.1021/jp902987s ↗
84. 10.1016/j.apcatb.2017.08.02510.1016/j.apcatb.2017.08.025 ↗
85. Gale, R. J. Reactive and Nonreactive Scattering of Modulated Molecular Beams from well Characterized Platinum Single Crystal Surfaces ; IAEA, 2011.
86. 10.1002/qua.2540710.1002/qua.25407 ↗
87. 10.1021/acs.jpcc.9b0098110.1021/acs.jpcc.9b00981 ↗
88. 10.1063/1.43778710.1063/1.437787 ↗
89. 10.1039/D1CP02974F10.1039/D1CP02974F ↗
90. 10.1103/PhysRevB.79.19542510.1103/PhysRevB.79.195425 ↗
91. 10.1038/srep0208110.1038/srep02081 ↗
92. 10.1039/C6CP07334D10.1039/C6CP07334D ↗
93. 10.1016/j.apsusc.2016.10.09710.1016/j.apsusc.2016.10.097 ↗
94. 10.1103/PhysRevB.77.23543010.1103/PhysRevB.77.235430 ↗
95. 10.1039/c3cp51791h10.1039/c3cp51791h ↗
96. 10.1103/PhysRev.136.B86410.1103/PhysRev.136.B864 ↗
97. 10.1103/PhysRevLett.77.386510.1103/PhysRevLett.77.3865 ↗
98. 10.1103/PhysRevB.50.1795310.1103/PhysRevB.50.17953 ↗
99. 10.1103/PhysRevB.54.1116910.1103/PhysRevB.54.11169 ↗
100. 10.1103/PhysRevB.13.518810.1103/PhysRevB.13.5188 ↗