Zhendong Guo^1*, Francesco Ambrosio¹, Alfredo Pasquarello^1*

1 Chaire de Simulation à l’Echelle Atomique (CSEA), Ecole Polytechnique Fédérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland

* Corresponding authors emails: zhendongguozju@gmail.com, alfredo.pasquarello@epfl.ch

DOI10.24435/materialscloud:21-m1 [version v1]

Publication date: Nov 13, 2020

How to cite this record

Zhendong Guo, Francesco Ambrosio, Alfredo Pasquarello, Evaluation of photocatalysts for water splitting through combined analysis of surface coverage and energy-level alignment, Materials Cloud Archive 2020.145 (2020), doi: 10.24435/materialscloud:21-m1.

Description

To examine whether suitable conditions occur for the water splitting reaction at their interfaces with liquid water, we determine the pH-dependent surface coverage for a series of semiconductors, including GaAs, GaP, GaN, CdS, ZnO, SnO2, rutile and anatase TiO2. For this we calculate acidity constants at surface sites through ab initio molecular dynamics simulations and a grand-canonical formulation of adsorbates. The resulting pH values at the point of zero charge show excellent agreement with experiment and thereby support the validity of our approach. By combining information concerning the surface coverage with the alignment of the band edges with respect to the relevant redox levels, we scrutinize the potential of the considered semiconductors as photocatalysts and identify the corresponding optimal pH ranges for hydrogen and oxygen evolution. More specifically, our results indicate that GaN stands out among these semiconductors as the most promising candidate for the overall water splitting, with the potential of further improvement through alloying. With the surface coverage, our computational analysis brings a new descriptor that is at present beyond experimental reach.

Materials Cloud sections using this data

Files

File name	Size	Description
r-TiO2_H2O_mol_Ti_OH_1.xyz.zip MD5md5:bca98f565f920055918d14dbb85cf56d	119.8 MiB	The MD trajectory for the rutile TiO2-H2O interface showing the molecular adsorption mode of water with one proton removed from H2O adsorbed at the surface Ti site 1.
r-TiO2_H2O_mol_Ti_OH_2.xyz.zip MD5md5:db1e559fade840881965f7130dc47ec9	119.6 MiB	The MD trajectory for the rutile TiO2-H2O interface showing the molecular adsorption mode of water with one proton removed from H2O adsorbed at the surface Ti site 2.
r-TiO2_H2O_mol_O_H_1.xyz.zip MD5md5:5da0b0084dc5c8df07d776f5a50e5e65	119.9 MiB	The MD trajectory for the rutile TiO2-H2O interface showing the molecular adsorption mode of water with one extra proton attached to the surface O site 1.
r-TiO2_H2O_mol_O_H_2.xyz.zip MD5md5:d3990bd30bd0fd7cfe999a339727677e	119.9 MiB	The MD trajectory for the rutile TiO2-H2O interface showing the molecular adsorption mode of water with one extra proton attached to the surface O site 2.
GaP_H2O_mol_Ga_OH_1.xyz.zip MD5md5:6d39779a543f6263f1059567443241a6	84.3 MiB	The MD trajectory for the GaP-H2O interface showing the molecular adsorption mode of water with one proton removed from H2O adsorbed at the surface Ga site 1.
GaP_H2O_mol_Ga_OH_2.xyz.zip MD5md5:aee19d7a2dcf49e4c7f81b0c63a99364	73.4 MiB	The MD trajectory for the GaP-H2O interface showing the molecular adsorption mode of water with one proton removed from H2O adsorbed at the surface Ga site 2.
GaP_H2O_mol_P_H_1.xyz.zip MD5md5:8a5334a9631693f5be160f7b7dd52dc8	84.8 MiB	The MD trajectory for the GaP-H2O interface showing the molecular adsorption mode of water with one extra proton attached to the surface P site 1.
GaP_H2O_mol_P_H_2.xyz.zip MD5md5:5c62e4ffeebbb5c7af97b4b183e5f578	84.8 MiB	The MD trajectory for the GaP-H2O interface showing the molecular adsorption mode of water with one extra proton attached to the surface P site 2.
GaP_H2O_dis_Ga_H2O_1.xyz.zip MD5md5:d597f9cea07d7a6f221dd3c6eef16ff7	68.0 MiB	The MD trajectory for the GaP-H2O interface showing the dissociative adsorption mode of water with one extra proton bound to OH- adsorbed at the surface Ga site 1.
GaP_H2O_dis_Ga_H2O_2.xyz.zip MD5md5:a89e1f32728e77c21b5976eea6f26c81	67.9 MiB	The MD trajectory for the GaP-H2O interface showing the dissociative adsorption mode of water with one extra proton bound to OH- adsorbed at the surface Ga site 2.
GaP_H2O_dis_P_1.xyz.zip MD5md5:9ade570a9f5ca4947d31b4c2769c4cc0	84.8 MiB	The MD trajectory for the GaP-H2O interface showing the dissociative adsorption mode of water with one proton removed from the surface P site 1.
GaP_H2O_dis_P_2.xyz.zip MD5md5:666ab16183a74837c32ffd7e8a415cf7	70.4 MiB	The MD trajectory for the GaP-H2O interface showing the dissociative adsorption mode of water with one proton removed from the surface P site 2.
GaN_H2O_dis_Ga_H2O_1.xyz.zip MD5md5:5a015aefcf01ad89bd5424be95fd4ee6	94.0 MiB	The MD trajectory for the GaN-H2O interface showing the dissociative adsorption mode of water with one extra proton bound to OH- adsorbed at the surface Ga site 1.
GaN_H2O_dis_Ga_H2O_2.xyz.zip MD5md5:e7ba8005f3dca5b07fa670985140079a	93.2 MiB	The MD trajectory for the GaN-H2O interface showing the dissociative adsorption mode of water with one extra proton bound to OH- adsorbed at the surface Ga site 2.
GaN_H2O_dis_N_1.xyz.zip MD5md5:50efee0cc2da797efd93accee1febd9c	92.8 MiB	The MD trajectory for the GaN-H2O interface showing the dissociative adsorption mode of water with one proton removed from the surface N site 1.
GaN_H2O_dis_N_2.xyz.zip MD5md5:96589734a029a06000b54b1239804c19	77.5 MiB	The MD trajectory for the GaN-H2O interface showing the dissociative adsorption mode of water with one proton removed from the surface N site 2.
GaAs_H2O_mol_Ga_OH_1.xyz.zip MD5md5:d9d46da76159f2ad461cfe577184d937	105.2 MiB	The MD trajectory for the GaAs-H2O interface showing the molecular adsorption mode of water with one proton removed from H2O adsorbed at the surface Ga site 1.
GaAs_H2O_mol_Ga_OH_2.xyz.zip MD5md5:c41b53d39ff7303c782934b8d4d98e0d	105.2 MiB	The MD trajectory for the GaAs-H2O interface showing the molecular adsorption mode of water with one proton removed from H2O adsorbed at the surface Ga site 2.
GaAs_H2O_mol_As_H_1.xyz.zip MD5md5:64a5b8155bda7fcb99a50a575693a8a5	85.5 MiB	The MD trajectory for the GaAs-H2O interface showing the molecular adsorption mode of water with one extra proton attached to the surface As site 1.
GaAs_H2O_mol_As_H_2.xyz.zip MD5md5:4ab5ef7bcba3f6ff8f69e49d89cd6fa7	70.6 MiB	The MD trajectory for the GaAs-H2O interface showing the molecular adsorption mode of water with one extra proton attached to the surface As site 2.
GaAs_H2O_dis_Ga_H2O_1.xyz.zip MD5md5:14c5abf1ddc689a569a173d0972e2bb1	85.8 MiB	The MD trajectory for the GaAs-H2O interface showing the dissociative adsorption mode of water with one extra proton bound to OH- adsorbed at the surface Ga site 1.
GaAs_H2O_dis_Ga_H2O_2.xyz.zip MD5md5:120f969a20eab21ecf2e23fe150783f6	85.8 MiB	The MD trajectory for the GaAs-H2O interface showing the dissociative adsorption mode of water with one extra proton bound to OH- adsorbed at the surface Ga site 2.
GaAs_H2O_dis_As_1.xyz.zip MD5md5:4272d7ca8acf7ea40f18c105f939361e	85.2 MiB	The MD trajectory for the GaAs-H2O interface showing the dissociative adsorption mode of water with one proton removed from the surface As site 1.
GaAs_H2O_dis_As_2.xyz.zip MD5md5:11bddaa6acc28a8788d6b838a8bfd4a2	94.8 MiB	The MD trajectory for the GaAs-H2O interface showing the dissociative adsorption mode of water with one proton removed from the surface As site 2.
CdS_H2O_mol_Cd_OH_1.xyz.zip MD5md5:e1f359cbb320c4324ee0d5b42bdc071d	93.3 MiB	The MD trajectory for the CdS-H2O interface showing the molecular adsorption mode of water with one proton removed from H2O adsorbed at the surface Cd site 1.
CdS_H2O_mol_Cd_OH_2.xyz.zip MD5md5:9966eb3b0c59f70950ddb8a9da65fc8e	93.1 MiB	The MD trajectory for the CdS-H2O interface showing the molecular adsorption mode of water with one proton removed from H2O adsorbed at the surface Cd site 2.
CdS_H2O_mol_S_H_1.xyz.zip MD5md5:df4b02d50e7ab805af9ac7d6718812ed	93.8 MiB	The MD trajectory for the CdS-H2O interface showing the molecular adsorption mode of water with one extra proton attached to the surface S site 1.
CdS_H2O_mol_S_H_2.xyz.zip MD5md5:fbad5ec1edeebb6bf6412f3a9a6c1001	93.7 MiB	The MD trajectory for the CdS-H2O interface showing the molecular adsorption mode of water with one extra proton attached to the surface S site 2.
a-TiO2_H2O_mol_Ti_OH_1.xyz.zip MD5md5:66ac2ec19ce98c5cf4c657461b4d6133	103.4 MiB	The MD trajectory for the anatase TiO2-H2O interface showing the molecular adsorption mode of water with one proton removed from H2O adsorbed at the surface Ti site 1.
a-TiO2_H2O_mol_Ti_OH_2.xyz.zip MD5md5:9f04daccef1a5c1622e6af22edd9736b	103.7 MiB	The MD trajectory for the anatase TiO2-H2O interface showing the molecular adsorption mode of water with one proton removed from H2O adsorbed at the surface Ti site 2.
a-TiO2_H2O_mol_O_H_1.xyz.zip MD5md5:5bfd89107466b23409842d2f0d39f676	103.3 MiB	The MD trajectory for the anatase TiO2-H2O interface showing the molecular adsorption mode of water with one extra proton attached to the surface O site 1.
a-TiO2_H2O_mol_O_H_2.xyz.zip MD5md5:bd60ec66b6989471e86ee8c84f0a8549	103.3 MiB	The MD trajectory for the anatase TiO2-H2O interface showing the molecular adsorption mode of water with one extra proton attached to the surface O site 2.
a-TiO2_H2O_dis_Ti_H2O_1.xyz.zip MD5md5:3dbb1c55218b31eb06b7668921c3b47a	92.0 MiB	The MD trajectory for the anatase TiO2-H2O interface showing the dissociative adsorption mode of water with one extra proton bound to OH- adsorbed at the surface Ti site 1.
a-TiO2_H2O_dis_Ti_H2O_2.xyz.zip MD5md5:1d422d3fe8a4708e8d2df4296d13f1fd	93.0 MiB	The MD trajectory for the anatase TiO2-H2O interface showing the dissociative adsorption mode of water with one extra proton bound to OH- adsorbed at the surface Ti site 2.
a-TiO2_H2O_dis_O_1.xyz.zip MD5md5:280c5dc3f19205f84c2cdaf560ea46fb	86.2 MiB	The MD trajectory for the anatase TiO2-H2O interface showing the dissociative adsorption mode of water with one proton removed from the surface O site 1.
a-TiO2_H2O_dis_O_2.xyz.zip MD5md5:a71328cdadbd1e2da6ba04e2ed9771a7	85.8 MiB	The MD trajectory for the anatase TiO2-H2O interface showing the dissociative adsorption mode of water with one proton removed from the surface O site 2.
README.txt MD5md5:e6fd2c0df975f6015df984d4e927017f	917 Bytes	README file containing a description of all files in this record

License

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External references

Keywords

MD trajectory semiconductor-water interface thermodynamic integration deprotonation free energy rVV10 functional MARVEL CSCS EPFL