Atomic-level engineering of single Ag1+ site distribution on titanium–oxo cluster surfaces to boost CO2 electroreduction
Meng, Ru-Xin; Zhao, Lan-Cheng; Luo, Li-Pan; Tian, Yi-Qi; Shao, Yong-Liang; Tang, Qing; Wang, Likai; Yan, Jun; Liu, Chao; Chemical Science 16 (2025) 6845–6852; doi:10.1039/D4SC07186G

data_1573744
_publ_section_title
;
 Atomic-level engineering of single Ag1+ site distribution on
 titanium--oxo cluster surfaces to boost CO2 electroreduction
;
_journal_issue                   16
_journal_name_full               'Chemical Science'
_journal_page_first              6845
_journal_page_last               6852
_journal_paper_doi               10.1039/D4SC07186G
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C240 H264 O42 S24 Ti12, 36[CH3CN]'
_chemical_formula_sum            'C312 H372 N36 O42 S24 Ti12'
_chemical_formula_weight         6642.67
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2024-12-03
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-12-03 deposited with the CCDC.	2025-01-09 downloaded from the CCDC.
;
_cell_angle_alpha                64.820(9)
_cell_angle_beta                 76.693(10)
_cell_angle_gamma                77.002(9)
_cell_formula_units_Z            1
_cell_length_a                   20.926(5)
_cell_length_b                   20.984(5)
_cell_length_c                   21.932(5)
_cell_measurement_reflns_used    9243
_cell_measurement_temperature    150.00
_cell_measurement_theta_max      56.82
_cell_measurement_theta_min      3.85
_cell_volume                     8393(3)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2013/2 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      150.00
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.660
_diffrn_measured_fraction_theta_max 0.979
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34139
_diffrn_reflns_av_R_equivalents  0.0775
_diffrn_reflns_av_unetI/netI     0.0582
_diffrn_reflns_Laue_measured_fraction_full 0.660
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            100970
_diffrn_reflns_point_group_measured_fraction_full 0.660
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         44.909
_diffrn_reflns_theta_min         1.907
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           2.86
_diffrn_source_power             0.1997996
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           69.86
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.854
_exptl_absorpt_correction_T_max  0.7512
_exptl_absorpt_correction_T_min  0.5500
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1472 before and 0.1107 after correction.
The Ratio of minimum to maximum transmission is 0.7322.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear yellowish yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.314
_exptl_crystal_description       prism
_exptl_crystal_F_000             3480
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.5
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.691
_refine_diff_density_min         -1.238
_refine_diff_density_rms         0.138
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.955
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1768
_refine_ls_number_reflns         20045
_refine_ls_number_restraints     959
_refine_ls_restrained_S_all      0.938
_refine_ls_R_factor_all          0.1608
_refine_ls_R_factor_gt           0.1376
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.2000P)^2^+73.0000P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3421
_refine_ls_wR_factor_ref         0.3582
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15406
_reflns_number_total             20045
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc07186g2.cif
_cod_data_source_block           Ti12L6
_cod_depositor_comments
'Adding full bibliography for 1573744--1573747.cif.'
_cod_database_code               1573744
_shelxl_version_number           2013-2
_shelx_estimated_absorpt_t_max   0.763
_shelx_estimated_absorpt_t_min   0.330
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C7-C5
 2.5 with sigma of 0.01
 C64-C91
 2.5 with sigma of 0.01
 C43-C39
 2.2 with sigma of 0.01
 C43-C96
 2.2 with sigma of 0.01
 C30-C38
 2.2 with sigma of 0.01
 C99-C100
 2.5 with sigma of 0.01
 C87-C27
 1.5 with sigma of 0.01
 C19-C70
 1.45 with sigma of 0.01
 C42-C52
 1.5 with sigma of 0.01
 C56-C52
 1.5 with sigma of 0.01
 C29-C28
 1.5 with sigma of 0.01
 C26-C74
 2.5 with sigma of 0.01
 C76-C75
 2.5 with sigma of 0.01
 C85-C27
 1.5 with sigma of 0.01
 C63-C51
 1.5 with sigma of 0.01
 C15-C87
 2.5 with sigma of 0.01
 C74-C61
 1.5 with sigma of 0.01
 C61-C86
 1.5 with sigma of 0.01
 C72-C73
 2.5 with sigma of 0.01
 C50-C47
 2.5 with sigma of 0.01
 C38-C29
 1.5 with sigma of 0.01
 C62-C99
 2.5 with sigma of 0.01
 C65-C27
 1.5 with sigma of 0.01
 C1-C3 \\sim C1-C2
 with sigma of 0.02
 C1-C5 \\sim C1-C4
 with sigma of 0.02
 C1-C7 \\sim C1-C6
 with sigma of 0.02
 C48-C47 \\sim C48-C49
 with sigma of 0.02
 C48-C50 \\sim C48-C44
 with sigma of 0.02
 C48-C45 \\sim C48-C46
 with sigma of 0.02
 C28-C29 \\sim C30-C29
 with sigma of 0.02
 C29-C37 \\sim C29-C38
 with sigma of 0.02
 C29-C32 \\sim C29-C36
 with sigma of 0.02
 C52-C55 \\sim C52-C14
 with sigma of 0.02
 C52-C42 \\sim C52-C56
 with sigma of 0.02
 C52-C25 \\sim C52-C16
 with sigma of 0.02
 C63-C57 \\sim C63-C99
 with sigma of 0.02
 C63-C66 \\sim C63-C62
 with sigma of 0.02
 C63-C67 \\sim C63-C51
 with sigma of 0.02
 C61-C18 \\sim C61-C22
 with sigma of 0.02
 C61-C23 \\sim C61-C26
 with sigma of 0.02
 C61-C86 \\sim C61-C74
 with sigma of 0.02
 C72-C70 \\sim C68-C70
 with sigma of 0.02
 C70-C69 \\sim C70-C20
 with sigma of 0.02
 C70-C73 \\sim C70-C71
 with sigma of 0.02
 C27-C76 \\sim C27-C87
 with sigma of 0.02
 C27-C24 \\sim C27-C15
 with sigma of 0.02
 C27-C75 \\sim C27-C85
 with sigma of 0.02
 C84-C89 \\sim C84-C82
 with sigma of 0.02
 C84-C90 \\sim C84-C83
 with sigma of 0.02
 C84-C88 \\sim C84-C81
 with sigma of 0.02
 C80-C79 \\sim C80-C58
 with sigma of 0.02
 C80-C77 \\sim C80-C60
 with sigma of 0.02
 C80-C78 \\sim C80-C59
 with sigma of 0.02
 C95-C98 \\sim C95-C91
 with sigma of 0.02
 C95-C92 \\sim C95-C93
 with sigma of 0.02
 C95-C94 \\sim C95-C64
 with sigma of 0.02
 C40-C41 \\sim C40-C43
 with sigma of 0.02
 C40-C34 \\sim C40-C39
 with sigma of 0.02
 C40-C35 \\sim C40-C33
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C40 \\sim C34 \\sim C39 \\sim C35 \\sim C33 \\sim C41 \\sim C43: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C2 \\sim C5 \\sim C7 \\sim C4 \\sim C6 \\sim C3 \\sim C1: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
C64 \\sim C98 \\sim C91 \\sim C92 \\sim C93 \\sim C94 \\sim C95: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C40 \\sim C97 \\sim C96 \\sim C101 \\sim C11 \\sim C12 \\sim C13: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C88 \\sim C81 \\sim C89 \\sim C82 \\sim C90 \\sim C83 \\sim C84: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C77 \\sim C60 \\sim C79 \\sim C58 \\sim C78 \\sim C59 \\sim C80: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C71 \\sim C69 \\sim C20 \\sim C70 \\sim C72 \\sim C68 \\sim C73: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C15 \\sim C24 \\sim C27 \\sim C75 \\sim C85 \\sim C76 \\sim C87: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C38 \\sim C28 \\sim C29 \\sim C30 \\sim C32 \\sim C36 \\sim C37 \\sim C8 \\sim
C9 \\sim C10: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
C44 \\sim C45 \\sim C46 \\sim C47 \\sim C48 \\sim C49 \\sim C50: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C25 \\sim C16 \\sim C42 \\sim C52 \\sim C55 \\sim C56 \\sim C14: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C51 \\sim C57 \\sim C99 \\sim C66 \\sim C62 \\sim C63 \\sim C67: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C27: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C74 \\sim C23 \\sim C26 \\sim C61 \\sim C18 \\sim C86 \\sim C22: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(C38) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 C57, C66, C67
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C99, C62, C51
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C79, C77, C78
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C58, C60, C59
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C98, C92, C94
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C91, C93, C64
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(H2C)=Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=Sof(C4)=
 Sof(H4A)=Sof(H4B)=Sof(H4C)=1-FVAR(1)
 Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(H3C)=Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(H5C)=Sof(C7)=
 Sof(H7A)=Sof(H7B)=Sof(H7C)=FVAR(1)
 Sof(C46)=Sof(H46A)=Sof(H46B)=Sof(H46C)=Sof(C49)=Sof(H49A)=Sof(H49B)=Sof(H49C)=
 Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(H44C)=1-FVAR(2)
 Sof(C47)=Sof(H47A)=Sof(H47B)=Sof(H47C)=Sof(C50)=Sof(H50A)=Sof(H50B)=Sof(H50C)=
 Sof(C45)=Sof(H45A)=Sof(H45B)=Sof(H45C)=FVAR(2)
 Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(H30C)=Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(H36C)=
 Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(H38C)=1-FVAR(3)
 Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(H28C)=Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(H37C)=
 Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=FVAR(3)
 Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(H16C)=Sof(C56)=Sof(H56A)=Sof(H56B)=Sof(H56C)=
 Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H14C)=1-FVAR(4)
 Sof(C55)=Sof(H55A)=Sof(H55B)=Sof(H55C)=Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(H42C)=
 Sof(C25)=Sof(H25A)=Sof(H25B)=Sof(H25C)=FVAR(4)
 Sof(C51)=Sof(H51A)=Sof(H51B)=Sof(H51C)=Sof(C99)=Sof(H99A)=Sof(H99B)=Sof(H99C)=
 Sof(C62)=Sof(H62A)=Sof(H62B)=Sof(H62C)=1-FVAR(5)
 Sof(C57)=Sof(H57A)=Sof(H57B)=Sof(H57C)=Sof(C66)=Sof(H66A)=Sof(H66B)=Sof(H66C)=
 Sof(C67)=Sof(H67A)=Sof(H67B)=Sof(H67C)=FVAR(5)
 Sof(C74)=Sof(H74A)=Sof(H74B)=Sof(H74C)=Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(H26C)=
 Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(H22C)=1-FVAR(6)
 Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(H18C)=Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(H23C)=
 Sof(C86)=Sof(H86A)=Sof(H86B)=Sof(H86C)=FVAR(6)
 Sof(C71)=Sof(H71A)=Sof(H71B)=Sof(H71C)=Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(H20C)=
 Sof(C68)=Sof(H68A)=Sof(H68B)=Sof(H68C)=1-FVAR(7)
 Sof(C72)=Sof(H72A)=Sof(H72B)=Sof(H72C)=Sof(C69)=Sof(H69A)=Sof(H69B)=Sof(H69C)=
 Sof(C73)=Sof(H73A)=Sof(H73B)=Sof(H73C)=FVAR(7)
 Sof(C87)=Sof(H87A)=Sof(H87B)=Sof(H87C)=Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=
 Sof(C85)=Sof(H85A)=Sof(H85B)=Sof(H85C)=1-FVAR(8)
 Sof(C76)=Sof(H76A)=Sof(H76B)=Sof(H76C)=Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=
 Sof(C75)=Sof(H75A)=Sof(H75B)=Sof(H75C)=FVAR(8)
 Sof(C82)=Sof(H82A)=Sof(H82B)=Sof(H82C)=Sof(C83)=Sof(H83A)=Sof(H83B)=Sof(H83C)=
 Sof(C81)=Sof(H81A)=Sof(H81B)=Sof(H81C)=1-FVAR(9)
 Sof(C89)=Sof(H89A)=Sof(H89B)=Sof(H89C)=Sof(C90)=Sof(H90A)=Sof(H90B)=Sof(H90C)=
 Sof(C88)=Sof(H88A)=Sof(H88B)=Sof(H88C)=FVAR(9)
 Sof(C60)=Sof(H60A)=Sof(H60B)=Sof(H60C)=Sof(C58)=Sof(H58A)=Sof(H58B)=Sof(H58C)=
 Sof(C59)=Sof(H59A)=Sof(H59B)=Sof(H59C)=1-FVAR(10)
 Sof(C79)=Sof(H79A)=Sof(H79B)=Sof(H79C)=Sof(C77)=Sof(H77A)=Sof(H77B)=Sof(H77C)=
 Sof(C78)=Sof(H78A)=Sof(H78B)=Sof(H78C)=FVAR(10)
 Sof(C64)=Sof(H64A)=Sof(H64B)=Sof(H64C)=Sof(C91)=Sof(H91A)=Sof(H91B)=Sof(H91C)=
 Sof(C93)=Sof(H93A)=Sof(H93B)=Sof(H93C)=1-FVAR(11)
 Sof(C98)=Sof(H98A)=Sof(H98B)=Sof(H98C)=Sof(C92)=Sof(H92A)=Sof(H92B)=Sof(H92C)=
 Sof(C94)=Sof(H94A)=Sof(H94B)=Sof(H94C)=FVAR(11)
 Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(H33C)=Sof(C43)=Sof(H43A)=Sof(H43B)=Sof(H43C)=
 Sof(C39)=Sof(H39A)=Sof(H39B)=Sof(H39C)=1-FVAR(12)
 Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(H41C)=Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(H34C)=
 Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(H35C)=FVAR(12)
6.a Riding coordinates:
 C98(H98A,H98B,H98C), C28(H28A,H28B,H28C), C92(H92A,H92B,H92C), C94(H94A,H94B,
 H94C), C79(H79A,H79B,H79C), C89(H89A,H89B,H89C), C37(H37A,H37B,H37C), C32(H32A,
 H32B,H32C), C77(H77A,H77B,H77C), C78(H78A,H78B,H78C), C47(H47A,H47B,H47C),
 C90(H90A,H90B,H90C), C3(H3A,H3B,H3C), C50(H50A,H50B,H50C), C88(H88A,H88B,H88C),
  C5(H5A,H5B,H5C), C7(H7A,H7B,H7C), C45(H45A,H45B,H45C), C2(H2A,H2B,H2C),
 C6(H6A,H6B,H6C), C4(H4A,H4B,H4C), C46(H46A,H46B,H46C), C49(H49A,H49B,H49C),
 C44(H44A,H44B,H44C), C30(H30A,H30B,H30C), C36(H36A,H36B,H36C), C38(H38A,H38B,
 H38C), C55(H55A,H55B,H55C), C42(H42A,H42B,H42C), C25(H25A,H25B,H25C), C57(H57A,
 H57B,H57C), C66(H66A,H66B,H66C), C67(H67A,H67B,H67C), C16(H16A,H16B,H16C),
 C56(H56A,H56B,H56C), C14(H14A,H14B,H14C), C18(H18A,H18B,H18C), C23(H23A,H23B,
 H23C), C86(H86A,H86B,H86C), C51(H51A,H51B,H51C), C99(H99A,H99B,H99C), C62(H62A,
 H62B,H62C), C74(H74A,H74B,H74C), C26(H26A,H26B,H26C), C22(H22A,H22B,H22C),
 C72(H72A,H72B,H72C), C69(H69A,H69B,H69C), C73(H73A,H73B,H73C), C71(H71A,H71B,
 H71C), C20(H20A,H20B,H20C), C68(H68A,H68B,H68C), C76(H76A,H76B,H76C), C24(H24A,
 H24B,H24C), C75(H75A,H75B,H75C), C87(H87A,H87B,H87C), C15(H15A,H15B,H15C),
 C85(H85A,H85B,H85C), C82(H82A,H82B,H82C), C83(H83A,H83B,H83C), C81(H81A,H81B,
 H81C), C60(H60A,H60B,H60C), C58(H58A,H58B,H58C), C59(H59A,H59B,H59C), C64(H64A,
 H64B,H64C), C91(H91A,H91B,H91C), C93(H93A,H93B,H93C), C41(H41A,H41B,H41C),
 C34(H34A,H34B,H34C), C35(H35A,H35B,H35C), C33(H33A,H33B,H33C), C43(H43A,H43B,
 H43C), C39(H39A,H39B,H39C)
6.b Secondary CH2 refined with riding coordinates:
 C039(H03A,H03B)
6.c Aromatic/amide H refined with riding coordinates:
 C01B(H01B), C01I(H01I), C01P(H01P), C021(H021), C024(H024), C10(H10), C9(H9),
 C028(H028), C02B(H02B), C02D(H02D), C02E(H02E), C02G(H02G), C02H(H02H),
 C02I(H02I), C02R(H02R), C02W(H02W), C97(H97), C033(H033), C101(H101), C54(H54),
  C21(H21), C03E(H03E)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              42745
_shelx_hkl_checksum              9340
_shelx_fab_checksum              78589
_olex2_submission_special_instructions 'No special instructions were received'