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_1573745
_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         'C80 H88 Ag2 O11 S8 Ti2, 1[CH3CN]'
_chemical_formula_sum            'C82 H90.68 Ag2 N O11 S8 Ti2'
_chemical_formula_weight         1834.25
_space_group_crystal_system      monoclinic
_space_group_IT_number           12
_space_group_name_Hall           '-I 2y'
_space_group_name_H-M_alt        'I 1 2/m 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2024-03-28
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-04-19 deposited with the CCDC.	2025-01-09 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.8776(15)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.0181(3)
_cell_length_b                   18.7809(3)
_cell_length_c                   30.2892(5)
_cell_measurement_reflns_used    9800
_cell_measurement_temperature    150
_cell_measurement_theta_max      69.2800
_cell_measurement_theta_min      3.1760
_cell_volume                     9100.5(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.68a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.68a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.68a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      150
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.965
_diffrn_measured_fraction_theta_max 0.927
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -31.00  29.00   0.50    0.59    --    0.00  98.00 165.00  120
  2  \w    114.00 154.00   0.50    2.37    --   92.24  98.00 165.00   80
  3  \w    142.00 168.00   0.50    2.37    --   92.24  19.00 -30.00   52
  4  \w     80.00 120.00   0.50    2.37    --   92.24  19.00 -30.00   80
  5  \w     40.00  72.00   0.50    2.37    --   92.24 -77.00 120.00   64
  6  \w     52.00 100.00   0.50    2.37    --   92.24 -98.00  57.00   96
  7  \w     39.00  65.00   0.50    2.37    --   92.24 -57.00 120.00   52
  8  \w     21.00 105.00   0.50    2.37    --   92.24 -77.00  60.00  168
  9  \w     23.00  49.00   0.50    2.37    --   92.24 -57.00 -60.00   52
 10  \w     26.00  51.00   0.50    2.37    --   92.24 -57.00 -90.00   50
 11  \w     -6.00  72.00   0.50    0.59    --    0.00  37.00 -90.00  156
 12  \w     26.00  51.00   0.50    0.59    --    0.00  37.00-150.00   50
 13  \w    -39.00 -14.00   0.50    2.37    --  -86.25  37.00 -90.00   50
 14  \w    -39.00 -14.00   0.50    2.37    --  -86.25  37.00-150.00   50
 15  \w    -65.00 -15.00   0.50    2.37    --  -86.25  57.00 -90.00  100
 16  \w    -42.00 -14.00   0.50    2.37    --  -86.25  37.00   0.00   56
 17  \w    -42.00 -17.00   0.50    2.37    --  -86.25  37.00  30.00   50
 18  \w    -42.00 -14.00   0.50    2.37    --  -86.25  37.00  90.00   56
 19  \w    -81.00 -40.00   0.50    2.37    --  -86.25  98.00 165.00   82
 20  \w    -64.00  -9.00   0.50    0.59    --    0.00 -57.00  60.00  110
 21  \w     21.00  55.00   0.50    2.37    --   92.24 -57.00  90.00   68
 22  \w   -141.00 -82.00   0.50    2.37    --  -86.25 -98.00  57.00  118
 23  \w   -151.00 -75.00   0.50    2.37    --  -86.25 -37.00  90.00  152
;
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0677478000
_diffrn_orient_matrix_UB_12      0.0286613000
_diffrn_orient_matrix_UB_13      -0.0296514000
_diffrn_orient_matrix_UB_21      0.0012726000
_diffrn_orient_matrix_UB_22      -0.0719295000
_diffrn_orient_matrix_UB_23      -0.0244061000
_diffrn_orient_matrix_UB_31      -0.0684132000
_diffrn_orient_matrix_UB_32      0.0270990000
_diffrn_orient_matrix_UB_33      -0.0334480000
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0412
_diffrn_reflns_av_unetI/netI     0.0535
_diffrn_reflns_Laue_measured_fraction_full 0.965
_diffrn_reflns_Laue_measured_fraction_max 0.927
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            27913
_diffrn_reflns_point_group_measured_fraction_full 0.965
_diffrn_reflns_point_group_measured_fraction_max 0.927
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.878
_diffrn_reflns_theta_min         2.769
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_exptl_absorpt_coefficient_mu    6.985
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.58573
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.68a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_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    1.339
_exptl_crystal_description       block
_exptl_crystal_F_000             3775
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.972
_refine_diff_density_min         -0.705
_refine_diff_density_rms         0.116
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.075
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     627
_refine_ls_number_reflns         8405
_refine_ls_number_restraints     328
_refine_ls_restrained_S_all      1.074
_refine_ls_R_factor_all          0.1023
_refine_ls_R_factor_gt           0.0905
_refine_ls_shift/su_max          0.008
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0962P)^2^+103.7029P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2424
_refine_ls_wR_factor_ref         0.2488
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7190
_reflns_number_total             8405
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc07186g2.cif
_cod_data_source_block           Ti2Ag2
_cod_depositor_comments
'Adding full bibliography for 1573744--1573747.cif.'
_cod_original_cell_volume        9100.6(3)
_cod_database_code               1573745
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         CHONTiSAg
_shelx_estimated_absorpt_t_max   0.228
_shelx_estimated_absorpt_t_min   0.128
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H,H,H) groups
2. Restrained distances
 C13-C16
 2.4 with sigma of 0.01
 C21-C23
 2.4 with sigma of 0.01
 C15-C18
 2.4 with sigma of 0.01
 C27-C14
 2.4 with sigma of 0.01
 C30-C27
 1.45 with sigma of 0.01
 C17-C25
 2.4 with sigma of 0.01
 C17-C22
 2.4 with sigma of 0.01
 C24-C28 \\sim C24-C29
 with sigma of 0.02
 C18-C15 \\sim C16-C13
 with sigma of 0.02
 C24-C18 \\sim C24-C16
 with sigma of 0.04
 C24-C15 \\sim C24-C13
 with sigma of 0.04
 C26-C25 \\sim C26-C11
 with sigma of 0.02
 C26-C17 \\sim C26-C21
 with sigma of 0.02
 C26-C22 \\sim C26-C23
 with sigma of 0.02
 O8-Ti2 \\sim O7-Ti2
 with sigma of 0.02
 O8-C8 \\sim O7-C8
 with sigma of 0.04
 O8-C32 \\sim O7-C32
 with sigma of 0.04
 O8-Ag \\sim O7-Ag
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C24 \\sim C15 \\sim C18 \\sim C28 \\sim C13 \\sim C16 \\sim C29: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C34 \\sim C33 \\sim C35 \\sim C36 \\sim C32 \\sim C8 \\sim O7 \\sim O8: within
2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C19 \\sim C20 \\sim C30 \\sim C12 \\sim C14 \\sim C27: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
C1 \\sim C3 \\sim C5 \\sim C10 \\sim C4 \\sim C6 \\sim C9 \\sim C31 \\sim C7
\\sim C2: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
C26 \\sim C17 \\sim C22 \\sim C25 \\sim C11 \\sim C21 \\sim C23: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
4. Others
 Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(H13C)=Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(H16C)=
 Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(H29C)=1-FVAR(1)
 Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(H18C)=
 Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(H28C)=FVAR(1)
 Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(H11C)=Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(H21C)=
 Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(H23C)=1-FVAR(2)
 Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(H17C)=Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(H22C)=
 Sof(C25)=Sof(H25A)=Sof(H25B)=Sof(H25C)=FVAR(2)
 Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(H1C)=Sof(H10)=Sof(C31)=Sof(H31)=1-FVAR(3)
 Sof(H3BD)=Sof(H3BF)=Sof(H3BE)=Sof(C7)=Sof(C2)=0.5*(1-FVAR(4))
 Sof(H3AC)=Sof(H3AA)=Sof(H3AB)=Sof(H5A)=Sof(H5B)=Sof(H5C)=Sof(C4)=Sof(C6)=0.5*
 FVAR(4)
 Sof(C5)=Sof(C9)=Sof(H9)=FVAR(3)
 Sof(O7)=1-FVAR(4)
 Sof(O8)=FVAR(4)
 Fixed Sof: O2(0.25) O1(0.25) H30(0.5) C12(0.5) H12A(0.5) H12B(0.5) H12C(0.5)
 C14(0.5) H14A(0.5) H14B(0.5) H14C(0.5) C27(0.5) H27A(0.5) H27B(0.5) H27C(0.5)
 Ag(0.5) Ti2(0.5) O3(0.25) O4(0.25)
5.a Riding coordinates:
 C15(H15A,H15B,H15C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C22(H22A,H22B,
 H22C), C25(H25A,H25B,H25C), C28(H28A,H28B,H28C), C11(H11A,H11B,H11C), C13(H13A,
 H13B,H13C), C16(H16A,H16B,H16C), C21(H21A,H21B,H21C), C23(H23A,H23B,H23C),
 C29(H29A,H29B,H29C), C01A(H01A,H01B,H01C), C1(H1A,H1B,H1C), C3(H3AC,H3AA,H3AB),
  C3(H3BD,H3BF,H3BE), C5(H5A,H5B,H5C), C015(H01D,H01E,H01F), C019(H01G,H01H,
 H01I), C12(H12A,H12B,H12C), C14(H14A,H14B,H14C), C27(H27A,H27B,H27C)
5.b Ternary CH refined with riding coordinates:
 C10(H10), C30(H30)
5.c Aromatic/amide H refined with riding coordinates:
 C00L(H00L), C00T(H00T), C00W(H00W), C011(H011), C35(H35), C34(H34), C19(H19),
 C9(H9), C31(H31)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              186
_shelx_hkl_checksum              80758
_shelx_fab_checksum              72915
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.508
_oxdiff_exptl_absorpt_empirical_full_min 0.696