A　solid-state　pulsed　laser　technique　was　developed　to　in　situ　grow　arbitrary　immobilized　catalysts　(Fe3O4,　CeO2,　WO3　etc.)　on　the　inner　surface　of　quartz　tube　with　robust　adhering　strength.　In　a　case　study,　anatase/rutile　hetero-phase　TiO2　film　was　deposited　to　serve　as　immobilized　photocatalysts　for　the　effective　removal　of　antibiotics　from　aqueous　environment.　The　X-ray　absorption　spectroscopy,　low　temperature　electron　paramagnetic　resonance　and　the　density　functional　theory　simulation　directly　confirm　a　defect-assisted　type-II　band　alignment　was　established　to　facilitate　the　charge　transfer　at　the　hereto-interphase.　In　addition,　the　oxygen　vacancy　enriched　anatase　phase　with　greater　binding　energy　towards　the　dissolved　oxygen　facilitated　the　[rad]O2–　generation.　Meanwhile,　the　rutile　phase　enriched　with　Ti3+　could　effectively　activate　the　antibiotics　to　promote　the　direct　h+　mediated　oxidation.　Such　integration　of　unique　atomic　vacancies　prevent　defects　from　becoming　electron-hole　recombination　centers　and　consequently　extend　the　lifetime　of　the　photoexcited　charge　carrier.　The　degradation　mechanism　of　oxytetracycline　was　thoroughly　examined　by　ultra-high　resolution　electrospray　time-of-flight　mass　spectrometry　and　Fukui　function,　while　the　ecological　structure–activity　relationships　program　assessed　the　toxicity　of　contaminant　to　the　environment.　Milewhile,　a　continuous　water　treatment　apparatus　employing　the　catalytic　tubes　as　reactors　was　established　and　demonstrated　a　∼　95　%　OTC　degradation　under　the　natural　sunlight　adopting　river　water　as　the　background.　The　experimental　studies　also　claimed　that　∼　90　%　of　the　initial　activity　could　be　retained　after　100　cycles　reuse,　which　permits　their　great　potential　for　the　applicational　scenarios.　©　2024