Kuputswa kwemethylene blue nefotokatalisisi: kududzira zvabuda pakubvisa dhayi

Rabhoritari inoedza makatelisiti maviri pakuputswa kwemethylene blue kunobatsirwa nechiedza. Katelisiti A inobvisa 95 muzana yeruvara rwebhuruu muawa imwe. Katelisiti B inokwanisa chete 60 muzana. Chikwata chinoti A ndiyo yakunda, chinonyora izvi mumushumo, uye chinoodha imwe yakawanda. Mwedzi yakati gare gare, ongororo yekabhoni inoratidza chokwadi: dhayi yakawanda yakabviswa naA yakanga yakangonamatira pamusoro pechinhu chakasimba isina kuchinja, nepo B yakanga yaputsa mamorekuru edhayi akawanda. Kurongwa kwacho kwakanga kwakapidiguka nokuti chikwata chakayera chinhu chimwe asi chikachipa zita rechimwe.

Chikanganiso ichi chakajairika nokuti pfungwa ina dzakasiyana dzinogona kuratidza chinhu chimwe chete chinoonekwa: mvura yebhuruu inocheneruka. Kunamatira pamusoro, kupera kweruvara, kuputswa kwemamorekuru, uye kushandurwa kuita inorganic zvose zvinogona kukonzera izvi, asi chimwe nechimwe chinoreva chinhu chakasiyana nezvakaitika kudhayi. Methylene blue ndeimwe yezvinhu zvinoshandiswa mukushandiswa pakuongorora nemuzvidzidzo zvezvakatipoteredza umo dhayi ine basa rakanyatsotsanangurwa; pano inoshandiswa semuenzaniso wechinhu chinosvibisa chiri kubviswa kana kushandurwa. Usati waenzanisa makatelisiti kana kubudisa chikamu muzana chekubviswa, sarudza kuti zviyero zvako zvinonyatsotsigira mugumisiro upi.

Migumisiro mina, zvirevo zvina zvakasiyana

Funga nezvazvo sepfungwa ina dzine misimboti yakasiyana yekuyedza. Imwe neimwe inopindura mubvunzo wakasiyana, uye imwe neimwe inoda humbowo hwayo.

Kunamatira pamusoro kunoreva kuti mamorekuru edhayi anobuda mumhinduro yemvura onamatira pachinhu chakasimba pasina hazvo kushanduka kwemakemikari. Chiedzo chacho chinoitwa murima kusvikira huwandu hunotorwa hwanyatsosvika padanho husingachawedzeri, uye humbowo hwakavimbika hunosanganisira dhayi inodzorerwa kubva pachinhu chakasimba nokuisunungura pamusoro pacho kana kuibudisa nechinonyungudutsa. Nguva yakatarwa ye30 maminitsi murima haisi humbowo hwekuti kuenzana kwasvikwa pachinhu chose, uye hurukuro yemazuva ano pamusoro penzira dzekuyedza inoratidza kuti kusvetuka danho iri kunokonzera kurongwa kwemakatelisiti zvisizvo kana huwandu hunotorwa murima hwakasiyana pakati pezvinhu.

Kupera kweruvara kunoreva kurasika kwechikamu chemamorekuru chinopa ruvara runoonekwa, kazhinji kuchiteverwa pedyo nebhandi guru rekutora chiedza riri paanenge 664 nm. Kunamatira pamusoro, ridakisheni, N-demethylation, uye kuputswa kwechikamu chinopa ruvara zvose zvinogona kuderedza kuverengwa ikoko, saka kukosha kwakayerwa pawavelength imwe chete hakugoni kuzivisa chikonzero. Nyora masipekitiramu akazara pane kunyora nhamba imwe chete: kutamira kwepamusoro pesipekitiramu kudivi reblue kunoenderana nezvigadzirwa zvemhuri yeAzure zvakabviswa mapoka emethyl. Mugumisiro unonzi 95 muzana yekubviswa pa664 nm unofanira kunzi 95 muzana yekupera kweruvara, kwete 95 muzana yekuputswa kwemamorekuru.

Kuputswa kwemamorekuru kunoreva kuti morekuru rekutanga remethylene blue rashandurwa nemakemikari. Humbowo hunobva pakromatogirafi: dhayi isina kuchinja inonyangarika paHPLC kana UPLC apo zvigadzirwa zvekushandurwa zvinooneka zvobva zvazoputswawo, zvichinyatsozivikanwa neLC-MS kana zvichibvira. Zviratidzo zvinobatsira zvinosanganisira ayoni yemorekuru iri pedyo nem/z 284 yedhayi yekutanga, uye nhevedzano yekubviswa kwemapoka emethyl padanho nedanho: Azure B pedyo ne270, Azure A pedyo ne256, Azure C pedyo ne242, uye thionine pedyo ne228. Pane izvi, shanduko dzeLC-MS/MS dzakasimbiswa dzemadhayi ari mumvura dzakabudiswa.

Kushandurwa kuita inorganic kunoreva kuti kabhoni yeorganic yashandurwa kuita zvigadzirwa zvekupedzisira zveinorganic, zvikuru carbon dioxide nekabhoni yeinorganic, huku nitrogen nesulfur zvichipedzisira zviri mumhando dzakadai seammonium, nitrate, nesulfate. Kurasika kwekabhoni yose yeorganic (TOC) ndicho chiyero chekabhoni chinowanzoshandiswa. Kuderedzwa kwehuwandu hweokisijeni hunodiwa nemakemikari (COD) kunoratidza kuderera kwehuwandu hwezvinhu zvinogona kuitwa oxidation, asi hakusi kuenzana kwemass yekabhoni uye pachako hakusimbisi kushandurwa kwakakwana kuita inorganic. Kromatogirafi yemaayoni esulfate, nitrate, neammonium inosimbisa chirevo chacho.

Mhando dzemakatelisiti, dzakadai setitania yakaiswa zvimwe zvinhu, zvinhu zvakasanganiswa, zvinhu zvinotsigirwa nekabhoni, nezvimwe zvakafanana, dzinofanira kuenzaniswa pamwe chete chete kana mhando yose ichiyedzwa nemigumisiro nezviedzo zvekuenzanisa zvakafanana. Chinhu chakasanganiswa chinonamatisa dhayi zvakanyanya chinogara chichiratidzika sechinoshanda nokukurumidza muchiedzo cheruvara. Ndicho chikonzero rondedzero iri pasi apa ichiparadzanisa kutorwa kwedhayi nekuita kwemakemikari kusati kwarongwa makatelisiti.

Mashandiro ekuputswa kwemethylene blue nefotokatalisisi

Mhuri yenzira dzinogamuchirwa apo semiconductor inomutswa nechiedza zvechokwadi inopfupikiswa muongororo inowanzotaurwa yekuputswa kwemadhayi nefotokatalisisi pazvinhu zvakavakirwa patitania. Mafotoni anotorwa anogadzira maerekitironi mubhandi rinofambisa magetsi nemakomba mubhandi revalence. Makomba anoita oxidation yemvura kana hydroxide zviri pamusoro, achigadzira hydroxyl radicals, uku maerekitironi achiita ridakisheni yeokisijeni yakanyunguduka kuti iite superoxide. Mamwe maitiro emakemikari anopfuura nemuhydroperoxyl radicals nehydrogen peroxide achigadzira mamwe hydroxyl radicals. Mhando idzi dzeokisijeni dzinokurumidza kuita makemikari, pamwe nemakomba acho pachawo, dzinobva dzarwisa dhayi.

Kushandurwa kwemethylene blue kunowanzotanga nekubviswa kwemapoka emethyl paN zvakatevedzana kuburikidza neAzure B, Azure A, neAzure C kusvika kuthionine, pamwe neoxidation yephenothiazine chromophore inopa ruvara. Kumwe kurwisa kwemaradical kunoputsa zvisungo zvekabhoni nesulfur uye zvekabhoni nenitrogen, kunovhura maringi earomatic, uye kunogadzira makombaundi emhando yephenol neaniline, aldehydes, uye carboxylic acids ane uremu hwemamorekuru hushoma, kusati kwazoitika kushandurwa kuita inorganic. Ongororo yakanangana nezvimiro zvemethylene blue nenzira dzekuputswa kwayo nechiedza inotsanangura mhuri iyi zvakadzama. Zviyero chaizvo zvemapazi enzira idzi zvinoenderana nekatelisiti, pH, kuwanikwa kweokisijeni, uye kupiwa kwechiedza, saka tora chirongwa ichi semhuri yenzira dzinogona kuitika, kwete nhevedzano imwe inosungirwa.

Zvinhu zviviri zvemuchiedzo zvinoda kutariswa nokuti zvinoshandura kumhanya kunoonekwa kwemaitiro pasina kuchinja katelisiti pachayo. pH inoshandura chaji yepamusoro petitania uye kuwanda kwemapoka ehydroxyl pamusoro payo, izvo zvinoshandura kunamatira kwedhayi ine chaji yakanaka, zvobva zvachinja kumhanya kunoonekwa; enzanisa zvinhu pa pH yakafanana uye nyora kukosha kwekutanga nekwekupedzisira. Munyu wakanyunguduka nemabuffer zvinoitawo zvakafanana: chloride, phosphate, carbonate, nesulfate zvinogona kugara panzvimbo dzepamusoro zvoshandura maitiro emaradical. Chidzidzo chakanangana nemunyu weinorganic mufotokatalisisi yetitania chinonyora izvi zvakananga pamethylene blue.

Musungo wechiedza chinoonekwa

Titania isina kugadziridzwa inoda kumutswa nechiedza chiri pedyo neUV, asi mishumo yakawanda inoratidza kupera kweruvara rwemethylene blue pasi pemarambi anopa chiedza chinoonekwa chete, yoti katelisiti ndiyo inoshanda nechiedza chinoonekwa. Mashandiro angangove aripo ndeekumutswa kunobatsirwa nedhayi: dhayi yakamutswa inopinza erekitironi musemiconductor, uye erekitironi iyoyo inoita ridakisheni yeokisijeni, ichipedza ruvara pasina kumutswa chaiko kwechinhu chakasimba kuyambuka band gap. Basa rezviedzo rakachengetwa naOhtani nevamwe pamusoro pedambudziko rechiedza chinoonekwa rakaratidza mugumisiro uyu unogona kutsausa. Uye tsananguro yenzvimbo inoshandiswa ISO 10678 inoisa muganhu pachena nokubvumira nzira yayo yekuyedza nemethylene blue pachiedza cheUV chete, ichisiya kunze zvirevo zvekushanda nechiedza chinoonekwa.

Chiedzo chinoshanda chiri nyore. Dzokorora chiedzo uchishandisa chinhu chekuyedza chisina ruvara uye chisingatori chiedza chinoonekwa, woenzanisa kuchinja kwekumhanya zvichienderana newavelength nesipekitiramu yekutora chiedza yekatelisiti. Kana kushanda kuchitevera kutorwa kwechiedza nedhayi panzvimbo pekutorwa kwacho nekatelisiti, mugumisiro unotsigira kumutswa kunobatsirwa nedhayi, kwete fotokatalisisi yechiedza chinoonekwa inobva pakatelisiti pachayo. Rangarira chiedzo ichi paunoverenga zvirevo zvevatengesi pamusoro pemhando dzemakatelisiti anoshanda nechiedza chinoonekwa.

Rondedzero yekuongorora migumisiro

Shandisa rondedzero iyi usati waronga makatelisiti kana kunyora chirevo chekubviswa kwedhayi. Ichi ndicho chinhu chiri papeji ino chinogona kushandiswa kakawanda: chiedzo chose chekuputswa kwemethylene blue chinofanira kuzadzisa mutsetse mumwe nomumwe.

1. Chiedzo chekuenzanisa kunamatira murima: dhayi pamwe nekatelisiti, pasina chiedza, zvichikurungidzwa kusvikira zvayerwa kuti huwandu hunotorwa hahuchawedzeri, pamwe nekudzorerwa kwedhayi kubva pachinhu chakasimba, kwete kungofungidzira kubva panguva yakatarwa.
2. Chiedzo chekuenzanisa kuputswa nechiedza chete: dhayi pamwe nechiedza, pasina katelisiti, kuti uyere kupera kweruvara kunokonzerwa nerambi rako nechimiro chegadziriro yechiedzo.
3. Chiedzo cheongororo chisina dhayi: katelisiti pamwe nechiedza, pasina dhayi, kuti utore zviratidzo zvinobva pane zvimwe zvinhu muTOC, maayoni, nemasipekitiramu.
4. Mamiriro ekuita makemikari akafanana: sipekitiramu yerambi, kuyerera kwemafotoni, tembiricha, kukurungidza, okisijeni yakanyunguduka, chimiro chemudziyo wekuita makemikari, kuwanda kwedhayi pakutanga, huwandu hwekatelisiti, pH, uye musanganiswa wakatakura dhayi zvinofanira kuramba zvakafanana pamhando dzose.
5. Kupatsanura chinhu chakasimba pamberi pekuyera masipekitiramu: sefa kana shandisa centrifuge kuitira kuti kupararira kwechiedza kusaverengwa sekutorwa kwechiedza.
6. Masipekitiramu akazara, kwete wavelength imwe chete: shuma scan yacho kuitira kuti kutama kwepamusoro pemasipekitiramu nemabhandi matsva zvirambe zvichionekwa.
7. Kusimbisa nekromatogirafi chirevo chipi zvacho chekuputswa kwemamorekuru: kurasika kwedhayi yekutanga isina kuchinja, pamwe nezvigadzirwa zvinoteverwa.
8. Kuverenga kabhoni pachirevo chipi zvacho chekushandurwa kuita inorganic: TOC pamwe nezviedzo zvisina dhayi, uye kuongorora kuti kabhoni inonzi yabviswa haisati yangotamira pachinhu chakasimba.
9. Kuongorora kusununguka kwezvinhu zvichinyunguduka: bvisa chinhu chakasimba zvachose nechiedzo chakafanana nekusefa kuchipisa, ipa mvura yasefwa chiedza, uye ongorora simbi dzakanyunguduka; kuramba kuchiitika kwemakemikari kunoratidza kuti zvinhu zvakanyunguduka zvinobatsirawo.
10. Kutumidza nokutendeseka: mugumisiro we664 nm uti kupera kweruvara, mugumisiro wekromatogirafi uti kuputswa kwemamorekuru, uye mugumisiro weTOC uti kushandurwa kuita inorganic.

Chidzidzo chemazuva ano chemudziyo weUV-LED wekuita makemikari nechiedza chinobatanidza zviedzo zvekunamatira pamusoro, kupatsanura katelisiti, UV-vis, neTOC chinoratidza kuti zvikamu izvi zvinobatana sei muchikamu chimwe chinotsanangura nzira dzakashandiswa.

Muenzaniso wakashandwa wekuenzana kwemass

Ngatitii chiedzo che100 mL chinotanga chine methylene blue yakawanda 10 mg/L, saka mudziyo wekuita makemikari une 1.0 mg yedhayi. Mushure mokusvika pakuenzana murima, mhinduro yemvura inoverengwa se8.0 mg/L, zvichireva kuti 0.2 mg iri pachinhu chakasimba uye 0.8 mg yasara yakanyunguduka. Mushure meawa imwe yokupiwa chiedza, ongororo yemhinduro yemvura yasefwa inopa 2.0 mg/L yedhayi isina kuchinja nekromatogirafi (0.2 mg mumhinduro yemvura), kusunungura dhayi yakanamatira kunodzoreredza 0.1 mg yedhayi isina kuchinja kubva pachinhu chakasimba, uye TOC inoratidza kuti 40 muzana yekabhoni yeorganic yekutanga yabuda mugadziriro inosanganisa mhinduro yemvura nechinhu chakasimba yava kabhoni yeinorganic.

Kuenzana kwakavakirwa pakabhoni kunoverengwa seizvi: kabhoni yekutanga yakaenzana nedhayi yekutanga iri mumhinduro yemvura, pamwe nedhayi yekutanga yakanamatira pamusoro, pamwe nezvigadzirwa zveorganic zvepakati, pamwe nekabhoni yakashandurwa kuita inorganic. Pano 20 muzana yemass yedhayi yekutanga yasara iri dhayi yekutanga isina kuchinja (0.2 mg mumativi ose ari maviri), 40 muzana yashandurwa kuita inorganic, uye 40 muzana yasara zvigadzirwa zveorganic zvakabva pakushandurwa (zvigadzirwa zvepakati zviri mumhinduro yemvura kana pachinhu chakasimba, zvakasimbiswa nepamusoro pemasipekitiramu zvinoratidza zvigadzirwa). Mushumo wakarurama ndewekuti dhayi yekutanga yaputswa ne80 muzana uye 40 muzana yashandurwa kuita inorganic, kwete 95 muzana yechinhu chipi zvacho. Cherechedza musungo wacho: dai TOC yakayerwa pamvura yepamusoro yasefwa chete, zvinhu zveorganic zvakanamatira pamusoro zvingadai zvakaverengwa sezvaparadzwa, zvichikwidza nhamba yekushandurwa kuita inorganic zvisizvo. Yera kabhoni yemusanganiswa wose une zvikamu zvakasimba kana zvichibvira, kana kuti wedzera pachena chikamu chakabatirira pachinhu chakasimba pakuverenga.

Mutemo wekushuma

Taura mugumisiro usingade humbowo hwakasimba kupfuura hwaunahwo, wobva wawedzera zvirevo zvakasimba chete kana chikamu chimwe nechimwe chezviyero chazvisimbisa. Basa rekuputswa kwemethylene blue rinowana kuvimbwa nenzira imwe chete nedzimwe nzira dzinoshandisa dhayi: nokuenzanisa mugumisiro nechimiro chinonyatsoyerwa nenzira yacho. Gwaro rinoperekedza iri rekuverenga zvirevo zvekutsvakurudza kunoshandisa dhayi rinowedzera kurongeka kumwe chete pakugadzirwa kwezvidzidzo, uye nzira inoshanda yekuongorora mamiriro ezviedzo inobata maitiro ekugadzirisa kururama kwezviyereso anogona kushandiswa zvakananga mubasa remidziyo yekuita makemikari nechiedza.