過氧化氫作為一種可再生能源載體和清潔綠色的氧化劑，廣泛應(yīng)用于精細化工,、生物制藥,、環(huán)境修復(fù)等領(lǐng)域[1-3],。H?O?發(fā)生反應(yīng)只會產(chǎn)生O?和H?O反應(yīng)副產(chǎn)物,，不會對環(huán)境造成環(huán)境污染[4,5],。
目前工業(yè)上最常見的生產(chǎn)H?O?的方法是蒽醌法,，主要包括氫化、氧化,、取代和循環(huán)四個步驟,。雖然蒽醌法可以大規(guī)模生產(chǎn)，但是能耗巨大,，且需要使用有毒的有機原料和溶劑,，會導(dǎo)致嚴重的環(huán)境污染，不符合綠色化學(xué)的發(fā)展要求[6-8],。因此,，開發(fā)綠色H?O?制取方法具有非常重要的意義[9-11]。
近年來,，越來越多的研究表明,，通過光催化技術(shù)可以合成H?O?，且其原料僅為水和O?[12,13],。一般來說，光催化H?O?合成包括光吸收,、電荷載流子的產(chǎn)生和分離,、表面氧化還原反應(yīng)等多個步驟[14-18]。光催化生產(chǎn)H?O?具有環(huán)保性,、高效性,、靈活性、可持續(xù)性和創(chuàng)新性等多重優(yōu)勢,，是一種具有廣闊應(yīng)用前景和可持續(xù)發(fā)展?jié)摿Φ男滦铜h(huán)保技術(shù),。
在光照條件下，光催化劑會產(chǎn)生許多光生電子-空穴對,。位于光催化劑的導(dǎo)帶上的光電子具有較強的還原性,，位于價帶上的光生空穴具有較強的氧化性[19]。光生電子驅(qū)動氧還原反應(yīng)（ORR）和光生空穴誘導(dǎo)水氧化反應(yīng)（WOR）都是重要的表面氧化還原反應(yīng),，是光催化過氧化氫演化的主要原因（圖1）,。
圖1.半導(dǎo)體上光催化H?O?合成示意圖
具體來說，光催化H?O?合成的兩種方式ORR和WOR,，光催化劑在光照條件下產(chǎn)生光生電子和空穴,，光生電子能夠?qū)?還原為H?O?，而光生空穴能夠?qū)?O氧化為H?O?[20-22],。如圖2所示,，光生電子和空穴應(yīng)當(dāng)具有適當(dāng)?shù)难趸€原電位，才能夠滿足ORR和WOR反應(yīng)的發(fā)生條件[8,23]。
圖2.能級示意圖
可以看到H?O?合成的ORR是雙電子過程,，可以將其看做直接雙電子過程或兩個單電子過程（間接雙電子過程）[8,24],。對于兩個單電子過程，O?˙?是一個重要的中間產(chǎn)物[25],。O?/H?O?的氧化還原電位（0.68 V vs. NHE）比O?/O?˙?（-0.33 V vs. NHE）,根據(jù)熱力學(xué)原理,，直接雙電子過程更容易發(fā)生[8]。
在光催化O?還原過程中,，存在H?O?合成反應(yīng)的競爭反應(yīng),，即O?可以通過光生電子進一步還原為H?O（四電子ORR）[26-27]。O?/H?O（1.23 V vs. NHE）的氧化還原電勢比O?/H?O?的氧化還原電勢更正,，從熱力學(xué)角度來看,，四電子ORR更易發(fā)生[28]。通常光催化劑對氧的吸附能較低,，使得產(chǎn)物易于解吸,。總的來說,，兩個單電子過程在動力學(xué)上更有可能發(fā)生,。同時，O?極易與光生空穴發(fā)生反應(yīng),，產(chǎn)生單線態(tài)氧（¹O?,，O?˙?/¹O? 0.34 V vs. NHE），會導(dǎo)致H?O?產(chǎn)量降低,。
總的來說,，光催化H?O?合成的直接雙電子過程在熱力學(xué)上更易發(fā)生，但是在動力學(xué)觀點上,，兩個單電子過程更有利,。無論直接雙電子過程還是兩個單電子過程，都存在一些競爭反應(yīng),。因此,，抑制四電子氧還原反應(yīng)和¹O?的形成，高選擇性的產(chǎn)生H?O?是光催化H?O?合成的關(guān)鍵之一,。雙電子WOR與光催化H?O?合成中的雙電子ORR類似,。
光催化劑在光催化H?O?氧化反應(yīng)中起著核心作用。到目前為止已經(jīng)開發(fā)出各種功能材料作為光催化劑來生產(chǎn)H?O?,，并且取得了一些良好的結(jié)果[29-31],。通常為了提高光催化H?O?合成效率主要有兩種方法，即反應(yīng)條件的優(yōu)化和光催化劑的改性[32],。
No.1 反應(yīng)條件的優(yōu)化
• 溶劑類型
一般來說,，合適的溶劑不僅能夠作為電子供體來捕獲空穴并提供足夠的質(zhì)子,，還有助于分離光生載流子。目前最常用的溶劑是醇類,，如乙醇和異丙醇,。醇可以氧化成醛，產(chǎn)生質(zhì)子還原O?,。Yamashita[33]等人采用樣品法制備了一種疏水性鈦摻雜鋯基MOF,，這種MOF在芐醇水溶液中經(jīng)可見光照射能夠獲得很高的H?O?產(chǎn)率（9700.00 μmol L?¹ h?¹)。但是醇類的使用也會帶來的高成本和純化過程復(fù)雜問題,。Lan[34]等人構(gòu)建了穩(wěn)定的鈷基金屬有機籠,，金屬-非金屬活性位點協(xié)同作用，反應(yīng)底物可以通過籠的配位化學(xué)與活性位點接觸,。在純水中光催化H?O?產(chǎn)生的速率高達146.60 μmol L?¹ h?¹,。除此之外，采用海水光催化H?O?生產(chǎn)也是一種可行的方法,。Das[35]等人合成了一種g-C?N?催化劑,，這種催化劑在光催化H?O?產(chǎn)生中表現(xiàn)出優(yōu)異的活性。使用純水或海水光催化H?O?具有很好的應(yīng)用前景,，但是低效率是實際應(yīng)用的最大障礙,。
• pH值
反應(yīng)體系的pH值也是影響光催化H?O?生產(chǎn)的催化劑性能，很多研究工作忽略了這一點,。Wang[36]等人制備了有機聚合物點（PFB-PCBM Pdots）,，PFBT-PCBM Pdots在堿性條件下才能實現(xiàn)光催化H?O?產(chǎn)生（圖3a）。Mao[37]等人的研發(fā)線環(huán)糊精嘧啶聚合物在酸性條件下具有更高的光催化H?O?產(chǎn)率（圖3b）,。與堿性反應(yīng)環(huán)境相比，酸性反應(yīng)環(huán)境中會有更多的質(zhì)子,，同時光催化劑的活性位點可能會受到pH值的影響,，因此pH值的改變可能會對生成途徑產(chǎn)生影響。
圖3.(a)pH值對光催化H?O?產(chǎn)率的影響[38],；(b)pH值對光催化H?O?產(chǎn)生的影響[39],；(c)光催化H?O?產(chǎn)生的示意圖[40]；(d)在二氧化鈦納米棒上制備超小BiOI納米點的反應(yīng)物預(yù)固定策略示意圖,，以及樣品的掃描電鏡,、透射電鏡圖像和紫外-可見光譜[41]；(e)“瓶中船”和“船中瓶”示意圖,；(f)光催化劑的TEM圖像和光催化H?O?合成示意圖[42]
• O?含量
對于雙電子ORR,，O?是關(guān)鍵的原料。由于水中溶解氧很少,，將氧氣注入反應(yīng)系統(tǒng)是提高光催化H?O?產(chǎn)率的一種有效的方法,。由空穴觸發(fā)的四電子氧化還原反應(yīng)可以為雙電子氧化還原反應(yīng)提供氧氣,。Domen[43]等人的研究中，CoOx/Mo:BiVO?/Pd產(chǎn)生的空穴可以將水氧化形成氧氣,，然后通過雙電子氧化還原反應(yīng)將獲得的氧氣進一步還原為H?O?（圖3c）,。
No.2 光催化劑改性
• 吸收光線的增強
強光吸收能力是光催化劑的必要屬性。一般來說,，光催化劑的光吸收特性主要有能帶結(jié)構(gòu)決定,。為了提高光催化劑的光吸收能力，提出了一些有效的策略來修飾光催化劑的能帶結(jié)構(gòu),，例如表面改性工程,、負載量子點、摻雜和局域表面等離子體共振（LSPR）效應(yīng),。光敏劑的引入是最常見的表面改性工程之一,。Feng[44]通過在TiO?納米棒組裝的微型花朵上均勻裝飾BiOI納米點，制備了具有代表性的納米區(qū)域光催化異質(zhì)結(jié)構(gòu)（圖3d）,，可見光敏化納米點很好的分散在TiO?納米棒表面,，有效的增強TiO?的可見光捕獲能力。量子點是在納米尺度上具有獨特光學(xué)性質(zhì)的半導(dǎo)體,，負載量子點被認為是提高催化劑光吸收能力的可行策略,。目前已報道的兩種典型的將量子點負載到催化劑上的方法，即“瓶中船”和“船中瓶”方法（圖3e）,。Cao[45]等人采用了一種簡單的方法來構(gòu)建磷摻雜的多孔g-C?N?（圖3f）,，具有典型的孔結(jié)構(gòu)，g-C?N?的光吸收能力也得到了提高,。最高H?O?產(chǎn)率可達到1968 μmol g?¹ h?¹,，光催化產(chǎn)H?O?的途徑包括雙電子ORR和雙電子WOR。
當(dāng)入射光子的頻率與金屬內(nèi)部等離子體的振蕩頻率相同時,，會發(fā)生共振,，導(dǎo)致入射光的強烈吸收，這種現(xiàn)象稱為LSPR效應(yīng)（圖4a）,。Li[46]等人通過用Au納米顆粒封裝在NH?-UiO-66納米籠中,，制備了Au@NH?-UiO-66/CdS復(fù)合材料，引入的金納米粒子在523 nm處表現(xiàn)出明顯的LSPR特征峰,。由于金納米顆粒的LSPR效應(yīng),，Au@NH?-UiO-66/CdS復(fù)合材料在析氫反應(yīng)中表現(xiàn)出優(yōu)異的催化性能，金納米粒子在波長523 nm表現(xiàn)出明顯的LSPR特征峰（圖4b）,，Au@NH?-UiO-66/CdS復(fù)合材料在析氫反應(yīng)中表現(xiàn)出優(yōu)異的催化性能,。
圖4.(a)表面等離子共振效應(yīng)示意圖；(b)樣品的TEM圖像和紫外可見光譜[47],；(c)樣品光譜及模擬機理[48],；(d)不同催化劑光催化H?O?演化比較[49]
• 電荷分離的改善
光生電子和空穴易復(fù)合是一個不可避免的問題,，嚴重限制了光催化劑的工程應(yīng)用。
由于某些金屬離子具有多層價態(tài),，金屬離子可通過氧化還原偶聯(lián)在電子傳遞中起一定作用,。因此，摻雜金屬離子被認為是抑制光誘導(dǎo)電子和空穴重組的有效途徑,。Xue[50]等利用卟啉鈷用一種簡單的方法來裝飾金納米粒子,，由于鈷離子在電子轉(zhuǎn)移中的作用，金納米粒子上的電荷分離效率明顯提高,，光催化H?O?產(chǎn)率高達235.93 μmol L?¹（圖4c）,。
異質(zhì)結(jié)的構(gòu)建也可以提高電荷分離效率。兩種材料結(jié)合會在界面處形成異質(zhì)結(jié),，通過不同組分之間的異質(zhì)結(jié)可以實現(xiàn)光生載流子的相互傳輸,。Wang[51]等人的研究中，基于原位生長方法制備了灌裝氮化碳（TCN）/ZnIn?S?（ZIS）異質(zhì)結(jié),。由于形成了II型異質(zhì)結(jié),，電荷分離能力得到改善，在TCN/ZIS上可以實現(xiàn)2.77 mmol g?¹ h?¹的H?O?產(chǎn)率（圖4d）,。Ye[52]等人通過耦合g-C?N?和Zn聚菲咯啉制備了一種新型的Z-scheme異質(zhì)結(jié),，在純水中可以實現(xiàn)114 μmol g?¹ h?¹ H?O?的產(chǎn)率。
• 表面光催化反應(yīng)的增強
普遍認為光催化H?O?合成的途徑主要涉及雙電子ORR和雙電子WOR,，這些反應(yīng)通常發(fā)生在催化劑的表面,，因此增強表面光催化反應(yīng)對光催化劑上H?O?的產(chǎn)生有積極影響。
• 抑制H?O?分解
在堿性環(huán)境或高溫下,，H?O?容易分解為H?O和O?,。同時在光催化劑表面形成的H?O?可以與光生電子或空穴進一步反應(yīng)。因此及時從光催化劑表面脫附H?O?非常重要,。Yamashita[53]等人將十八烷基磷酸用于對鈦摻雜的Zr基MOF進行改性,，使其具有疏水性，光催化和H?O?分散在苯基乙醇和水中,，從而抑制了H?O?的分解。
太陽能驅(qū)動的光催化過程為生產(chǎn)H?O?提供了一種有前途的綠色方法,。盡管過去的幾十年,，許多研究人員致力于探索光催化H?O?產(chǎn)生在工程應(yīng)用的可行性。盡管取得了顯著的進展,，光催化H?O?生產(chǎn)仍有很長的路要走,。眾所周知，光催化H?O?合成的核心是光催化劑,，然而目前大多數(shù)光催化劑還沒有強光吸收能力和高電子-空穴對分離效率,，未來研究可以繼續(xù)關(guān)注這些問題,。此外，表面光催化反應(yīng)的改善對光催化劑H?O?合成具有積極影響,。除上述問題外,，缺乏合適的反應(yīng)器，使得光催化劑的回收和再生困難,，限制了光催化H?O?合成在實際工程中的應(yīng)用,。雖然有許多挑戰(zhàn)和問題阻礙光催化H?O?合成進一步發(fā)展，但光催化H?O?合成仍然是一個有吸引力的領(lǐng)域,。
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